Organotin compounds cause structure-dependent induction of progesterone in human choriocarcinoma Jar cells.

Science.gov (United States)

Hiromori, Youhei; Yui, Hiroki; Nishikawa, Jun-ichi; Nagase, Hisamitsu; Nakanishi, Tsuyoshi

2016-01-01

Organotin compounds, such as tributyltin (TBT) and triphenyltin (TPT), are typical environmental contaminants and suspected endocrine-disrupting chemicals because they cause masculinization in female mollusks. In addition, previous studies have suggested that the endocrine disruption by organotin compounds leads to activation of peroxisome proliferator-activated receptor (PPAR)γ and retinoid X receptor (RXR). However, whether organotin compounds cause crucial toxicities in human development and reproduction is unclear. We here investigated the structure-dependent effect of 12 tin compounds on mRNA transcription of 3β-hydroxysteroid dehydrogenase type I (3β-HSD I) and progesterone production in human choriocarcinoma Jar cells. TBT, TPT, dibutyltin, monophenyltin, tripropyltin, and tricyclohexyltin enhanced progesterone production in a dose-dependent fashion. Although tetraalkyltin compounds such as tetrabutyltin increased progesterone production, the concentrations necessary for activation were 30-100 times greater than those for trialkyltins. All tested active organotins increased 3β-HSD I mRNA transcription. We further investigated the correlation between the agonistic activity of organotin compounds on PPARγ and their ability to promote progesterone production. Except for DBTCl2, the active organotins significantly induced the transactivation function of PPARγ. In addition, PPARγ knockdown significantly suppressed the induction of mRNA transcription of 3β-HSD I by all active organotins except DBTCl2. These results suggest that some organotin compounds promote progesterone biosynthesis in vitro by inducing 3β-HSD I mRNA transcription via the PPARγ signaling pathway. The placenta represents a potential target organ for these compounds, whose endocrine-disrupting effects might cause local changes in progesterone concentration in pregnant women. Copyright © 2014 Elsevier Ltd. All rights reserved.

SYNTHESIS, REACTIVITY AND BIOLOGICAL ACTIVITY OF QUINOXALIN-2-ONE DERIVATIVES

Directory of Open Access Journals (Sweden)

El Mokhtar Essassi

2010-04-01

Full Text Available Quinoxalines have a great interest in various fields and particularly in chemistry, biology and pharmacology. It enabled the researchers to develop many methods for their preparations and to seek new fields of application. In this review, we’ll expose different methods of synthesis of the quinoxalin-2-one, its reactivity and finally we’ll discuss the various biological activities of its derivatives.

Nuclear magnetic resonance of organofluorine compounds: a challenge in the teaching of spectroscopy; Ressonância magnética nuclear de substâncias organofluoradas: um desafio no ensino de espectroscopia

Energy Technology Data Exchange (ETDEWEB)

Branco, Frederico Silva Castelo; Boechat, Núbia [Instituto de Tecnologia de Fármacos, Fundação Oswaldo Cruz, Farmanguinhos - Fiocruz, Rio de Janeiro – RJ (Brazil); Silva, Bárbara V.; Rio, Gabriel Freitas do; Pinto, Angelo C. [Instituto de Química, Universidade Federal do Rio de Janeiro, RJ (Brazil); Santana, Mábio João; Queiroz Júnior, Luiz Henrique Keng; Lião, Luciano Morais, E-mail: lucianoliao@ufg.br [Instituto de Química, Universidade Federal de Goiás, GO (Brazil)

2015-11-15

Nuclear magnetic resonance is a technique that is widely used for elucidating and characterizing organic substances. Organofluorine substances have applications in many areas from drugs to liquid crystals, but their NMR spectra are often challenging due to fluoride coupling with other nuclei. For this reason, NMR spectra of this class of substances are not commonly covered in undergraduate and graduate chemistry courses and related fields. Thus, the aim of this work was the presentation and discussion of {sup 1}H, {sup 13}C, and {sup 19}F NMR spectra of eleven organofluorine substances which, in the case of {sup 1}H and {sup 13}C nuclei, showed classic patterns of first-order coupling and the effects of the fluorine nucleus in different chemical and magnetic environments. In addition, the observation of long distance coupling constants was possible through the use of apodization functions in the processing of the spectra. It is expected that the examples presented herein can be utilized and discussed in undergraduate and graduate NMR spectroscopy disciplines and thus improve the teaching and future research of organofluorine compounds. (author)

Long-Term Spatio-Temporal Trends of Organotin Contaminations in the Marine Environment of Hong Kong.

Directory of Open Access Journals (Sweden)

Kevin K Y Ho

Full Text Available Hong Kong imposed a partial restriction on application of organotin-based antifouling paints in 1992. Since September 2008, the International Maritime Organization prohibited the use of such antifouling systems on all sea-going vessels globally. Therefore, it is anticipated a gradual reduction of organotin contamination in Hong Kong's marine waters. Using the rock shell Reishia clavigera as a biomonitor, we evaluated the organotin contamination along Hong Kong's coastal waters over the past two decades (1990-2015. In 2010 and 2015, adult R. clavigera were examined for imposex status and analysed for tissue concentrations of six organotins. We consistently found 100% imposex incidence in female R. clavigera across all sites. Tissue triphenyltin (TPT concentrations were high in most samples. A probabilistic risk assessment showed that there were over 69% of chance that local R. clavigera would be at risk due to exposure to phenyltins. Comparing with those of previous surveys (2004-2010, both imposex levels and tissue concentrations of organotins did not decline, while the ecological risks due to exposure to organotins were increasing. We also observed high concentrations of monobutyltin and TPT in seawater and sediment from locations with intense shipping activities and from stormwater or sewage discharge. Overall, organotins are still prevalent in Hong Kong's marine waters showing that the global convention alone may be inadequate in reducing organotin contamination in a busy international port like Hong Kong. Appropriate management actions should be taken to control the use and release of organotins in Hong Kong and South China.

Hydrolysis of Some C,N-Chelated Organotin(IV) Species Used in Catalysis

OpenAIRE

Švec, P.

2012-01-01

This work deals with the reactivity of the selected C, N-chelated organotin (IV) species towards cyclohexene oxide, ethylene carbonate, and CO2. Structure of organotin(IV) hydrolytic products isolated from respective reaction mixtures was described.

Joy and flustration with organofluorine compounds - a fluorous autobiography.

Science.gov (United States)

Seebach, Dieter

2014-01-01

An overview is given about our work on fluoro-organic compounds, published or described in PhD theses between 1977 and 2013. After a discussion of structural F-effects and F-tagging applications the material is ordered by the various areas of our research, in which we have used and/or prepared F-derivatives: Li- and Ti-organic compounds and reagents, polylithiated hydroxy-esters and nitroalkanes, the enantiopure trifluoro-lactic, -Roche, and -3-hydroxy-butanoic acids as toolbox for the preparation of numerous F₃C-substituted compounds, including natural products and dendrimers, and fluoro-α-, -β-, and -δ-amino acids, as well as peptides with back-bond-bound fluorine. The strong influence on β-peptide folding by fluoro-substituents in the α-position of β-amino-acid residues is discussed in terms of the α-fluoro-amide conformational effect. Finally, some cases of totally unexpected effects on reactivity and structure exerted by fluoro-substitution are presented and taken as examples for our use of the terms flustrate and flustration in connection with organo-fluorine chemistry.

The synthesis of imidazo[4',5':5,6]cycloocta[1,2- B ]quinoxaline-2 ...

African Journals Online (AJOL)

-2-ones (-2-thione) with an additional double bond in the eight-membered ring via the reaction of a quinoxaline-fused cyclooctane-1,2-dione with urea (or thiourea) and N,N'-dimethylurea. KEY WORDS: Quinoxaline, Imidazolone, ...

An Efficient Protocol for the Synthesis of Quinoxaline Derivatives at Room Temperature Using Recyclable Alumina-Supported Heteropolyoxometalates

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Diego M. Ruiz

2012-01-01

Full Text Available We report a suitable quinoxaline synthesis using molybdophosphovanadates supported on commercial alumina cylinders as catalysts. These catalysts were prepared by incipient wetness impregnation. The catalytic test was performed under different reaction conditions in order to know the performance of the synthesized catalysts. The method shows high yields of quinoxaline derivatives under heterogeneous conditions. Quinoxaline formation was obtained using benzyl, o-phenylenediamine, and toluene as reaction solvent at room temperature. The CuH2PMo11VO40 supported on alumina showed higher activity in the tested reaction. Finally, various quinoxalines were prepared under mild conditions and with excellent yields.

The addition of organotin hydrides to isocyanates and isothiocyanates: synthesis and structure of some organotin-substituted amides

NARCIS (Netherlands)

Noltes, J.G.; Janssen, M.J.

Organotin hydrides add across the carbon---nitrogen double bond of aryl isocyanates (tin---nitrogen bond formation) and hexyl isocyanate (tin---carbon bond formation) and across the carbon---sulfur double bond of phenyl isothiocyanate (tin---sulfur bond formation) to afford in excellent yield 1:1

Structural basis for PPARγ transactivation by endocrine-disrupting organotin compounds

Science.gov (United States)

Harada, Shusaku; Hiromori, Youhei; Nakamura, Shota; Kawahara, Kazuki; Fukakusa, Shunsuke; Maruno, Takahiro; Noda, Masanori; Uchiyama, Susumu; Fukui, Kiichi; Nishikawa, Jun-Ichi; Nagase, Hisamitsu; Kobayashi, Yuji; Yoshida, Takuya; Ohkubo, Tadayasu; Nakanishi, Tsuyoshi

2015-02-01

Organotin compounds such as triphenyltin (TPT) and tributyltin (TBT) act as endocrine disruptors through the peroxisome proliferator-activated receptor γ (PPARγ) signaling pathway. We recently found that TPT is a particularly strong agonist of PPARγ. To elucidate the mechanism underlying organotin-dependent PPARγ activation, we here analyzed the interactions of PPARγ ligand-binding domain (LBD) with TPT and TBT by using X-ray crystallography and mass spectroscopy in conjunction with cell-based activity assays. Crystal structures of PPARγ-LBD/TBT and PPARγ-LBD/TPT complexes were determined at 1.95 Å and 1.89 Å, respectively. Specific binding of organotins is achieved through non-covalent ionic interactions between the sulfur atom of Cys285 and the tin atom. Comparisons of the determined structures suggest that the strong activity of TPT arises through interactions with helix 12 of LBD primarily via π-π interactions. Our findings elucidate the structural basis of PPARγ activation by TPT.

Health Risk Assessment for Organotins in Textiles

NARCIS (Netherlands)

Janssen PJCM; van Veen MP; Speijers GJA; CSR; LBM

2000-01-01

In januari 1998 werd het RIVM gevraagd een voorlopige risicobeoordeling uit te voeren voor organische tinverbindingen (organotins) in textiel. Metingen uitgevoerd door de Inspectie Gezondheidsbescherming, Waren en Veterinaire Zaken wezen op de aanwezigheid van deze potentieel toxische verbindingen

Synthetic Methods and Exploring Biological Potential of Various Substituted Quinoxalin-2-one Derivatives

OpenAIRE

Mohammad Asif

2016-01-01

Substituted quinoxaline have considerable interest in chemistry, biology and pharmacology. Quinoxaline derivatives are capable with variety of biological activities and possess different biological activities, of which the most potent are anti-microbial, analgesic and anti-inflammatory activities. It facilitated the researchers to develop various methods for their synthesis and their applications. In this review represented different methods of synthesis, reactivity and various biological act...

Speciation of organotin compounds by capillary electrophoresis: comparison of aqueous and mixed organic-aqueous systems

Energy Technology Data Exchange (ETDEWEB)

Guo, Lei; Matysik, Frank-Michael; Glaeser, Petra [Universitaet Leipzig, Institut fuer Analytische Chemie, Leipzig (Germany)

2004-10-01

A capillary electrophoresis method with direct ultraviolet detection was developed for the analysis of organotin species. Despite the fact that direct detection of organotin compounds by ultraviolet absorption is difficult because most organotins possess poor chromophoric properties, the application of low wavelength ({lambda}=200 nm) and mixed organic-aqueous media enabled a significant enhancement in sensitivity. A mixed organic-aqueous system (10% methanol/40% acetonitrile/50% H{sub 2}O) containing acetic acid and tetrabutylammonium perchlorate formed the basis for rapid, efficient and sensitive determinations of organotin cations such as tripropyltin, tributyltin, triphenyltin and diphenyltin. The concentration limits of detection (LOD) for the four organotin compounds were in the range of 0.4-14 {mu}M, comparable to that obtained with the most sensitive indirect UV method reported until now, and took advantage of a stable baseline, a symmetric peak shape and an absence of disturbing system peaks. The relative standard deviations (n=7) for the relative peak time and peak area were 0.44-0.77 and 4.8-5.8%, respectively. In addition to sensitivity enhancements, the use of organic-aqueous systems instead of pure aqueous media resulted in improved selectivity and efficiency of separations. (orig.)

Synthesis and Characterization of Organotin Containing Copolymers: Reactivity Ratio Studies

Directory of Open Access Journals (Sweden)

Mohamed H. El-Newehy

2010-03-01

Full Text Available Organotin monomers containing dibutyltin groups – dibutyltin citraconate (DBTC as a new monomer and dibutyltin maleate (DBTM – were synthesized. Free radical copolymerizations of the organotin monomers with styrene (ST and butyl acrylate (BA were performed. The overall conversion was kept low (≤15% wt/wt for all studied samples and the copolymers composition was determined from tin analysis using the Gillman and Rosenberg method. The reactivity ratios were calculated from the copolymer composition using the Fineman-Ross (FR method. The synthesized monomers were characterized by elemental analysis, 1H-, 13C-NMR and FTIR spectroscopy.

SYNTHESIS OF BIS-QUINOXALINE DERIVATIVES USING TONSIL ...

African Journals Online (AJOL)

A convenient and efficient synthesis of new bis-quinoxaline is described, involving ... the following composition (in %): SiO2: 74.5, Al2O3: 9.3, MgO: 0.4, Fe2O3: 1.3, CaO: 4.0, K2O: 0.4 and .... Tonsil clay is a nanoparticle with layered structure.

Preparation of radiohalogenated biomolecules via organotin intermediates. Ch. 8

International Nuclear Information System (INIS)

Hanson, R.N.

1991-01-01

The purpose of this review is to describe the specific application of organotin chemistry to the preparation of radiohalogenated bio-organic compounds as radiotracers. Although the research group was the first to apply the radiohalodestannylation methodology to the synthesis of a labeled compound of biological interest, iodotamoxifen, and subsequently extended its use to the labeled hormones, dopamine receptor antagonists and perfusion agents, the versatility of the method has subsequently found broad acceptance. For many situations in which high specific activity, rapidity of incorporation and labeling site specificity are required, electrophilic destannylation is the method of choice. The sections that follow provide a description of the development of radiohalodestannylation and its application in radiopharmaceutical chemistry. The first section will briefly review the criteria that define the radionuclidic, biochemical and chemical limits associated with radiopharmaceuticals. The next section describes the rationale for the choice of organotin intermediates and highlights the methods available for their synthesis. Following that section are several areas of biomedical research interest that illustrate how organotin chemistry has been applied in the preparation of specific radiohalogenated compounds. Although the examples will focus primarily on situations that require high affinity and specific activity, labeled derivatives which were prepared to evaluate more general physiological properties will also be reviewed. (author). 171 refs

Inorganic tin and organotin interactions with candida maltosa

Energy Technology Data Exchange (ETDEWEB)

White, J.S.; Tobin, J.M. [School of Biotechnology, Dublin City Univ., Dublin (Ireland)

2004-07-01

As a consequence of the widespread industrial and agricultural applications of organotins, contamination of various ecosystems has occurred in recent decades. Understanding how these compounds interact with microorganisms is important in assessing the risks of organotin pollution. The organotins, tributyltin (TBT), trimethyltin (TMT) and inorganic tin, Sn(IV), were investigated for their physical interactions with non-metabolising cells and protoplasts of the yeast candida maltosa, an organism that is often associated with contaminated environments. Uptake, toxicity and membrane-acting effects of these compounds, at concentrations approximating those found in polluted environments, were assessed. Sn(IV) and TBT uptake occurred by different mechanisms. Uptake of Sn(IV) was 2-fold greater in intact cells than protoplasts, underlining the importance of cell wall binding, whereas TBT uptake levels by both cell types were similar. TBT uptake resulted in cell death and extensive K{sup +} leakage, while Sn(IV) uptake had no effect. TMT did not interact with cells. Of the three compounds, TBT alone altered membrane fluidity, as measured by the fluorescence anisotropy of 1,6-diphenyl-1,3,5-hexatriene incorporated into cells. Anisotropy of 1-(4-trimethylaminophenyl-6-phenyl-1,3,5-hexatriene) was not affected, implying that TBT is not confined to the surface of the cytoplasmic membrane, but acts within membrane lipids. These results indicate that the cell wall is the dominant site of Sn(IV) interactions with yeast, while lipophilic interactions play an important role in uptake and toxicity of TBT. (orig.)

Fast and effective low-temperature freezing extraction technique to determine organotin compounds in edible vegetable oil.

Science.gov (United States)

Liu, Yingxia; Ma, Yaqian; Wan, Yiqun; Guo, Lan; Wan, Xiaofen

2016-06-01

Most organotin compounds that have been widely used in food packaging materials and production process show serious toxicity effects to human health. In this study, a simple and low-cost method based on high-performance liquid chromatography with inductively coupled plasma mass spectrometry for the simultaneous determination of four organotins in edible vegetable oil samples was developed. Four organotins including dibutyltin dichloride, tributyltin chloride, diphenyltin dichloride, and triphenyltin chloride were simultaneously extracted with methanol using the low-temperature precipitation process. After being concentrated, the extracts were purified by matrix solid-phase dispersion using graphitized carbon black. The experimental parameters such as extraction solvent and clean-up material were optimized. To evaluate the accuracy of the new method, the recoveries were investigated. In addition, a liquid chromatography with tandem mass spectrometry method was also proposed for comparison. The procedures of extracting and purifying samples for the analysis were simple and easy to perform batch operations, also showed good efficiency with lower relative standard deviation. The limits of detection of the four organotins were 0.28-0.59 μg/L, and the limits of quantification of the four organotins were 0.93-1.8 μg/L, respectively. The proposed method was successfully applied to the simultaneous analysis of the four organotins in edible vegetable oil. Some analytes were detected at the level of 2.5-28.8 μg/kg. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Activation of RXR–PPAR heterodimers by organotin environmental endocrine disruptors

Science.gov (United States)

le Maire, Albane; Grimaldi, Marina; Roecklin, Dominique; Dagnino, Sonia; Vivat-Hannah, Valérie; Balaguer, Patrick; Bourguet, William

2009-01-01

The nuclear receptor retinoid X receptor-α (RXR-α)–peroxisome proliferator-activated receptor-γ (PPAR-γ) heterodimer was recently reported to have a crucial function in mediating the deleterious effects of organotin compounds, which are ubiquitous environmental contaminants. However, because organotins are unrelated to known RXR-α and PPAR-γ ligands, the mechanism by which these compounds bind to and activate the RXR-α–PPAR-γ heterodimer at nanomolar concentrations has remained elusive. Here, we show that tributyltin (TBT) activates all three RXR–PPAR-α, -γ, -δ heterodimers, primarily through its interaction with RXR. In addition, the 1.9 Å resolution structure of the RXR-α ligand-binding domain in complex with TBT shows a covalent bond between the tin atom and residue Cys 432 of helix H11. This interaction largely accounts for the high binding affinity of TBT, which only partly occupies the RXR-α ligand-binding pocket. Our data allow an understanding of the binding and activation properties of the various organotins and suggest a mechanism by which these tin compounds could affect other nuclear receptor signalling pathways. PMID:19270714

The cyto- and genotoxicity of organotin compounds is dependent on the cellular uptake capability

International Nuclear Information System (INIS)

Dopp, E.; Hartmann, L.M.; Recklinghausen, U. von; Florea, A.M.; Rabieh, S.; Shokouhi, B.; Hirner, A.V.; Obe, G.; Rettenmeier, A.W.

2007-01-01

Organotin compounds have been widely used as stabilizers and anti-fouling agents with the result that they are ubiquitously distributed in the environment. Organotins accumulate in the food chain and potential effects on human health are disquieting. It is not known as yet whether cell surface adsorption or accumulation within the cell, or indeed both is a prerequisite for the toxicity of organotin compounds. In this study, the alkylated tin derivatives monomethyltin trichloride (MMT), dimethyltin dichloride (DMT), trimethyltin chloride (TMT) and tetramethyltin (TetraMT) were investigated for cyto- and genotoxic effects in CHO-9 cells in relation to the cellular uptake. To identify genotoxic effects, induction of micronuclei (MN), chromosome aberrations (CA) and sister chromatid exchanges (SCE) were analyzed and the nuclear division index (NDI) was calculated. The cellular uptake was assessed using ICP-MS analysis. The toxicity of the tin compounds was also evaluated after forced uptake by electroporation. Our results show that uptake of the organotin compounds was generally low but dose-dependent. Only weak genotoxic effects were observed after exposure of cells to DMT and TMT. MMT and TetraMT were negative in the test systems. After forced uptake by electroporation MMT, DMT and TMT induced significant DNA damage at non-cytotoxic concentrations. The results presented here indicate a considerable toxicological potential of some organotin species but demonstrate clearly that the toxicity is modulated by the cellular uptake capability

4-Chlorotetrazolo[1,5-a]quinoxaline inhibits activation of Syk kinase to suppress mast cells in vitro and mast cell-mediated passive cutaneous anaphylaxis in mice

Energy Technology Data Exchange (ETDEWEB)

Park, Kui Lea [Center for Drug Development Assistance, National Institute of Food Drug Safety Evaluation (NIFDS), KFDA, Cheongwon-gun (Korea, Republic of); Ko, Na Young; Lee, Jun Ho; Kim, Do Kyun; Kim, Hyuk Soon; Kim, A-Ram; Her, Erk; Kim, Bokyung [Department of Immunology and physiology, College of Medicine, Konkuk University, Chungju (Korea, Republic of); Kim, Hyung Sik [College of Pharmacy, Pusan National University, Busan (Korea, Republic of); Moon, Eun-Yi [Department of Bioscience and Biotechnology, College of Biological Science, Sejong University, Seoul (Korea, Republic of); Kim, Young Mi [College of Pharmacy, Duksung Women' s University, Seoul (Korea, Republic of); Kim, Hang-Rae, E-mail: hangrae2@snu.ac.kr [Department of Anatomy, Seoul National University College of Medicine, Seoul (Korea, Republic of); Choi, Wahn Soo, E-mail: wahnchoi@kku.ac.kr [Department of Immunology and physiology, College of Medicine, Konkuk University, Chungju (Korea, Republic of)

2011-12-15

4-Chlorotetrazolo[1,5-a]quinoxaline is a quinoxaline derivative. We aimed to study the effects of 4-chlorotetrazolo[1,5-a]quinoxaline on activation of mast cells in vitro and in mice. 4-Chlorotetrazolo[1,5-a]quinoxaline reversibly inhibited degranulation of mast cells in a dose-dependent manner, and also suppressed the expression and secretion of TNF-{alpha} and IL-4 in mast cells. Mechanistically, 4-chlorotetrazolo[1,5-a]quinoxaline inhibited activating phosphorylation of Syk and LAT, which are crucial for early Fc{epsilon}RI-mediated signaling events, as well as Akt and MAP kinases, which play essential roles in the production of various pro-inflammatory cytokines in mast cells. Notably, although 4-chlorotetrazolo[1,5-a]quinoxaline inhibited the activation of Fyn and Syk, minimal inhibition was observed in mast cells in the case of Lyn. Furthermore, consistent with its in vitro activity, 4-chlorotetrazolo[1,5-a]quinoxaline significantly suppressed mast cell-mediated passive cutaneous anaphylaxis in mice. In summary, the results from this study demonstrate that 4-chlorotetrazolo[1,5-a]quinoxaline shows an inhibitory effect on mast cells in vitro and in vivo, and that this is mediated by inhibiting the activation of Syk in mast cells. Therefore, 4-chlorotetrazolo[1,5-a]quinoxaline could be useful in the treatment of mast cell-mediated allergic diseases. -- Highlights: Black-Right-Pointing-Pointer 4-chlorotetrazolo[1,5-a]quinoxaline is a quinoxaline derivative. Black-Right-Pointing-Pointer The effect of 4-chlorotetrazolo[1,5-a]quinoxaline on mast cells was investigated. Black-Right-Pointing-Pointer 4-chlorotetrazolo[1,5-a]quinoxaline reversibly inhibited Syk activation. Black-Right-Pointing-Pointer 4-chlorotetrazolo[1,5-a]quinoxaline could be useful for IgE-mediated allergy.

4-Chlorotetrazolo[1,5-a]quinoxaline inhibits activation of Syk kinase to suppress mast cells in vitro and mast cell-mediated passive cutaneous anaphylaxis in mice

International Nuclear Information System (INIS)

Park, Kui Lea; Ko, Na Young; Lee, Jun Ho; Kim, Do Kyun; Kim, Hyuk Soon; Kim, A-Ram; Her, Erk; Kim, Bokyung; Kim, Hyung Sik; Moon, Eun-Yi; Kim, Young Mi; Kim, Hang-Rae; Choi, Wahn Soo

2011-01-01

4-Chlorotetrazolo[1,5-a]quinoxaline is a quinoxaline derivative. We aimed to study the effects of 4-chlorotetrazolo[1,5-a]quinoxaline on activation of mast cells in vitro and in mice. 4-Chlorotetrazolo[1,5-a]quinoxaline reversibly inhibited degranulation of mast cells in a dose-dependent manner, and also suppressed the expression and secretion of TNF-α and IL-4 in mast cells. Mechanistically, 4-chlorotetrazolo[1,5-a]quinoxaline inhibited activating phosphorylation of Syk and LAT, which are crucial for early FcεRI-mediated signaling events, as well as Akt and MAP kinases, which play essential roles in the production of various pro-inflammatory cytokines in mast cells. Notably, although 4-chlorotetrazolo[1,5-a]quinoxaline inhibited the activation of Fyn and Syk, minimal inhibition was observed in mast cells in the case of Lyn. Furthermore, consistent with its in vitro activity, 4-chlorotetrazolo[1,5-a]quinoxaline significantly suppressed mast cell-mediated passive cutaneous anaphylaxis in mice. In summary, the results from this study demonstrate that 4-chlorotetrazolo[1,5-a]quinoxaline shows an inhibitory effect on mast cells in vitro and in vivo, and that this is mediated by inhibiting the activation of Syk in mast cells. Therefore, 4-chlorotetrazolo[1,5-a]quinoxaline could be useful in the treatment of mast cell-mediated allergic diseases. -- Highlights: ► 4-chlorotetrazolo[1,5-a]quinoxaline is a quinoxaline derivative. ► The effect of 4-chlorotetrazolo[1,5-a]quinoxaline on mast cells was investigated. ► 4-chlorotetrazolo[1,5-a]quinoxaline reversibly inhibited Syk activation. ► 4-chlorotetrazolo[1,5-a]quinoxaline could be useful for IgE-mediated allergy.

Studies on electrochemical treatment of wastewater contaminated with organotin compounds

Energy Technology Data Exchange (ETDEWEB)

Arevalo, Eduardo [Hamburg University of Technology, Institute of Environmental Technology and Energy Economics, Eissendorfer Strasse 40, D-21073 Hamburg (Germany); Calmano, Wolfgang [Hamburg University of Technology, Institute of Environmental Technology and Energy Economics, Eissendorfer Strasse 40, D-21073 Hamburg (Germany)]. E-mail: calmano@tuhh.de

2007-07-31

Different anode materials were tested to evaluate their suitability to eliminate organotin compounds electrochemically from shipyard process waters. The capacity of two types of anode materials was investigated: niobium coated with boron-doped diamond (BDD) and titanium coated with iridium dioxide (Ti/IrO{sub 2}). The aim of this work was to characterize the performance of the process using both anode materials at different current densities, and also to evaluate the generation of by-products. A further objective of this work was to evaluate if operating at low potentials with BDD anodes (to avoid the generation of elemental oxygen) the consumption of energy for degradation of pollutants could be minimized. The processes were tested on synthetic and real shipyard water containing approximately 25,000 ng L{sup -1} of tributyltin (TBT) (as Sn) and 5000 ng L{sup -1} dibutyltin. The range of current densities was between 6 and 70 mA cm{sup -2}. The results showed that electrochemical treatment is suitable to eliminate organotins down to very low concentrations following a stepwise debutylation mechanism. Both anode materials exhibited a similar performance with energy consumption in the range of 7-10 kWh m{sup -3} in order to decrease organotins down to 100 ng L{sup -1} (as Sn). For the water composition tested, BDD did not outperform Ti/IrO{sub 2} as initially expected, most probably because organotins were not only oxidized by {center_dot}OH, but also by active chlorine compounds generated by the oxidation of chloride present in the wastewater (1.6 g L{sup -1}, Cl{sup -}) with both anode materials. It was also found that the residual oxidants remaining in the treated effluent had to be eliminated if the water is to be discharged safely in the aquatic environment.

Studies on electrochemical treatment of wastewater contaminated with organotin compounds

International Nuclear Information System (INIS)

Arevalo, Eduardo; Calmano, Wolfgang

2007-01-01

Different anode materials were tested to evaluate their suitability to eliminate organotin compounds electrochemically from shipyard process waters. The capacity of two types of anode materials was investigated: niobium coated with boron-doped diamond (BDD) and titanium coated with iridium dioxide (Ti/IrO 2 ). The aim of this work was to characterize the performance of the process using both anode materials at different current densities, and also to evaluate the generation of by-products. A further objective of this work was to evaluate if operating at low potentials with BDD anodes (to avoid the generation of elemental oxygen) the consumption of energy for degradation of pollutants could be minimized. The processes were tested on synthetic and real shipyard water containing approximately 25,000 ng L -1 of tributyltin (TBT) (as Sn) and 5000 ng L -1 dibutyltin. The range of current densities was between 6 and 70 mA cm -2 . The results showed that electrochemical treatment is suitable to eliminate organotins down to very low concentrations following a stepwise debutylation mechanism. Both anode materials exhibited a similar performance with energy consumption in the range of 7-10 kWh m -3 in order to decrease organotins down to 100 ng L -1 (as Sn). For the water composition tested, BDD did not outperform Ti/IrO 2 as initially expected, most probably because organotins were not only oxidized by ·OH, but also by active chlorine compounds generated by the oxidation of chloride present in the wastewater (1.6 g L -1 , Cl - ) with both anode materials. It was also found that the residual oxidants remaining in the treated effluent had to be eliminated if the water is to be discharged safely in the aquatic environment

Electrochemical Behavior of Quinoxalin-2-one Derivatives at Mercury Electrodes and Its Analytical Use

OpenAIRE

Zimpl, Milan; Skopalova, Jana; Jirovsky, David; Bartak, Petr; Navratil, Tomas; Sedonikova, Jana; Kotoucek, Milan

2012-01-01

Derivatives of quinoxalin-2-one are interesting compounds with potential pharmacological activity. From this point of view, understanding of their electrochemical behavior is of great importance. In the present paper, a mechanism of electrochemical reduction of quinoxalin-2-one derivatives at mercury dropping electrode was proposed. Pyrazine ring was found to be the main electroactive center undergoing a pH-dependent two-electron reduction process. The molecule protonization of nitrogen in th...

In vitro and in vivo assessment of newer quinoxaline-oxadiazole hybrids as antimicrobial and antiprotozoal agents.

Science.gov (United States)

Patel, Navin B; Patel, Jignesh N; Purohit, Amit C; Patel, Vatsal M; Rajani, Dhanji P; Moo-Puc, Rosa; Lopez-Cedillo, Julio Cesar; Nogueda-Torres, Benjamin; Rivera, Gildardo

2017-09-01

A new series of N-(substituted-phenyl)-2-[5-(quinoxalin-2-yloxymethyl)-[1,3,4] oxadiazol-2-ylsulfanyl]-acetamides (5a-o) was designed and synthesised from the parent compound 2-hydroxy quinoxaline (1) through a multistep reaction sequence and was characterised by spectral and elemental analyses. All of the compounds synthesised were evaluated for their antimicrobial and antiprotozoal activities. The results revealed that quinoxaline-based 1,3,4-oxadiazoles displayed promising antibacterial, antifungal and anti-Trypanosoma cruzi activities compared with reference drugs, particularly the lead compound 5l in a short-term in vivo model in T. cruzi. Copyright © 2017 Elsevier B.V. and International Society of Chemotherapy. All rights reserved.

Asymmetric Hydrogenation of Quinoxalines Catalyzed by Iridium/PipPhos

NARCIS (Netherlands)

Mrsic, Natasa; Jerphagnon, Thomas; Minnaard, Adriaan J.; Feringa, Ben L.; de Vries, Johannes G.

2009-01-01

A catalyst made in situ from the (cyclooctadiene)iridium chloride dimer, [Ir(COD)Cl](2), and the monodentate phosphoramidite ligand (S)-PipPhos was used in the enantioselective hydrogenation of 2- and 2,6-substituted quinoxalines. In the presence of piperidine hydrochloride as additive full

Organotin analysis by gas chromatography-pulsed flame-photometric detection (GC-PFPD)

Energy Technology Data Exchange (ETDEWEB)

Leermakers, M.; Nuyttens, J.; Baeyens, W. [Vrije Universiteit Brussel, Analytical and Environmental Chemistry (ANCH), Brussel (Belgium)

2005-03-01

Monobutyltin (MBuT), dibutyltin (DBuT), and tributyltin (TBuT) mixtures have been separated and quantified by gas chromatography with pulsed flame-photometric detection (GC-PFPD). The compounds were first derivatized with NaBEt{sub 4}, then extracted with hexane and injected into the GC in splitless mode. Optimum GC and detector conditions were established. For GC, various injector temperatures and oven temperature programs were tested. For the PFPD detector, gate settings (gate delay and gate width) and detector temperature were optimized. A very good linearity was obtained up to 100-150 ppb for all organotin compounds. The detection limits obtained were: MBuT (0.7 ppb), DBuT (0.8 ppb), and TBuT (0.6 ppb). RSD for repeatability and reproducibility were well below 20% when the instrument was in routine operation. A biological sample (CRM 477) was also analyzed for organotins. Extraction from the biological matrix was performed with TMAH. Besides the increased risk of contamination, the derivatization step seemed to be critical. pH and amount of derivatizing agent were tested. When using an internal standard (TPrT) between 90% and 110% of the certified amounts of organotin were recovered. (orig.)

One-pot three-component synthesis of quinoxaline and phenazine ring systems using Fischer carbene complexes

Directory of Open Access Journals (Sweden)

Priyabrata Roy

2010-05-01

Full Text Available One-pot three-component coupling of o-alkynylheteroaryl carbonyl derivatives with Fischer carbene complexes and dienophiles leading to the synthesis of quinoxaline and phenazine ring systems has been investigated. This involves the generation of furo[3,4-b]pyrazine and furo[3,4-b]quinoxaline as transient intermediates, which were trapped with Diels–Alder dienophiles. This is the first report on furo[3,4-b]pyrazine intermediates.

Development of quinoxaline based polymers for photovoltaic applications

Czech Academy of Sciences Publication Activity Database

Yuan, J.; Ouyang, J.; Cimrová, Věra; Leclerc, M.; Najari, A.; Zou, Y.

2017-01-01

Roč. 5, č. 8 (2017), s. 1858-1879 ISSN 2050-7526 R&D Projects: GA ČR(CZ) GA13-26542S Institutional support: RVO:61389013 Keywords : conjugated polymers * quinoxaline based * photovoltaic s Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 5.256, year: 2016

Aromatic quinoxaline as corrosion inhibitor for bronze in aqueous ...

Indian Academy of Sciences (India)

Administrator

These compounds act through the formation of a protective film on the surface of the ... Bronze; inhibitors; quinoxalin compounds; chloride solution; electrochemical studies. 1. ... elements such as aluminum, nickel and iron offer a good ... cations such as pump casting, valves and heat exchanger. ..... to investigate this layer.

C-shaped diastereomers containing cofacial thiophene-substituted quinoxaline rings: synthesis, photophysical properties, and X-ray crystallography.

Science.gov (United States)

DeBlase, Catherine R; Finke, Ryan T; Porras, Jonathan A; Tanski, Joseph M; Nadeau, Jocelyn M

2014-05-16

Synthesis and characterization of two diastereomeric C-shaped molecules containing cofacial thiophene-substituted quinoxaline rings are described. A previously known bis-α-diketone was condensed with an excess of 4-bromo-1,2-diaminobenzene in the presence of zinc acetate to give a mixture of two C-shaped diastereomers with cofacial bromine-substituted quinoxaline rings. After chromatographic separation, thiophene rings were installed by a microwave-assisted Suzuki coupling reaction, resulting in highly emissive diastereomeric compounds that were studied by UV-vis, fluorescence, and NMR spectroscopy, as well as X-ray crystallography. The unique symmetry of each diastereomer was confirmed by NMR spectroscopy. NMR data indicated that the syn isomer has restricted rotation about the bond connecting the thiophene and quinoxaline rings, which was also observed in the solid state. The spectroscopic properties of the C-shaped diastereomers were compared to a model compound containing only a single thiophene-substituted quinoxaline ring. Ground state intramolecular π-π interactions in solution were detected by NMR and UV-vis spectroscopy. Red-shifted emission bands, band broadening, and large Stokes shifts were observed, which collectively suggest excited state π-π interactions that produce excimer-like emissions, as well as a remarkable positive emission solvatochromism, indicating charge-transfer character in the excited state.

3-{2-[(3-{(E-2-[4-(Dimethylaminophenyl]ethenyl}quinoxalin-2-yloxy]ethyl}-1,3-oxazolidin-2-one monohydrate

Directory of Open Access Journals (Sweden)

Youssef Ramli

2012-01-01

Full Text Available In the title compound, C23H24N4O3·H2O, the 1,3-oxazoline ring is nearly planar [maximum deviation = 0.059 (2 Å] and its mean plane is twisted by 30.12 (8° with respect to the quinoxaline fused-ring system; the benzene ring is nearly coplanar with the quinoxaline fused-ring system [dihedral angle = 2.52 (2°]. The water molecule of crystallization is hydrogen-bond donor to an N atom of the quinoxaline ring system as well as an O atom of the oxazolinone unit, the two hydrogen bonds generating a chain running along the c axis.

Acute effects of organotins on brain, liver and kidney in rats

Energy Technology Data Exchange (ETDEWEB)

Dwivedi, R.S.; Kaur, G.; Srivastava, R.C.; Srivastava, T.N.

1985-01-01

Effects of dioctyltin oxide (DOTO) tricyclohexyltin hydroxide (TCHTOH) and tributyltin oxide (TBTO) were examined on some enzymic activities in liver and kidney and biogenic amines level in brain of rats at 24 hours after single subcutaneous administration (25 ..mu..mole/100 g B. Wt.). All the organotin compounds produced a significant increase in the activity of alkaline phosphatase and adenosin triphosphatase and decrease in monoamine oxidase in both liver and kidney. DOTO and TCHTOH were more effective in impairing the activity of succinate dehydrogenase in liver. Concentrations of ..gamma..-aminobutyric acid (GABA) and dopamine were found to be significantly decreased in brain however, acetylcholine concentration remained unaltered. These results suggest that organotin compounds DOTO and TCHTOH are more toxic to rats than TBTO. 30 references, 3 tables.

Facile, eco-friendly, catalyst-free synthesis of polyfunctionalized quinoxalines.

Science.gov (United States)

Zhang, Yaohong; Luo, Mengqiang; Li, Yan; Wang, Hai; Ren, Xiaorong; Qi, Chenze

2018-02-01

A novel, facile and eco-friendly synthesis of quinoxalines from [Formula: see text] and 1,2-diamines was developed. An attractive feature of this protocol is that the desired products could be generated efficiently in water and without any catalyst, which is in accordance with the aim of green chemistry. A plausible mechanism has been proposed.

Plasma biomarkers in juvenile marine fish provide evidence for endocrine modulation potential of organotin compounds.

Science.gov (United States)

Min, Byung Hwa; Kim, Bo-Mi; Kim, Moonkoo; Kang, Jung-Hoon; Jung, Jee-Hyun; Rhee, Jae-Sung

2018-08-01

Organotin compounds, such as tributyltin (TBT) and triphenyltin (TPT), have been widely used to control marine fouling. Here, we show that organotin stimulation reduces the hormone levels in the plasma of two economically important aquaculture fish. Blood plasma samples were collected from juvenile red seabream and black rockfish exposed to environmentally realistic concentrations of TBT and TPT for 14 days. The levels of two plasma biomarkers, namely the yolk protein precursor vitellogenin (VTG) and the sex steroid 17β-estradiol (E2), were measured to determine the endocrine disrupting potential of the organotin compounds. Both organotin compounds were dose-dependently accumulated in the blood of two fish. Exposure to waterborne TBT and TBT significantly decreased the plasma VTG levels in both the juvenile fish in a dose-dependent manner. In contrast, the treatment with E2, a well-known VTG inducer, significantly increased the plasma VTG levels in both the fish. In addition, the mRNA levels of vtg were also downregulated in the liver tissues of both the fish at 100 and/or 1000 ng L -1 of TBT or TPT exposure. The plasma E2 titers were significantly suppressed at 100 and/or 1000 ng L -1 of TBT or TPT exposure for 14 days compared to their titer in the control. Since estrogen directly regulates vtg gene expression and VTG synthesis, our results reveal the endocrine disrupting potential of organotin compounds, and subsequently the endocrine modulation at early stage of fish can trigger further fluctuations in sexual differentiation, maturation, sex ration or egg production. In addition, the results demonstrate their effects on non-target organisms, particularly on animals reared in aquaculture and fisheries. Copyright © 2018 Elsevier Inc. All rights reserved.

A green protocol for the synthesis of quinoxaline derivatives catalyzed by polymer supported sulphanilic acid

Directory of Open Access Journals (Sweden)

Umesh P. Tarpada

2017-05-01

Full Text Available Polymer supported sulphanilic acid was found to be an effective heterogeneous catalyst for one pot synthesis of various quinoxaline derivatives from the condensation reaction between 1,2-diamines and 1,2-dicarbonyl compounds in ethanol. Synthesis was attempted under reflux as well as at room temperature using ethanol as the solvent to afford excellent yields. Heterogeneity of the catalyst allowed its recycling for five times with almost retention in catalytic activity. Prepared quinoxaline derivatives were also tested for their antioxidant activity by the FRAP assay method.

Synthesis, characterization and antimicrobial activity of potential bioactive organotin(iv) dithiocarboxylates

International Nuclear Information System (INIS)

Abbas, S.M.; Sirajuddin, M.; Shah, F.A.

2013-01-01

A series of newly synthesized organotin(IV) compounds; Me/sub 2/SnClL (1) Bu2SnClL (2), Ph/sub 2/SnClL (3), Me/sub 3/SnL (4), Ph3SnL (5) have been derived from the reaction of organotin(IV) chlorides with 4-formylpiperazinium 4-formylpiperazine-1-carbodithioate (L) in the appropriate molar ratio. Their spectroscopic investigations have been carried out in solution state. Based on spectroscopic results, the ligand appeared to coordinate to the Sn atom through the CSS moiety. Bioassay results have revealed that these compounds have good antibacterial and antifungal activities and may well be the basis for a new class of antimicrobial drugs. The triorganotin(IV) derivatives in particular, were found to be more active than diorganotin(IV) compounds. (author)

Anti-Mycobacterium tuberculosis Activity of Esters of Quinoxaline 1,4-Di-N-Oxide

Directory of Open Access Journals (Sweden)

Isidro Palos

2018-06-01

Full Text Available Tuberculosis continues to be a public health problem in the world, and drug resistance has been a major obstacle in its treatment. Quinoxaline 1,4-di-N-oxide has been proposed as a scaffold to design new drugs to combat this disease. To examine the efficacy of this compound, this study evaluates methyl, ethyl, isopropyl, and n-propyl esters of quinoxaline 1,4-di-N-oxide derivatives in vitro against Mycobacterium tuberculosis (pansusceptible and monoresistant strains. Additionally, the inhibitory effect of esters of quinoxaline 1,4-di-N-oxide on M. tuberculosis gyrase supercoiling was examined, and a stability analysis by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS was also carried out. Results showed that eight compounds (T-007, T-018, T-011, T-069, T-070, T-072, T-085 and T-088 had an activity similar to that of the reference drug isoniazid (minimum inhibitory concentration (MIC = 0.12 µg/mL with an effect on nonreplicative cells and drug monoresistant strains. Structural activity relationship analysis showed that the steric effect of an ester group at 7-position is key to enhancing its biological effects. Additionally, T-069 showed a high stability after 24 h in human plasma at 37 °C.

Synthesis of quinoxaline derivatives from terminal alkynes and o ...

Indian Academy of Sciences (India)

Akhil V Nakhate

2017-11-02

Nov 2, 2017 ... Special Issue on Recent Trends in the Design and Development of ... reported Fe3O4@Cu2O supported on the graphene oxide ..... new quinoxaline-based dyes for dye sensitized solar cell .... Zheng L, Cheng X, Yu Y, Xie Y, Li X and Wang Z 2015. Controlled direct growth of Al2O3 -doped HfO2 films on.

Inhibitory effect of organotin compounds on rat neuronal nitric oxide synthase through interaction with calmodulin

International Nuclear Information System (INIS)

Ohashi, Koji; Kominami, Shiro; Yamazaki, Takeshi; Ohta, Shigeru; Kitamura, Shigeyuki

2004-01-01

Organotin compounds, triphenyltin (TPT), tributyltin, dibutyltin, and monobutyltin (MBT), showed potent inhibitory effects on both L-arginine oxidation to nitric oxide and L-citrulline, and cytochrome c reduction catalyzed by recombinant rat neuronal nitric oxide synthase (nNOS). The two inhibitory effects were almost parallel. MBT and TPT showed the highest inhibitory effects, followed by tributyltin and dibutyltin; TPT and MBT showed inhibition constant (IC 50 ) values of around 10 μM. Cytochrome c reduction activity was markedly decreased by removal of calmodulin (CaM) from the complete mixture, and the decrease was similar to the extent of inhibition by TPT and MBT. The inhibitory effect of MBT on the cytochrome c reducing activity was rapidly attenuated upon dilution of the inhibitor, and addition of a high concentration of CaM reactivated the cytochrome c reduction activity inhibited by MBT. However, other cofactors such as FAD, FMN or tetrahydrobiopterin had no such ability. The inhibitory effect of organotin compounds (100 μM) on L-arginine oxidation of nNOS almost vanished when the amount of CaM was sufficiently increased (150-300 μM). It was confirmed by CaM-agarose column chromatography that the dissociation of nNOS-CaM complex was induced by organotin compounds. These results indicate that organotin compounds disturb the interaction between CaM and nNOS, thereby inhibiting electron transfer from the reductase domain to cytochrome c and the oxygenase domain

Photostabilizing Efficiency of Poly(vinyl chloride in the Presence of Organotin(IV Complexes as Photostabilizers

Directory of Open Access Journals (Sweden)

Mustafa M. Ali

2016-08-01

Full Text Available Three organotin complexes containing furosemide as a ligand (L, Ph3SnL, Me2SnL2 and Bu2SnL2, were synthesized and characterized. Octahedral geometry was proposed for the Me2SnL2 and Bu2SnL2, while the Ph3SnL complex has trigonal bipyramid geometry. The synthesized organotin complexes (0.5% by weight were used as additives to improve the photostability of poly(vinyl chloride, PVC, (40 μm thickness upon irradiation. The changes imposed on functional groups, weight loss and viscosity average molecular weight of PVC films were monitored. The experimental results show that the rate of photodegradation was reduced in the presence of the organotin additives. The quantum yield of the chain scission was found to be low (9.8 × 10−7 when Ph3SnL was used as a PVC photostabilizer compared to controlled PVC (5.18 × 10−6. In addition, the atomic force microscope images for the PVC films containing Ph3SnL2 after irradiation shows a smooth surface compared to the controlled films. The rate of PVC photostabilization was found to be highest for Ph3SnL followed by Bu2SnL2 and Me2SnL2. It has been suggested that the organotin complexes could act as hydrogen chloride scavengers, ultraviolet absorbers, peroxide decomposers and/or radical scavengers.

Organotin compounds in precipitation, fog and soils of a forested ecosystem in Germany

International Nuclear Information System (INIS)

Huang, J.-H.; Schwesig, David; Matzner, Egbert

2004-01-01

Organotin compounds (OTC) are highly toxic pollutants and have been mostly investigated so far in aquatic systems and sediments. The concentrations and fluxes of different organotin compounds, including methyl-, butyl-, and octyltin species in precipitation and fog were investigated in a forested catchment in NE Bavaria, Germany. Contents, along with the vertical distribution and storages in two upland and two wetland soils were determined. During the 1-year monitoring, the OTC concentrations in bulk deposition, throughfall and fog ranged from 1 ng Sn l -1 to several ten ng Sn l -1 , but never over 200 ng Sn l -1 . The OTC concentrations in fog were generally higher than in throughfall and bulk deposition. Mono-substituted species were the dominant Sn species in precipitation (up to 190 ng Sn l -1 ) equaling a flux of up to 70 mg Sn ha -1 a -1 . In upland soils, OTC contents peaked in the forest floor (up to 30 ng Sn g -1 ) and decreased sharply with the depth. In wetland soils, OTC had slightly higher contents in the upper horizons. The dominance of mono-substituted species in precipitation is well reflected in the contents and storages of OTC in both upland and wetland soils. The ratios of OTC soil storages to the annual throughfall flux ranged from 20 to 600 years. These high ratios are probably due to high stability and low mobility of OTC in soils. No evidence was found for methylation of tin in the wetland soils. In comparison with sediments, concentrations and contents of organotin in forest soils are considerably lower, and the dominant species are less toxic. It is concluded that forested soils may act as sinks for OTC deposited from the atmosphere. - Forested soils may act as sinks for atmospherically deposited organotin compounds

Development and evaluation of a new diffusive gradients in thin-films technique for measuring organotin compounds in coastal sediment pore water

DEFF Research Database (Denmark)

Cole, Russell F.; Mills, Graham A.; Hale, Michelle S.

2018-01-01

in thin-films (DGT) adsorption gels to pre-concentrate five organotins (monobutlytin (MBT), dibutyltin (DBT), tributyltin (TBT), diphenyltin (DPhT), triphenyltin (TPhT)) found frequently in coastal sediment. C8 sorbent showed optimum performance in uptake and recovery of organotins for pH and ionic...

Organotin levels in seafood and its implications for health risk in high-seafood consumers

Energy Technology Data Exchange (ETDEWEB)

Guerin, T. [Agence francaise de securite sanitaire des aliments - Afssa, Unites CIME et PASER, AFSSA-LERQAP, 23 Av. du G. de Gaulle, 94706 Maisons-Alfort Cedex (France)], E-mail: t.guerin@afssa.fr; Sirot, V.; Volatier, J.-L.; Leblanc, J.-C. [Agence francaise de securite sanitaire des aliments - Afssa, Unites CIME et PASER, AFSSA-LERQAP, 23 Av. du G. de Gaulle, 94706 Maisons-Alfort Cedex (France)

2007-12-15

Fish and fishery products are considered as the main source of organotin compounds (OTC). Unfortunately, little national contamination data is available to assess food exposure of organotins from French consumers. To provide a more accurate estimate of risks to human health, the butyltin, phenyltin and octyltin compounds sampling in four French coastal areas were measured in 159 composite samples (96 fresh and frozen fish, 28 mollusks, 14 crustaceans, 1 echinoderm, 11 canned foods, 4 smoked fish, 5 prepared seafood-based dishes) by capillary gas chromatography coupled with a microwave induced plasma atomic-emission spectrometer (CGC-MIP-AES). In these samples, butyltins were usually predominant and the range of the contamination levels was generally below those of earlier studies (fish: mean 5.6; min-max 1.1-23 {mu}g/kg; fishery products: mean 6; min-max 0.8-14 {mu}g/kg). Fish, especially tuna, salmon, mackerel, saithe/coalfish and cod were largely the main contributors (38%) to the total organotin exposure. With the supplementary contribution of great scallop, surimi, squid and oysters, the exposure exceeded 50% in all. However, the utmost OTC exposure was lesser than 47% of the provisional tolerable weekly intake [EFSA (European Food Safety Agency). Opinion of the Scientific Panel on Contaminants in the food chain on a request from the Commission to assess the health risks to consumers associated with exposure to organotins in foodstuffs. (Question N{sup o}EFSA-Q-2003-110). The EFSA Journal, 102, 1-119, 2004. (http://www.efsa.eu.int)]. Nobody would exceed this limit. Finally, as this study has some limitations and since some other sources and health effects have not been clearly evaluated, it appears rational from public health and environmental viewpoints to continue to reduce the OTC levels in the environment.

Organotin levels in seafood and its implications for health risk in high-seafood consumers

International Nuclear Information System (INIS)

Guerin, T.; Sirot, V.; Volatier, J.-L.; Leblanc, J.-C.

2007-01-01

Fish and fishery products are considered as the main source of organotin compounds (OTC). Unfortunately, little national contamination data is available to assess food exposure of organotins from French consumers. To provide a more accurate estimate of risks to human health, the butyltin, phenyltin and octyltin compounds sampling in four French coastal areas were measured in 159 composite samples (96 fresh and frozen fish, 28 mollusks, 14 crustaceans, 1 echinoderm, 11 canned foods, 4 smoked fish, 5 prepared seafood-based dishes) by capillary gas chromatography coupled with a microwave induced plasma atomic-emission spectrometer (CGC-MIP-AES). In these samples, butyltins were usually predominant and the range of the contamination levels was generally below those of earlier studies (fish: mean 5.6; min-max 1.1-23 μg/kg; fishery products: mean 6; min-max 0.8-14 μg/kg). Fish, especially tuna, salmon, mackerel, saithe/coalfish and cod were largely the main contributors (38%) to the total organotin exposure. With the supplementary contribution of great scallop, surimi, squid and oysters, the exposure exceeded 50% in all. However, the utmost OTC exposure was lesser than 47% of the provisional tolerable weekly intake [EFSA (European Food Safety Agency). Opinion of the Scientific Panel on Contaminants in the food chain on a request from the Commission to assess the health risks to consumers associated with exposure to organotins in foodstuffs. (Question N o EFSA-Q-2003-110). The EFSA Journal, 102, 1-119, 2004. (http://www.efsa.eu.int)]. Nobody would exceed this limit. Finally, as this study has some limitations and since some other sources and health effects have not been clearly evaluated, it appears rational from public health and environmental viewpoints to continue to reduce the OTC levels in the environment

Structure activity relationships of quinoxalin-2-one derivatives as platelet-derived growth factor-beta receptor (PDGFbeta R) inhibitors, derived from molecular modeling.

Science.gov (United States)

Mori, Yoshikazu; Hirokawa, Takatsugu; Aoki, Katsuyuki; Satomi, Hisanori; Takeda, Shuichi; Aburada, Masaki; Miyamoto, Ken-ichi

2008-05-01

We previously reported a quinoxalin-2-one compound (Compound 1) that had inhibitory activity equivalent to existing platelet-derived growth factor-beta receptor (PDGFbeta R) inhibitors. Lead optimization of Compound 1 to increase its activity and selectivity, using structural information regarding PDGFbeta R-ligand interactions, is urgently needed. Here we present models of the PDGFbeta R kinase domain complexed with quinoxalin-2-one derivatives. The models were constructed using comparative modeling, molecular dynamics (MD) and ligand docking. In particular, conformations derived from MD, and ligand binding site information presented by alpha-spheres in the pre-docking processing, allowed us to identify optimal protein structures for docking of target ligands. By carrying out molecular modeling and MD of PDGFbeta R in its inactive state, we obtained two structural models having good Compound 1 binding potentials. In order to distinguish the optimal candidate, we evaluated the structural activity relationships (SAR) between the ligand-binding free energies and inhibitory activity values (IC50 values) for available quinoxalin-2-one derivatives. Consequently, a final model with a high SAR was identified. This model included a molecular interaction between the hydrophobic pocket behind the ATP binding site and the substitution region of the quinoxalin-2-one derivatives. These findings should prove useful in lead optimization of quinoxalin-2-one derivatives as PDGFb R inhibitors.

Polyethers for biomedical applications. Polymerization of propylene oxide by organozinc/organotin catalysts

NARCIS (Netherlands)

Bots, Jan Gert; van der Does, L.; Bantjes, Adriaan; Broersma, Jaap

1987-01-01

The polymerization of propylene oxide to obtain a high-molecular-weight polymer with an atactic structure required for the application as artificial blood vessels was investigated using combinations of organozinc and organotin compounds as catalyst. The composition of the most active catalyst,

The synthesis of benzimidazoles and quinoxalines from aromatic diamines and alcohols by iridium-catalyzed acceptorless dehydrogenative alkylation.

Science.gov (United States)

Hille, Toni; Irrgang, Torsten; Kempe, Rhett

2014-05-05

Benzimidazoles and quinoxalines are important N-heteroaromatics with many applications in pharmaceutical and chemical industry. Here, the synthesis of both classes of compounds starting from aromatic diamines and alcohols (benzimidazoles) or diols (quinoxalines) is reported. The reactions proceed through acceptorless dehydrogenative condensation steps. Water and two equivalents of hydrogen are liberated in the course of the reactions. An Ir complex stabilized by the tridentate P^N^P ligand N(2) ,N(6) -bis(di-isopropylphosphino)pyridine-2,6-diamine revealed the highest catalytic activity for both reactions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

One-pot efficient green synthesis of 1,4-dihydro-quinoxaline-2,3 ...

Indian Academy of Sciences (India)

Unknown

Thermal and powder X-ray diffraction analysis was carried out for some hydrated crystals. Keywords. Green chemistry ... Elemental analyses were done using Carlo–Erba 1108 and Perkin–Elmer series II 2400 instruments. 2.3 General synthesis of quinoxaline derivatives ... with a pestle in a mortar at room temperature in an.

Determination of organotin compounds by headspace solid-phase microextraction-gas chromatography-pulsed flame-photometric detection (HS-SPME-GC-PFPD)

Energy Technology Data Exchange (ETDEWEB)

Bravo, Manuel [Universite de Pau et des Pays de L' Adour, Laboratoire de Chimie Analytique, LCABIE, UMR CNRS 5034, Pau (France); Pontificia Universidad Catolica de Valparaiso, Laboratorio de Quimica Analitica y Ambiental, Instituto de Quimica, Valparaiso (Chile); Lespes, Gaetane; Gautier, Martine Potin [Pontificia Universidad Catolica de Valparaiso, Laboratorio de Quimica Analitica y Ambiental, Instituto de Quimica, Valparaiso (Chile); Gregori, Ida de; Pinochet, Hugo [Universite de Pau et des Pays de L' Adour, Laboratoire de Chimie Analytique, LCABIE, UMR CNRS 5034, Pau (France)

2005-12-01

A method based on Headspace solid-phase microextraction (HS-SPME, with a 100 {mu}m PDMS-fiber) in combination with gas-chromatography and pulsed flame-photometric detection (GC-PFPD) has been investigated for simultaneous determination of eight organotin compounds. Monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), monophenyltin (MPhT), and the semi-volatile diphenyltin (DPhT), triphenyltin (TPhT), monooctyltin (MOcT), and dioctyltin (DOcT) were determined after derivatization with sodium tetraethylborate. The conditions used for the extraction and preconcentration step were optimised by experimental design methodology. Tripropyltin (TPrT) and diheptyltin (DHepT) were used as internal standards for quantification of volatile and semi-volatile organotin compounds, respectively. The analytical precision (RSD) for ten successive injections of a standard mixture containing all the organic tin compounds ranged between 2 and 11%. The limits of detection for all the organotin compounds were sub ng (Sn) L{sup -1} in water and close to ng (Sn) kg{sup -1} in sediments. The accuracy of the method was evaluated by analysis of two certified reference material (CRM) sediment samples. The HS-SPME-GC-PFPD was then applied to the analysis of three harbour sediment samples. The results showed that headspace SPME is an attractive tool for analysis of organotin compounds in solid environmental matrices. (orig.)

Organotins Are Potent Activators of PPARγ and Adipocyte Differentiation in Bone Marrow Multipotent Mesenchymal Stromal Cells

Science.gov (United States)

Yanik, Susan C.; Baker, Amelia H.; Mann, Koren K.; Schlezinger, Jennifer J.

2011-01-01

Adipocyte differentiation in bone marrow is potentially deleterious to both bone integrity and lymphopoiesis. Here, we examine the hypothesis that organotins, common environmental contaminants that are dual ligands for peroxisome proliferator–activated receptor (PPAR) γ and its heterodimerization partner retinoid X receptor (RXR), are potent activators of bone marrow adipogenesis. A C57Bl/6-derived bone marrow multipotent mesenchymal stromal cell (MSC) line, BMS2, was treated with rosiglitazone, a PPARγ agonist, bexarotene, an RXR agonist, or a series of organotins. Rosiglitazone and bexarotene potently activated adipocyte differentiation; however, bexarotene had a maximal efficacy of only 20% of that induced by rosiglitazone. Organotins (tributyltin [TBT], triphenyltin, and dibutyltin) also stimulated adipocyte differentiation (EC50 of 10–20nM) but with submaximal, structure-dependent efficacy. In coexposures, both bexarotene and TBT enhanced rosiglitazone-induced adipogenesis. To investigate the contribution of PPARγ to TBT-induced adipogenesis, we examined expression of PPARγ2, as well as its transcriptional target FABP4. TBT-induced PPARγ2 and FABP4 protein expression with an efficacy intermediate between rosiglitazone and bexarotene, similar to lipid accumulation. A PPARγ antagonist and PPARγ-specific small hairpin RNA suppressed TBT-induced differentiation, although to a lesser extent than rosiglitazone-induced differentiation, suggesting that TBT may engage alternate pathways. TBT and bexarotene, but not rosiglitazone, also induced the expression of TGM2 (an RXR target) and ABCA1 (a liver X receptor target). The results show that an environmental contaminant, acting with the same potency as a therapeutic drug, induces PPARγ-dependent adipocyte differentiation in bone marrow MSCs. Activation of multiple nuclear receptor pathways by organotins may have significant implications for bone physiology. PMID:21622945

[Simultaneous determination of ten organotin compounds in polyvinyl chloride plastics using gas chromatography-mass spectrometry].

Science.gov (United States)

Li, Ying; Li, Bin; Liu, Li; Zhang, Chen; Wu, Jingwu; Liu, Zhihong; Li, Xintian

2009-01-01

A rapid and effective gas chromatography coupled with mass spectrometry method has been developed systematically and studied for the simultaneous determination of 10 organotin compounds, dibutyltin-dichloride (DBT), n-butyltin-trichloride (MBT), triethyltinchloride (TET), fentin-chloride (TPhT), chlorotributylstannane (TBT), tri-n-propyltinchloride (TPrT), diphenyltin-dichloride (DPhT), tetrabutyltin (TeBT), di-n-octyltin-dichloride (DOT), phenyltin trichloride (MPhT)), in polyvinyl chloride (PVC) plastics. The PVC sample was dissolved with tetrahydrofuran and the polymer in the sample was precipitated with methanol, and then the target compounds were derivatized with sodium tetraethylborate and extracted with hexane under ultrasonication. The qualitative and quantitative analysis were carried out by GC-MS and the total ion chromatogram and selected ion chromatogram were obtained. The derivatization and extraction conditions, such as the derivatization time, derivatization pH value, dosages of derivatization reagent and precipitation reagent were optimized. The good linearities, recoveries and precisions were obtained. The linearity ranges were 0.5 - 50 mg/L. The linearity correlation coefficients of 10 organotin compounds were between 0.997 8 and 0.999 7. The average recoveries were 84.23% - 109.1% with relative standard deviations of 4.24% - 10.75%. The established method has been successfully applied to the determination of organotin compounds in PVC plastics.

Synthesis, characterization, crystal structures, QSAR study and antibacterial activities of organotin bisphosphoramidates

Czech Academy of Sciences Publication Activity Database

Gholivand, K.; Valmoozi, A.A.E.; Gholami, A.; Dušek, Michal; Eigner, Václav; Abolghasemi, S.

2016-01-01

Roč. 806, Mar (2016), s. 33-44 ISSN 0022-328X R&D Projects: GA ČR GA15-12653S Institutional support: RVO:68378271 Keywords : bisphosphoramidate * organotin compounds * crystal structure * antibacterial activity * QSAR Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.184, year: 2016

Radiation-induced reduction of quinoxalin-2-one derivatives in aqueous solutions

Science.gov (United States)

Skotnicki, Konrad; De la Fuente, Julio R.; Cañete, Alvaro; Bobrowski, Krzysztof

2016-07-01

Quinoxaline-2-one derivatives have been proposed as potential drugs in treatments of various diseases since some of them showed a variety of pharmacological properties. The kinetics and spectral characteristics of the transients formed in the reactions of hydrated electrons (eaq-) with quinoxalin-2-(1H)-one (Q) and its methyl derivative, 3-methyl quinoxalin-2-(1H)-one (3-MeQ) were studied by pulse radiolysis in aqueous solutions at pH ranging from 5 to 14. The transient absorption spectra recorded in the reactions of (eaq-) with Q and 3-MeQ at pH 7 consisted of a broad, almost flat band in the range 390-450 nm and were assigned to the respective protonated radical anions (QH•/3-MeQH•) at N4 atom in a pyrazin-2-one ring. On the other hand, the transient absorption spectra recorded in the reactions of (eaq-) with Q and 3-MeQ at pH 13 are characterized by a broad band with a much better pronounced maximum at λmax=390 nm and higher intensity (in comparison to that at pH 7) and were assigned to the respective radical anions (Q•-/3-MeQ•-). Both forms are involved in the prototropic equilibrium with the pKa located at pH≥13.5. The rate constants of the reactions of (eaq-) with Q and 3-MeQ were found to be at pH 7 (2.6±0.1)×1010 M-1 s-1 and (2.1±0.1)×1010 M-1 s-1 and at pH 13 (1.6±0.1)×1010 M-1 s-1 and (1.3±0.1)×1010 M-1 s-1, respectively. Semi-empirical quantum mechanical calculations reproduce fairly well the spectral features of the experimental absorption spectra and show that protonated radical anions at nitrogen atom (N4) in both molecules are the most stable hydrogenated radicals.

Synthesis, coordination and biological aspects of organotin(IV derivatives of 4-[(2,4-dinitrophenylamino]-4-oxo-2-butenoic acid and 2-{[(2,4-dinitrophenylamino]carbonyl}benzoic acid

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KHADIJA SHAHID

2009-02-01

Full Text Available New series of organotin(IV complexes of aniline derivatives, R2SnL2 and R3SnL [where R = Me, n-Bu, Ph, n-Oct] have been synthesized by the reaction of HL1 and HL2 with respective organotin halides or oxides. Experimental details for the preparation and characterization (including elemental analysis, IR and multinuclear NMR (1H-, 13C- and 119Sn- spectra in CDCl3 and EI mass spectra of both series are provided. The binding sites of the ligands were identified by means of FTIR spectroscopic measurements. It was found that in all cases the organotin(IV moiety reacts with the oxygen of COO– group to form new complexes. In the diorganotin complexes, the COO– group is coordinated to the organotin(IV centres in a bidentate manner in the solid state. The 119Sn NMR data and the nJ(13C‑119/117Sn coupling constant support the tetrahedral coordination geometry of the organotin complexes in non-coordinating solvents. Biological activities (antibacterial, antifungal, cytotoxicity, antileishmanial and insecticidal of these compounds are also reported.

Biological activity of 2,3-Di (quinolyl-2)-6-methyl quinoxaline

International Nuclear Information System (INIS)

Ansar, N.; Kaban, S.; Ahmed, R.

2003-01-01

The biological activities of the nitrogen containing conjugated heterocyclic compounds are considerably used pharmaceutically as antiulcer, antimalarial, tubercluocidal and sedatives besides their uses as dyes in the textile industries, pesticides, stabilizers and inhibitors etc. 2.3-Di(quinolyl-2)-6-methyl quinoxaline was synthesized by condensation followed by ring closure reaction when 1,2-di(quinolyl-2)-1,2 ethanedione was treated with methyl and substituted o-phenylenediamine. (author)

Biological activity of 2,3-Di (quinolyl-2)-6-methyl quinoxaline

Energy Technology Data Exchange (ETDEWEB)

Ansar, N [Adamjee Government Science College, Karachi (Pakistan). Dept. of Chemistry; Kaban, S [Yildiz Technical Univ., Istanbul (Turkey). Dept. of Chemistry; Ahmed, R [University of Karachi, Karachi (Pakistan). Dept. of Chemistry

2003-06-01

The biological activities of the nitrogen containing conjugated heterocyclic compounds are considerably used pharmaceutically as antiulcer, antimalarial, tubercluocidal and sedatives besides their uses as dyes in the textile industries, pesticides, stabilizers and inhibitors etc. 2.3-Di(quinolyl-2)-6-methyl quinoxaline was synthesized by condensation followed by ring closure reaction when 1,2-di(quinolyl-2)-1,2 ethanedione was treated with methyl and substituted o-phenylenediamine. (author)

THE DETERMINATION OF NON-PESTICIDAL AND PESTICIDAL ORGANOTIN COMPOUNDS IN WATER BY GAS CHROMATOGRAPHY WITH [PULSED] FLAME PHOTOMETRIC DETECTION (GS/PFPD): THE EFFECTS OF "MASS" DISCRIMINATION

Science.gov (United States)

Capillary gas chromatography with GC/PFPD was used in the development of analytical methodology for determining both non-pesticidal and pesticidal organotin compounds in drinking water and other aqueous matrices. The method involves aqueous ethylation of organotin analytes with ...

Organotin(IV complexes derived from N-ethyl-N-phenyldithiocarbamate: Synthesis, characterization and thermal studies

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Jerry O. Adeyemi

2018-05-01

Full Text Available Organotin(IV dithiocarbamate complexes, RSnClL2 and R2SnL2 (R = Me, Bu, Ph, and L = N-ethyl-N-phenyldithiocarbamate, have been synthesized by the reaction of mono- and disubstituted organotin(IV with ammonium dithiocarbamate. The complexes were characterized by elemental analyses, and spectroscopic techniques (1H, 13C NMR and FTIR. The structures of Me2SnL2 and Bu2SnL2 were further established by single crystal X-ray diffraction technique. The crystal structure analysis showed that both complexes (Me2SnL2 and Bu2SnL2 exist as monomers. One of the dithiocarbamate ligands formed a chelate, while the other dithiocarbamate bonded to the central tin atom through one of the sulfur atoms and the second sulfur atom existed as a pendant to form distorted trigonal bipyramidal geometry. The thermal stability of all the complexes was studied using simultaneous thermogravimetry (TG and differential scanning calorimetry (DSC. The TG-DSC results showed that Me2SnL2, BuSnClL2, Bu2SnL2, and PhSnClL2 displayed similar decomposition pathway via isothiocyanate intermediate, while MeSnClL2 and Ph2SnL2 showed decomposition pathways different from the rest of the complexes. All the complexes resulted in SnS as the final product of the thermal decomposition process. Keywords: Organotin, Dithiocarbamate, Crystal structure, Thermal studies

Preparation and structural studies on organotin(IV) complexes with flavonoids

International Nuclear Information System (INIS)

Nagy, L.; Christy, A.A.; Sletten, E.; Andersen, Q.M.; Edelmann, F.T.

1998-01-01

Fourteen complexes of di-n-butyltin(IV) 2+ cations with flavonoid glycosides (rutin, hesperidin, 2',4',3-trihydroxy-5',4-dimetoxychalkone 4-rutinoside) and flavonoid aglycones (quercetin, morin, hesperitin and sorte flavones) were prepared. The composition of the complexes was determined by standard analytical methods. The results showed that complexes containing diorganotin(IV) 2+ moiety and the ligand in 1:1, 2:1 or 3:1 ratio are formed. The FTIR spectra were consistent with the presence of Sn-O (phenol or carbohydrate) vibration in the compounds. The structure of the complexes was measured by Moessbauer spectroscopy. Comparison of the experimental quadrupole splitting with those calculated on the basis of partial quadrupole splitting concept revealed that the complexes are of four types: with the central tin atoms surrounded by donor atoms in a purely trigonal-bipyramidal, octahedral+trigonal-bipyramidal, trigonal-bipyramidal+tetrahedral and octahedral+tetrahedral arrangement. This procedure also distinguished between the different structural isomers of both trigonal-bipyramidal and octahedral complexes. Conclusions could therefore be drawn on the factors determining which of the isomers are formed in the systems. The Moessbauer parameters obtained for organotin(IV)-flavonoid complexes were compared with those measured for organotin(IV)-carbohydrate complexes. (author)

Preliminary investigation of a sensitive biomarker of organotin pollution in Chinese coastal aquatic environment and marine organisms

International Nuclear Information System (INIS)

Zhou Qunfang; Li Zhongyang; Jiang Guibin; Yang Ruiqiang

2003-01-01

A new sensitive biomarker can be potentially used to indicate the pollution status of organotin in oceanic environment. - In nine batches of sea bivalves collected from Chinese coastal cities during the year of 2000 to 2002, a special sample named Mya arenaria was found to have strong ability of butyltin accumulation compared with the other sampled bivalves in the corresponding batches. Tributyltin compound was the predominant pollutant with the detection rate high up to 100%. Special high levels of μg Sn/g were detected in some Mya arenaria samples. The results obtained showed that Mya arenaria was potentially a biomarker to indicate organotin pollution in coastal aquatic environment

C,N-Chelated Organotin(IV) Azides: Synthesis, Structure and Use within the Click Chemistry.

Czech Academy of Sciences Publication Activity Database

Švec, P.; Bartoš, K.; Růžičková, Z.; Cuřínová, Petra; Dušek, L.; Turek, J.; de Proft, F.; Růžička, A.

2016-01-01

Roč. 40, č. 7 (2016), s. 5808-5817 ISSN 1144-0546 Grant - others:FWO(BE) 12T6615N Institutional support: RVO:67985858 Keywords : organotin(IV)azides * click chemistry * chelation Subject RIV: CC - Organic Chemistry Impact factor: 3.269, year: 2016

Assessment of organotin and tin-free antifouling paints contamination in the Korean coastal area.

Science.gov (United States)

Lee, Mi-Ri-Nae; Kim, Un-Jung; Lee, In-Seok; Choi, Minkyu; Oh, Jeong-Eun

2015-10-15

Twelve organotins (methyl-, octyl-, butyl-, and phenyl-tin), and eight tin-free antifouling paints and their degradation products were measured in marine sediments from the Korean coastal area, and Busan and Ulsan bays, the largest harbor area in Korea. The total concentration of tin-free antifouling paints was two- to threefold higher than the total concentration of organotins. Principal component analysis was used to identify sites with relatively high levels of contamination in the inner bay area of Busan and Ulsan bays, which were separated from the coastal area. In Busan and Ulsan bays, chlorothalonil and DMSA were more dominant than in the coastal area. However, Sea-Nine 211 and total diurons, including their degradation products, were generally dominant in the Korean coastal area. The concentrations of tin and tin-free compounds were significantly different between the east and west coasts. Copyright © 2015 Elsevier Ltd. All rights reserved.

Electrochemical Behavior of Quinoxalin-2-one Derivatives at Mercury Electrodes and Its Analytical Use

Czech Academy of Sciences Publication Activity Database

Zimpl, M.; Skopalová, J.; Jirovský, D.; Barták, P.; Navrátil, Tomáš; Sedoníková, J.; Kotouček, M.

2012-01-01

Roč. 2012, č. 2012 (2012), s. 409378 ISSN 1537-744X R&D Projects: GA AV ČR IAA400400806 Institutional research plan: CEZ:AV0Z40400503 Keywords : electrochemistry * quinoxalin -2- one * electrodes Subject RIV: CG - Electrochemistry Impact factor: 1.730, year: 2012 http://www.tswj.com/2012/409378/

An Efficient and Recyclable Nanoparticle-Supported Cobalt Catalyst for Quinoxaline Synthesis

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Fatemeh Rajabi

2015-11-01

Full Text Available The syntheses of quinoxalines derived from 1,2-diamine and 1,2-dicarbonyl compounds under mild reaction conditions was carried out using a nanoparticle-supported cobalt catalyst. The supported nanocatalyst exhibited excellent activity and stability and it could be reused for at least ten times without any loss of activity. No cobalt contamination could be detected in the products by AAS measurements, pointing to the excellent activity and stability of the Co nanomaterial.

Crystal and molecular structure of 2,2’-(quinoxaline-2,3-diyl)dipyridinium dinitrate (H_2L)(NO_3)_2

International Nuclear Information System (INIS)

Egorova, O. A.; Polyakova, I. N.; Sergienko, V. S.; Davydov, V. V.

2016-01-01

The crystal structure of 2,2’-(quinoxaline-2,3-diyl)dipyridinium dinitrate (H_2L)(NO_3)_2 is studied by X-ray diffraction (T = 150 K, R1 = 0.0467). The H_2L"2"+ cation is located on the twofold rotation axis and connected with two NO_3"− anions by strong N–H···O hydrogen bonds. Planar quinoxaline fragments of cations form stacks with the interplanar spacing of 3.308 Å. The structure of the diprotonated H_2L"2"+ cation is compared with those of the monoprotonated H_2L"2"+ cation and neutral L molecule.

Electrochemical Behavior of Quinoxalin-2-one Derivatives at Mercury Electrodes and Its Analytical Use

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Milan Zimpl

2012-01-01

Full Text Available Derivatives of quinoxalin-2-one are interesting compounds with potential pharmacological activity. From this point of view, understanding of their electrochemical behavior is of great importance. In the present paper, a mechanism of electrochemical reduction of quinoxalin-2-one derivatives at mercury dropping electrode was proposed. Pyrazine ring was found to be the main electroactive center undergoing a pH-dependent two-electron reduction process. The molecule protonization of nitrogen in the position 4 precedes the electron acceptance forming a semiquinone radical intermediate which is relatively stable in acidic solutions. Its further reduction is manifested by separated current signal. A positive mesomeric effect of the nonprotonized amino group in the position 7 of the derivative III accelerates the semiquinone reduction yielding a single current wave. The suggested reaction mechanism was verified by means of direct current polarography, differential pulse, cyclic and elimination voltammetry, and coulometry with subsequent GC/MS analysis. The understanding of the mechanism was applied in developing of analytical method for the determination of the studied compounds.

Electrochemical behavior of quinoxalin-2-one derivatives at mercury electrodes and its analytical use.

Science.gov (United States)

Zimpl, Milan; Skopalova, Jana; Jirovsky, David; Bartak, Petr; Navratil, Tomas; Sedonikova, Jana; Kotoucek, Milan

2012-01-01

Derivatives of quinoxalin-2-one are interesting compounds with potential pharmacological activity. From this point of view, understanding of their electrochemical behavior is of great importance. In the present paper, a mechanism of electrochemical reduction of quinoxalin-2-one derivatives at mercury dropping electrode was proposed. Pyrazine ring was found to be the main electroactive center undergoing a pH-dependent two-electron reduction process. The molecule protonization of nitrogen in the position 4 precedes the electron acceptance forming a semiquinone radical intermediate which is relatively stable in acidic solutions. Its further reduction is manifested by separated current signal. A positive mesomeric effect of the nonprotonized amino group in the position 7 of the derivative III accelerates the semiquinone reduction yielding a single current wave. The suggested reaction mechanism was verified by means of direct current polarography, differential pulse, cyclic and elimination voltammetry, and coulometry with subsequent GC/MS analysis. The understanding of the mechanism was applied in developing of analytical method for the determination of the studied compounds.

Determination of organotin compounds in the foodweb of a shallow freshwater lake in the Netherlands

NARCIS (Netherlands)

Stäb, J.A.; Traas, T.P.; Stroomberg, G.; van Kesteren, J.; Leonards, P.E.G.; van Hattum, A.G.M.; Brinkman, U.A.T.; Cofino, W.P.

1996-01-01

An extensive study on the presence of nine organotin compounds (OT) in a freshwater foodweb was made, using newly developed analytical procedures in order to obtain insight in accumulation and degradation processes. Tributyltin (TBT), Triphenyltin (TPT) and their degradation products were detected.

Organotins in North Sea brown shrimp (Crangon crangon L.) after implementation of the TBT ban

NARCIS (Netherlands)

Verhaegen, Y.; Monteyne, E.; Neudecker, T.; Tulp, I.Y.M.; Smagghe, G.; Cooreman, K.; Roose, P.; Parmentier, K.

2012-01-01

The organotin (OT) compounds tributyltin (TBT) and triphenyltin (TPhT) are potent biocides that have been used ubiquitously in antifouling paints and pesticides since the mid-1970s. These biocides are extremely toxic to marine life, particularly marine gastropod populations. The European Union

Organotin(IV) Carboxylates as Promising Potential Drug Candidates in the Field of Cancer Chemotherapy.

Science.gov (United States)

Sirajuddin, Muhammad; Ali, Saqib

2016-01-01

Medicinal inorganic chemistry plays an important role in exploring the properties of metal ions for the designing of new drugs. The field has been stimulated by the success of cis-platin, the world best selling anticancer drug and platinum complexes with reduced toxicity, oral activity and activity against resistant tumors are currently on clinical trial. The use of cis-platin is, however, severely limited by its toxic side-effects. This has stimulated chemists to employ different strategies in the development of new metal-based anticancer agents with different mechanisms of action. The discovery of new non-covalent interactions with the classical target, DNA, was the first developing step in the treatment of cancer. The use of organometallic compounds as a medicine is very common now a days because it offers potential advantages over the more common organic-based drugs. In this article we have highlighted the anticancer activity of the organotin(IV) carboxylates published in the last few years (from 2008 to 2016). In most cases they present lower IC50 values than those of cisplatin, which indicates their high activity against the cancer cell lines. The summarized data reveal that every year new organotin(IV) carboxylate complexes are synthesized with the aim of new anticancer agent with much better results than the than the corresponding activity of cis-platin or other clinically approved drugs. In addition to the advantages of high activity, compared to the platinum compound, tin complexes are much cheaper. Thus by using organotin carboxylate for clinical medicine, cost reduction, dosage reduction and effect enhancement will be reached. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Environmental Fate and Effects of Organotin Biocides: A Molecular and Microbiological Assessment.

Science.gov (United States)

1986-12-12

and effects of the toxic tributyltin species, an active agent in new ship antifouling coatings. -44-4eiped- vltratrace’butyltin measurement’ ehdl c d...environments. However, the environmental occurrence, fate and effects of the highly toxic tributyltin species leached from the paints was virtually unexplored...biodegradation of tributyltin species; and 4) provided novel molecular topological correlations between molecular geometry and toxicity of organotin

Synthesis of quinoxaline 1,4-di-n-oxide derivatives on solid support using room temperature and microwave-assisted solvent-free procedures

International Nuclear Information System (INIS)

Gomez-Caro, Lilia C.; Sanchez-Sanchez, Mario; Bocanegra-Garcia, Virgilio; Rivera, Gildardo; Monge, Antonio

2011-01-01

We describe the synthesis of 12 new ethyl and methyl quinoxaline-7-carboxylate 1,4-di-N-oxide derivatives on solid supports with room temperature and microwave-assisted solvent-free procedures. Results show that solid supports have good catalytic activity in the formation of quinoxaline 1,4-di-N-oxide derivatives. We found that florisil and montmorillonite KSF and K10 could be used as new, easily available, inexpensive alternatives of catalysts. Additionally, room temperature and microwave-irradiation solvent-free synthesis was more efficient than a conventional procedure (Beirut reaction), reducing reaction time and increasing yield. (author)

Synthesis of quinoxaline 1,4-di-n-oxide derivatives on solid support using room temperature and microwave-assisted solvent-free procedures

Energy Technology Data Exchange (ETDEWEB)

Gomez-Caro, Lilia C.; Sanchez-Sanchez, Mario; Bocanegra-Garcia, Virgilio; Rivera, Gildardo [Universidad Autonoma de Tamaulipas, Reynosa (Mexico). Dept. de Farmacia y Quimica Medicinal; Monge, Antonio [Universidad de Navarra, Pamplona (Spain). Centro de Investigacion en Farmacobiologia Aplicada. Unidad de Investigacion y Desarrollo de Medicamentos

2011-07-01

We describe the synthesis of 12 new ethyl and methyl quinoxaline-7-carboxylate 1,4-di-N-oxide derivatives on solid supports with room temperature and microwave-assisted solvent-free procedures. Results show that solid supports have good catalytic activity in the formation of quinoxaline 1,4-di-N-oxide derivatives. We found that florisil and montmorillonite KSF and K10 could be used as new, easily available, inexpensive alternatives of catalysts. Additionally, room temperature and microwave-irradiation solvent-free synthesis was more efficient than a conventional procedure (Beirut reaction), reducing reaction time and increasing yield. (author)

Solid phase microextraction and stir bar sorptive extraction for organotin compounds - a comparison (P9)

International Nuclear Information System (INIS)

Mothes, S.; Wennrich, R.

2002-01-01

Full text: Organotin compounds have been largely used in agricultural and industrial applications. Hyphenated techniques were developed for the sensitive and selective determination of such species. For this task GC has been coupled with atomic emission detection. Derivatization to transform the Sn-compounds into sufficiently volatile compounds was necessary and carried out using sodium tetrapropylborate. For sample preparation the application of solid phase microextraction (SPME) give recent advances in comparison to classical liquid-liquid extraction (LEE). A problem in the usage of SPME exists however in the small volume of the PDMS coating for enrichment the analytes. For improvement of both sample enrichment and extraction of the organotin compounds stir bar sorptive extraction (SBSE) was applied. It base on the application of stir bars coated with PDMS. Here the extraction yield is substantially higher. Aim of this study was to compare the capabilities of GC-AED in combination with SPME and SBSE. After optimization of the experimental parameters it was possible to reach detection limits in the pg / 1 - level. A comparison of both methods shows the expected results. By application of SBSE it was possible to increase the detection limits one order of magnitude. With SPME the reproducibility of the analytical results (in the 1 ng / 1 concentration range) was found to be between 10 and 15 %, it could be enhanced to 5-8 % by application of SBSE. These low limits of detection and the good reproducibility allowed the determination of organotin compounds according required regulations. Ref. 1 (author)

Speciation analysis of organotin compounds in human urine by headspace solid-phase micro-extraction and gas chromatography with pulsed flame photometric detection.

Science.gov (United States)

Valenzuela, Aníbal; Lespes, Gaëtane; Quiroz, Waldo; Aguilar, Luis F; Bravo, Manuel A

2014-07-01

A new headspace solid-phase micro-extraction (HS-SPME) method followed by gas chromatography with pulsed flame photometric detection (GC-PFPD) analysis has been developed for the simultaneous determination of 11 organotin compounds, including methyl-, butyl-, phenyl- and octyltin derivates, in human urine. The methodology has been validated by the analysis of urine samples fortified with all analytes at different concentration levels, and recovery rates above 87% and relative precisions between 2% and 7% were obtained. Additionally, an experimental-design approach has been used to model the storage stability of organotin compounds in human urine, demonstrating that organotins are highly degraded in this medium, although their stability is satisfactory during the first 4 days of storage at 4 °C and pH=4. Finally, this methodology was applied to urine samples collected from harbor workers exposed to antifouling paints; methyl- and butyltins were detected, confirming human exposure in this type of work environment. Copyright © 2014 Elsevier B.V. All rights reserved.

Developmental toxicity of organotin compounds in animals

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Lijiao eWu

2014-09-01

Full Text Available Organotin compounds (OTs have been used as biocides in antifouling paints and agriculture. The IMO introduced a global ban on the use of OTs in antifouling systems in 2001 due to their high toxicity. However, OTs have still been detected in the environment and pose a threat to the ecosystem. Several research groups have summarized the analytical methods, environmental fate, biochemistry, reproductive toxicity and mechanisms of actions of OTs. Here, we reviewed the developmental toxicity of OTs in various organisms such as sea urchin, ascidian, mussel and fish. The differences in sensitivity to OT exposure exist not only in different species but also at different stages in the same species. Though some hypotheses have been proposed to explain the developmental toxicity of OTs, the solid evidences are greatly in need.

Nanoparticles of novel organotin(IV) complexes bearing phosphoric triamide ligands

Science.gov (United States)

Asadi, Ebadullah; Tavasolinasab, Vahid; Gholivand, Khodayar

2013-01-01

Summary Four novel organotin(IV) complexes containing phosphoric triamide ligands were synthesized and characterized by multinuclear (1H, 31P, 13C) NMR, infrared, ultraviolet and fluorescence spectroscopy as well as elemental analysis. The 1H NMR spectra of complexes 1–4 proved that the Sn atoms adopt octahedral configurations. The nanoparticles of the complexes were also prepared by ultrasonication, and their SEM micrographs indicated identical spherical morphologies with particles sizes about 20–25 nm. The fluorescence spectra exhibited blue shifts for the maximum wavelength of emission upon complexation. PMID:23504649

Evaluation of cetacean exposure to organotin compounds in Brazilian waters through hepatic total tin concentrations

International Nuclear Information System (INIS)

Dorneles, Paulo R.; Lailson-Brito, Jose; Fernandez, Marcos A.S.; Vidal, Lara G.; Barbosa, Lupercio A.; Azevedo, Alexandre F.; Fragoso, Ana B.L.; Torres, Joao P.M.; Malm, Olaf

2008-01-01

In Brazil, there is no restriction to the use of organotins (OTs). Previous investigations have shown that hepatic ΣSn in cetaceans is predominantly organic. Hepatic ΣSn concentrations were determined by GFAAS in 67 cetaceans (13 species) that stranded on Rio de Janeiro (RJ) and Espirito Santo (ES) states. Concentrations (in ng/g wet wt.) of marine tucuxis (n = 20) from the highly contaminated Guanabara Bay (in RJ) varied from 1703 to 9638. Concentrations of three marine tucuxi foetuses and one newborn calf (all from Guanabara Bay) varied between 431 and 2107. Contrastingly, the maximum level among 19 oceanic dolphins was 346, and 15 out of these 19 specimens presented concentrations below detection limit. The levels of Sn in six marine tucuxis from a less contaminated area (ES) varied from below detection limit to 744. Comparing to the literature, coastal cetaceans from Brazil appear to be highly exposed to OTs. - Cetaceans from Brazil are highly exposed to organotin compounds

Evaluation of cetacean exposure to organotin compounds in Brazilian waters through hepatic total tin concentrations

Energy Technology Data Exchange (ETDEWEB)

Dorneles, Paulo R. [Laboratorio de Radioisotopos Eduardo Penna Franca, Instituto de Biofisica Carlos Chagas Filho, CCS, Universidade Federal do Rio de Janeiro (Brazil); Laboratorio de Mamiferos Aquaticos (MAQUA), Faculdade de Oceanografia, Universidade do Estado do Rio de Janeiro (Brazil)], E-mail: dornelespr@gmail.com; Lailson-Brito, Jose [Laboratorio de Radioisotopos Eduardo Penna Franca, Instituto de Biofisica Carlos Chagas Filho, CCS, Universidade Federal do Rio de Janeiro (Brazil); Laboratorio de Mamiferos Aquaticos (MAQUA), Faculdade de Oceanografia, Universidade do Estado do Rio de Janeiro (Brazil)], E-mail: lailson@uerj.br; Fernandez, Marcos A.S. [Laboratorio de Oceanografia Quimica, Faculdade de Oceanografia, Universidade do Estado do Rio de Janeiro (Brazil)], E-mail: hallfz@uerj.br; Vidal, Lara G. [Laboratorio de Mamiferos Aquaticos (MAQUA), Faculdade de Oceanografia, Universidade do Estado do Rio de Janeiro (Brazil)], E-mail: vidallara@yahoo.com.br; Barbosa, Lupercio A. [Instituto ORCA, Vila Velha, ES (Brazil)], E-mail: lupercio@orca.org.br; Azevedo, Alexandre F. [Laboratorio de Mamiferos Aquaticos (MAQUA), Faculdade de Oceanografia, Universidade do Estado do Rio de Janeiro (Brazil)], E-mail: alexandre.maqua@gmail.com; Fragoso, Ana B.L. [Laboratorio de Mamiferos Aquaticos (MAQUA), Faculdade de Oceanografia, Universidade do Estado do Rio de Janeiro (Brazil)], E-mail: abfragoso@gmail.com; Torres, Joao P.M. [Laboratorio de Radioisotopos Eduardo Penna Franca, Instituto de Biofisica Carlos Chagas Filho, CCS, Universidade Federal do Rio de Janeiro (Brazil)], E-mail: jptorres@biof.ufrj.br; Malm, Olaf [Laboratorio de Radioisotopos Eduardo Penna Franca, Instituto de Biofisica Carlos Chagas Filho, CCS, Universidade Federal do Rio de Janeiro (Brazil)], E-mail: olaf@biof.ufrj.br

2008-12-15

In Brazil, there is no restriction to the use of organotins (OTs). Previous investigations have shown that hepatic {sigma}Sn in cetaceans is predominantly organic. Hepatic {sigma}Sn concentrations were determined by GFAAS in 67 cetaceans (13 species) that stranded on Rio de Janeiro (RJ) and Espirito Santo (ES) states. Concentrations (in ng/g wet wt.) of marine tucuxis (n = 20) from the highly contaminated Guanabara Bay (in RJ) varied from 1703 to 9638. Concentrations of three marine tucuxi foetuses and one newborn calf (all from Guanabara Bay) varied between 431 and 2107. Contrastingly, the maximum level among 19 oceanic dolphins was 346, and 15 out of these 19 specimens presented concentrations below detection limit. The levels of Sn in six marine tucuxis from a less contaminated area (ES) varied from below detection limit to 744. Comparing to the literature, coastal cetaceans from Brazil appear to be highly exposed to OTs. - Cetaceans from Brazil are highly exposed to organotin compounds.

Hydrothermal synthesis and structure of a novel 3D framework based on ξ-octamolybdate chains: [Cu2(quinoxaline)2Mo4O13]n

International Nuclear Information System (INIS)

Chen Lijuan; Lu Canzhong; He Xiang; Zhang Quanzheng; Yang Wenbin; Lin Xinhua

2006-01-01

An unprecedented three-dimensional (3D) polymer [Cu 2 (quinoxaline) 2 Mo 4 O 13 ] n , formed from ξ-octamolybdate chains as building units and pairs of 1D [Cu(quinoxaline)] n n+ polymeric chains as linkers, provides the first example of an extended higher dimensional structure based on [Mo 8 O 26 ] n 4n- octamolybdate chain. The basic building block of the octamolybdate chain included in the title compound is first reported to be constructed from ξ-isomer of octamolybdate unit

Organotin pollution from pleasure craft at Paraty, a tourist area of Southeastern Brazil: amelioration or interference?

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Camila de Leon Lousada Borges

2013-09-01

Full Text Available Some organotin compounds, such as TBT, are endocrine disruptors and harm marine ecosystems. Even after the global ban on organotins, increasing imposex levels have been detected in Stramonita haemastoma analyzed in 2004 and 2011 in some locations at Paraty, a tourist area in southeastern Brazil. The results of this study indicate that particulate and dissolved organic carbon and xenoestrogens might be interfering in this syndrome's development, leading to underestimation of imposex evaluation. Chemical analysis of three mangrove swamp sediments in the area showed the presence of TBT (16.0 - 205.7 ng Sn g-1, DBT (10.1 - 16.4 ng Sn g-1 and MBT (10.1 - 10.2 ng Sn g-1 even at the reference sites. The concentrations of butyltins and the increased incidence of imposexat some stations indicate recent inputs of TBT in the study area due to its illegal use on small vessels.

The effect of organotin compounds on chloride secretion by the in vitro perfused rectal gland of Squalus acanthias

Energy Technology Data Exchange (ETDEWEB)

Solomon, R.; Lear, S.; Cohen, R.; Spokes, K.; Silva, P. Jr.; Silva, M.; Solomon, H.; Silva, P. (New York Medical College, Valhalla (USA))

1989-09-01

The effects of various organotins on membrane function and electrolyte transport were studied in the marine elasmobranch, Squalus acanthias. The isolated perfused rectal gland was used as a model of electrolyte transport. This gland can be stimulated to secrete chloride by atrial natriuretic peptide, veratrine, and vasoactive intestinal polypeptide although the mechanism of action of each secretagogue is different. By analysis of the inhibitory effect of an organotin in the presence of each secretagogue, the mechanism of inhibition can be inferred. Tributyltin (TBT) produced a reversible inhibition of epithelial transport at 10(-8) to 10(-7) M which resulted from inhibition of stimulus-secretion coupling in VIP-containing neurons within the gland. The transporting epithelial cells were unaffected at these concentrations. Trimethytin (TMT) produced inhibition at 10(-7) M which was not reversible and which affected primarily the transporting epithelial cells. Triethyltin and triphenyltin were without effect. The inhibitory effect of TBT and TMT was not affected by simultaneous administration of dithiothreitol. TBT also produced inhibition of oxygen consumption, Na+,K-ATPase, and proton ATPase in dispersed rectal gland cells. These results indicate that organotins are toxic to cell membrane functions which are intimately involved in the movement of electrolytes. This is the first evidence of toxicity to membrane transport functions in a marine species which is at risk from environmental exposure.

Striking antitumor activity of a methinium system with incorporated quinoxaline unit obtained by spontaneous cyclization

Czech Academy of Sciences Publication Activity Database

Bříza, T.; Králová, Jarmila; Dolenský, B.; Rimpelová, S.; Kejík, Z.; Ruml, T.; Hajdúch, M.; Džubák, P.; Mikula, I.; Martásek, P.; Poučková, P.; Král, V.

2015-01-01

Roč. 16, č. 4 (2015), s. 555-558 ISSN 1439-7633 R&D Projects: GA MŠk(CZ) CZ.1.05/2.1.00/01.0030; GA ČR(CZ) GAP303/11/1291; GA MŠk(CZ) ED1.1.00/02.0109 Institutional support: RVO:68378050 Keywords : cancer * methinium salt * quinoxaline Subject RIV: EB - Genetics ; Molecular Biology

[Study on the ultraviolet spectrum in a series of 2 (1H)-quinoxalin-2-one derivatives].

Science.gov (United States)

Yang, Xiao-bing; Ding, Song-tao; Wang, An-bang; Yang, Yu-sheng

2003-02-01

A series of 2 (1H)-quinoxalin-2-one derivatives: 1-alkyl-3-methyl-2 (1H)-quinoxalin-2-one (AMQ, alkyl = H, CH3, C2H5, n-C3H7, n-C5H11, n-C16H33) have been studied by ultraviolet spectrometry. They may be used as highly active fungicides, compounds inhibiting the growth of plants, neuroprotectant for cerebral ischemia, new fluorescent probes, selective antagonists to alpha-amino-3-hydroxy-5-methly-4-isoxazole propionic acid (AMPA) et al. Results show that as the length of the alky1 chain at the nitrogen on the 1-position increases, little changes have been found in the ultraviolet absorption spectra. All spectra have similar peak shape, a strong shoulder peak appears around 327 and 340 nm with a weaker peak around 280 nm. The peak about 340 nm in the UV spectrum is mainly due to the transition of n-->pi* and pi-->pi*, the intense absorption peak about 327 and 280 nm is as the result of the transition of pi-->pi*.

A new approach to construct a fused 2-ylidene chromene ring: highly regioselective synthesis of novel chromeno quinoxalines.

Science.gov (United States)

Kumar, K Shiva; Rambabu, D; Prasad, Bagineni; Mujahid, Mohammad; Krishna, G Rama; Rao, M V Basaveswara; Reddy, C Malla; Vanaja, G R; Kalle, Arunasree M; Pal, Manojit

2012-06-28

Regioselective construction of a fused 2-ylidene chromene ring was achieved for the first time by using AlCl(3)-induced C-C bond formation followed by Pd/C-Cu mediate coupling-cyclization strategy. A number of chromeno[4,3-b]quinoxaline derivatives were prepared by using this strategy. Single crystal X-ray diffraction study of a representative compound e.g. 6-(2,2-dimethylpropylidene)-4-methyl-6H-chromeno[4,3-b]quinoxalin-3-ol confirmed the presence of an exocyclic C-C double bond with Z-geometry. The crystal structure analysis and hydrogen bonding patterns of the same compound along with its structure elaboration via propargylation followed by Sonogashira coupling of the resulting terminal alkyne is presented. A probable mechanism for the formation of 2-ylidene chromene ring is discussed. Some of the compounds synthesized showed anticancer properties when tested in vitro.

Survey of organotin compounds in rivers and coastal environments in Portugal 1999-2000

Energy Technology Data Exchange (ETDEWEB)

Diez, Sergi [Department of Environmental Chemistry, IIQAB-CSIC, Jordi Girona 18-26, 08034 Barcelona (Spain)]. E-mail: sdsqam@cid.csic.es; Lacorte, Silvia [Department of Environmental Chemistry, IIQAB-CSIC, Jordi Girona 18-26, 08034 Barcelona (Spain); Viana, Paula [Direcao Geral do Ambiente, Ministerio do Ambiente, Rua da Murgueira, Zambujal, 2720 Amadora (Portugal); Barcelo, Damia [Department of Environmental Chemistry, IIQAB-CSIC, Jordi Girona 18-26, 08034 Barcelona (Spain); Bayona, Josep M. [Department of Environmental Chemistry, IIQAB-CSIC, Jordi Girona 18-26, 08034 Barcelona (Spain)

2005-08-15

In the period from April 1999 to May 2000, organotin pollution, namely butyl and phenyltins, was investigated in coastal and continental waters (46 stations), estuarine sediments (15 stations) and mussels (Mytilus galloprovincialis) (13 stations) throughout Portugal. Sampling points were chosen in areas of specific industrial, agricultural and harbor activities. Butyltins (BTs) were the only tin species identified of which tributyltin (TBT) was found in the whole area. Concentrations of TBT in river water ranged from 3 to 30 ng L{sup -1} (as Sn), marine sediment ranged from 4 to 12 {mu}g kg{sup -1} (as Sn), whereas concentrations in mussel tissue ranged from 2.5 to 490 {mu}g kg{sup -1} (as Sn). Given that some water samples appeared to be contaminated by higher monobutyltin (MBT) and dibutyltin (DBT) concentrations, the role of biological degradation and direct inputs from agricultural and industrial applications areas are discussed. The study compares depleted butyltin pollution in sediments and mussels of the Portuguese coastline associated with antifouling paints with previously reported levels. Inputs in river waters are more related to (i) PVC leaching and (ii) industrial sources, in some cases discharged by municipal wastewaters. - Survey data illustrate the complexities of organotin sources and cycling in coastal environments.

Survey of organotin compounds in rivers and coastal environments in Portugal 1999-2000

International Nuclear Information System (INIS)

Diez, Sergi; Lacorte, Silvia; Viana, Paula; Barcelo, Damia; Bayona, Josep M.

2005-01-01

In the period from April 1999 to May 2000, organotin pollution, namely butyl and phenyltins, was investigated in coastal and continental waters (46 stations), estuarine sediments (15 stations) and mussels (Mytilus galloprovincialis) (13 stations) throughout Portugal. Sampling points were chosen in areas of specific industrial, agricultural and harbor activities. Butyltins (BTs) were the only tin species identified of which tributyltin (TBT) was found in the whole area. Concentrations of TBT in river water ranged from 3 to 30 ng L -1 (as Sn), marine sediment ranged from 4 to 12 μg kg -1 (as Sn), whereas concentrations in mussel tissue ranged from 2.5 to 490 μg kg -1 (as Sn). Given that some water samples appeared to be contaminated by higher monobutyltin (MBT) and dibutyltin (DBT) concentrations, the role of biological degradation and direct inputs from agricultural and industrial applications areas are discussed. The study compares depleted butyltin pollution in sediments and mussels of the Portuguese coastline associated with antifouling paints with previously reported levels. Inputs in river waters are more related to (i) PVC leaching and (ii) industrial sources, in some cases discharged by municipal wastewaters. - Survey data illustrate the complexities of organotin sources and cycling in coastal environments

Structural investigation of 18-crown-6 complexes of Tri organotin carboxylate by 1H, 13C, 19F and 119Sn nuclear magnetic resonance spectroscopy

International Nuclear Information System (INIS)

Foladi, S.; Yousefi, M.; Mohammadpour Ammini, M. M.

2002-01-01

Single crystal structure determination of several 18-crown 6 complexes of orga nation derivatives reveals formation of aqua complex through hydrogen bonding to 18-crown-6, which is an important feature in their structure. In the majority of those studies, mono- and dichloro organotin have been used for complexation of them with crown ethers. In the present work, several 18-crown 6 complexes of tri organotin acetate[(C 6 H 5 ) 3 SnOCOCX 3 ] 2 , 18 C6 ], X=F, Cl, and H, have been prepared. The Lewis acidity of tin moiety in tri organotin carboxylate have been tailored by replacing hydrogen atoms of acetate group with chlorine and fluorine and influence of them in the formation of aqua complex with 18 C6 have been studied by infrared. 1 H, 13 C, 19 F and 119 Sn nuclear magnetic resonance spectroscopes. The effects of coordinating and non-coordinating solvent in status of structure in solution have been explored

A Portable Environment Test System: A Field Assessment of Organotin Leachates--Test and Evaluation.

Science.gov (United States)

1987-11-01

of organotin-based antifouling (AF) coatings, NOSC researchers used this facility to study the effects of tributyltin ( TBT ), the primary toxic ...Environmental Test System (PETS) was evaluated with tributyltin ( TBT ) anti oling leachates in Sin Diego Bay over a 7-month period. Overall mean test...EXECUTIVE SUMMARY A Portable Environmental Test System (PETS) was evaluated with tributyltin ( TBT ) antifouling leachates in San Diego Bay for 7

Distribution and accumulation of organotin species in seawater, sediments and organisms collected from a Taiwan mariculture area.

Science.gov (United States)

Liu, Li-Lian; Wang, Jih-Terng; Chung, Kuo-Nan; Leu, Ming-Yih; Meng, Pei-Jie

2011-01-01

The present study was undertaken to evaluate the distribution and accumulation of tributyltin (TBT) and triphenyltin (TPhT) in seawater, sediments and selected organisms from a cage mariculture area in southern Taiwan, Hsiao Liouchiou Island. Our results show that ΣOTs were found in concentrations as high as 196 ng/L in seawater collected from the sites in Pai-Sa harbor, and up 1040 ng/g dry wt. in sediments dredged from sites within Da-Fu harbor. Also, ΣOTs concentrations of 859 ng/g dry wt. were observed in the liver of cobia (Rachycentron canadum) from mariculture cages. As most published studies have focused on the acute toxicity and bioaccumulation of organotins in mussels, the effects of organotins on cobia and other marine fauna are still poorly understood. This study highlights the significance of ΣBTs accumulation in cobia, as well as in the sediments and seawater surrounding their culture facilities. Copyright © 2011 Elsevier Ltd. All rights reserved.

Design, synthesis, and biological evaluation of 3-vinyl-quinoxalin-2(1H-one derivatives as novel antitumor inhibitors of FGFR1

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Liu Z

2016-05-01

Full Text Available Zhiguo Liu,1,* Shufang Yu,1,* Di Chen,1 Guoliang Shen,1 Yu Wang,1 Leping Hou,2 Dan Lin,1 Jinsan Zhang,1 Faqing Ye1 1School of Pharmaceutical Sciences, Wenzhou Medical University, Wenzhou, 2Second Affiliated Hospital of Zhejiang University School of Medicine, Hangzhou, People’s Republic of China *These authors contributed equally to this work Abstract: FGFR1 is well known as a molecular target in anticancer drug design. TKI258 plays an important role in RTK inhibitors. Utilizing TKI258 as a lead compound that contains a quinazolinone nucleus, we synthesized four series of 3-vinyl-quinoxalin-2(1H-one derivatives, a total of 27 compounds. We further evaluated these compounds for FGFR1 inhibition ability as well as cytotoxicity against four cancer cell lines (H460, B16-F10, Hela229, and Hct116 in vitro. Some compounds displayed good-to-excellent potency against the four tested cancer cell lines compared with TKI258. Structure–activity relationship analyses indicated that small substituents at the side chain of the 3-vinyl-quinoxalin-2(1H-one were more effective than large substituents. Lastly, we used molecular docking to obtain further insight into the interactions between the compounds and FGFR1. Keywords: FGFR1, synthesis, quinoxaline, antitumor activity, kinase inhibitor

Effects of extraction and derivatization techniques on recovery of organotin species in environmental matrices (W3)

International Nuclear Information System (INIS)

Wahlen, R.; Catterick, T.

2002-01-01

Full text: Organotin (OT) contamination is still persistent in most coastal environments and estuaries and can be monitored accurately by analysis of sediments and sedentary aquatic animal populations. In addition to human exposure via contaminated seafood, there is increasing concern about OT compounds in man-made consumer products. Organotin analysis involves the extraction from the matrix, derivatization (for GC analysis), separation of the different species and detection. Commonly used extraction techniques are mechanical shaking, ultrasonic agitation and microwave leaching (open or closed vessel). Accelerated solvent extraction (ASE) has also been reported. In this study, closed-vessel microwave extraction and ASE methods are compared for OT analysis in environmental tissues using separation by gas chromatography (GC) and detection by inductively coupled plasma mass-spectrometry (ICP-MS). The efficiency of an ethylation procedure with sodiumtetraethylborate (NABEt 4 ) using different matrices and derivatization durations is monitored by comparing data obtained by external calibration with results by species-specific isotope dilution analysis (SS-IDMS) of dibutyltin (TBT) and dibutyltin (DBT) enriched with 117 Sn. Uncertainty estimates for both quantification techniques will be provided. (author)

Antiproliferative activity and interactions with cell-cycle related proteins of the organotin compound triethyltin(IV)lupinylsulfide hydrochloride.

Science.gov (United States)

Barbieri, F; Sparatore, F; Cagnoli, M; Bruzzo, C; Novelli, F; Alama, A

2001-03-14

Organotin compounds, particularly tri-organotin, have demonstrated cytotoxic properties against a number of tumor cell lines. On this basis, triethyltin(IV)lupinylsulfide hydrochloride (IST-FS 29), a quinolizidine derivative, was synthesized and developed as a potential antitumor agent. This tin-derived compound exhibited potent antiproliferative effects on three different human cancer cell lines: teratocarcinoma of the ovary (PA-1), colon carcinoma (HCT-8) and glioblastoma (A-172). Cytotoxic activity was assessed by MTT and cell count assays during time course experiments with cell recovery after compound withdrawal. Significant cell growth inhibition (up to 95% in HCT-8 after 72 h of exposure), which also persisted after drug-free medium change, was reported in all the cell lines by both assays. In addition, the cytocidal effects exerted by IST-FS 29 appeared more consistent with necrosis or delayed cell death, rather than apoptosis, as shown by morphologic observations under light microscope, DNA fragmentation analysis and flow cytometry. In the attempt to elucidate whether this compound might affect genes playing a role in G1/S phase transition, the expressions of p53, p21(WAF1), cyclin D1 and Rb, mainly involved in response to DNA-damaging stress, were analyzed by Western blot. Heterogeneous patterns of expression during exposure to IST-FS 29 were evidenced in the different cell lines suggesting that these cell-cycle-related genes are not likely the primary targets of this compound. Thus, the present data seem more indicative of a direct effect of IST-FS-29 on macromolecular synthesis and cellular homeostasis, as previously hypothesized for other organotin complexes.

Anti-leishmanial and structure-activity relationship of ring substituted 3-phenyl-1-(1,4-di-N-oxide quinoxalin-2-yl-2-propen-1-one derivatives

Directory of Open Access Journals (Sweden)

Asunción Burguete

2008-12-01

Full Text Available A series of ring substituted 3-phenyl-1-(1,4-di-N-oxide quinoxalin-2-yl-2-propen-1-one derivatives were synthesized and tested for in vitro leishmanicidal activity against amastigotes of Leishmania amazonensis in axenical cultures and murine infected macrophages. Structure-activity relationships demonstrated the importance of a radical methoxy at position R3', R4' and R5'. (2E-3-(3,4,5-trimethoxy-phenyl-1-(3,6,7-trimethyl-1,4-dioxy-quinoxalin-2-yl-propenone was the most active. Cytotoxicity on macrophages revealed that this product was almost six times more active than toxic.

Crystal and molecular structure of 2,2’-(quinoxaline-2,3-diyl)dipyridinium dinitrate (H{sub 2}L)(NO{sub 3}){sub 2}

Energy Technology Data Exchange (ETDEWEB)

Egorova, O. A. [People’s Friendship University of Russia (Russian Federation); Polyakova, I. N., E-mail: polyakova@igic.ras.ru; Sergienko, V. S. [Russian Academy of Sciences, Kurnakov Institute of General and Inorganic Chemistry (Russian Federation); Davydov, V. V. [People’s Friendship University of Russia (Russian Federation)

2016-07-15

The crystal structure of 2,2’-(quinoxaline-2,3-diyl)dipyridinium dinitrate (H{sub 2}L)(NO{sub 3}){sub 2} is studied by X-ray diffraction (T = 150 K, R1 = 0.0467). The H{sub 2}L{sup 2+} cation is located on the twofold rotation axis and connected with two NO{sub 3}{sup −} anions by strong N–H···O hydrogen bonds. Planar quinoxaline fragments of cations form stacks with the interplanar spacing of 3.308 Å. The structure of the diprotonated H{sub 2}L{sup 2+} cation is compared with those of the monoprotonated H{sub 2}L{sup 2+} cation and neutral L molecule.

Understanding the molecular behavior of organotin compounds to design their effective use as agrochemicals: exploration via quantum chemistry and experiments.

Science.gov (United States)

Ramalho, Teodorico C; Rocha, Marcus V J; da Cunha, Elaine F F; Oliveira, Luiz C A; Carvalho, Kele T C

2010-10-01

The high frequency of contamination by herbicides suggests the need for more active and selective agrochemicals. Organotin compounds are the active component of some herbicides, such as Du-Ter and Brestan, which is also a potent inhibitor of the F1Fo ATP Synthase. That is a key enzyme, because the ATP production is one of the major chemical reactions in living organisms. Thus ATP Synthase is regarded as a prime target for organotin compounds. In this line, molecular modeling studies and DFT calculations were performed in order to understand the molecular behavior of those compounds in solution. In addition, we investigated the reaction mechanism by ESI-MS analyses of the diphenyltin dichloride. Our findings indicate that an unstable key-intermediate generated in situ might take place in the reaction with ATP Synthase.

Microwave-Assisted Synthesis of Some Quinoxaline-Incorporated Schiff Bases and Their Biological Evaluation

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L. Achutha

2013-01-01

Full Text Available Quinoxaline-incorporated Schiff bases (4a–j were synthesized by the condensation of 2-[(3-methylquinoxalin-2-yloxy]acetohydrazide (3 with indole-3-carbaldehyde, furfuraldehyde, 5-(4-nitrophenyl-2-furfuraldehyde, and substituted benzaldehydes under conventional and microwave irradiation methods. The microwave method was found to be remarkably successful with higher yields, less reaction time, and environmentally friendly compared to conventional heating method. The chemical structures of the synthesized compounds have been confirmed by analytical and spectral data. All the compounds have been evaluated for antitubercular and anti-inflammatory activities.

The synthesis of new donor–acceptor polymers containing the 2,3-di(2-furyl) quinoxaline moiety: Fast-switching, low-band-gap, p- and n-dopable, neutral green-colored materials

International Nuclear Information System (INIS)

Xu, Zhen; Wang, Min; Fan, Weiyu; Zhao, Jinsheng; Wang, Huaisheng

2015-01-01

Highlights: • Three D-A type polymers based on 2,3-di(2-furyl) quinoxaline were synthesized and characterized. • The structure of substitution influences electrochromic properties of the polymers • All three polymers are both p- and n-type dopable and show excellent electrochromic properties. - Abstract: Three donor–acceptor type π-conjugated polymers were synthesized electrochemically:poly[2,3-di(2-furyl)-5,8-bis (2-(3,4-ethylenedioxythiophene)) quinoxaline] (PFETQ), poly[2,3-di(2-furyl)-5,8-bis(2-thienyl) quinoxaline] (PFTQ) and poly[2,3-di(2-furyl)-5,8-bis(2-(3-methoxythiophene)) quinoxaline] (PFMTQ). All of the synthesized polymers, contained the 2,3-di(2-furyl) quinoxaline moiety in the backbone as the acceptor unit and different thiophene derivatives as the donor units. The electroactivity of the monomers and the electrochemical properties of their polymers were investigated by cyclic voltammetry. The presence of the strong electron-donating ethylenedioxy and methoxy groups on the aromatic structure increased the electron density. Thus, the oxidation potential of FETQ and FMTQ shifted to a lower value than that of FTQ. The optical properties of the polymers were investigated by UV–vis–NIR spectroscopy. Both PFETQ and PFMTQ reveal two distinct absorption bands in the red and blue regions of the visible spectrum, while PFTQ has only one dominant wavelength at 596 nm in the visible region. The colorimetry analysis revealed that while PFTQ has a light blue color, PFETQ and PFMTQ are green in the neutral state. The optical band gaps, defined as the onset of the π–π* transition, were found to be 1.15 eV for PFETQ, 1.2 eV for PFMTQ and 1.34 eV for PFTQ. Moreover, all three polymers showed both n-doping and fast switching times

Hepatitis C Virus NS3/4A Protease Inhibitors Incorporating Flexible P2 Quinoxalines Target Drug Resistant Viral Variants.

Science.gov (United States)

Matthew, Ashley N; Zephyr, Jacqueto; Hill, Caitlin J; Jahangir, Muhammad; Newton, Alicia; Petropoulos, Christos J; Huang, Wei; Kurt-Yilmaz, Nese; Schiffer, Celia A; Ali, Akbar

2017-07-13

A substrate envelope-guided design strategy is reported for improving the resistance profile of HCV NS3/4A protease inhibitors. Analogues of 5172-mcP1P3 were designed by incorporating diverse quinoxalines at the P2 position that predominantly interact with the invariant catalytic triad of the protease. Exploration of structure-activity relationships showed that inhibitors with small hydrophobic substituents at the 3-position of P2 quinoxaline maintain better potency against drug resistant variants, likely due to reduced interactions with residues in the S2 subsite. In contrast, inhibitors with larger groups at this position were highly susceptible to mutations at Arg155, Ala156, and Asp168. Excitingly, several inhibitors exhibited exceptional potency profiles with EC 50 values ≤5 nM against major drug resistant HCV variants. These findings support that inhibitors designed to interact with evolutionarily constrained regions of the protease, while avoiding interactions with residues not essential for substrate recognition, are less likely to be susceptible to drug resistance.

Imposex induction in Stramonita haemastoma floridana (Conrad, 1837 (Mollusca: Gastropoda: Muricidae submitted to an organotin-contaminated diet

Directory of Open Access Journals (Sweden)

Aline Fernandes Alves de Lima

2006-03-01

Full Text Available Marine organisms are affected by organotin compounds due to the cumulative, deleterious effects of these latter. The most evident and well known consequence of organotin contamination is imposex, a hormonal disruption that causes a superimposition of sexual male features in females of prosobranchia neogastropod molluscs such as Stramonita haemastoma floridana. Molluscs accumulate organotins mainly because of their poor ability to eliminate TBT and DBT from their tissues. The aim of this study was to analyze organotin uptake by ingestion experimentally, using uncontaminated subjects (S. haemastoma floridana fed with organotin-contaminated oysters (Crassostrea rhizophorae. A total of 248 gastropods, distributed in 7 tanks with uncontaminated water and contaminated food, were used in this study, a control group being fed uncontaminated oysters. Every 15 days, the individuals of one of the tanks were examined for the presence of imposex. Development of imposex was measured using the VDSI, RPSI and RPLI indexes. The animals had already developed imposex within the first 15 days, all the indexes measured (RPLI, RPSI and VDSI having increased significantly with duration of exposure, indicating that the animals were probablycontaminated by the food and had accumulated the pollutant. New paths of imposex development were also observed.Organismos marinhos são afetados por compostos organoestânicos que causam uma série de efeitos deletérios aos mesmos. O mais conhecido efeito da contaminação por organoestânicos é o imposex. Esse fenômeno consiste na masculinização de fêmeas de moluscos neogastrópodes tais como Stramonita haemastoma floridana. Esses compostos tendem a se acumular em moluscos devido a sua baixa capacidade de eliminá-los. Um total de 248 indivíduos de S. haemastoma floridana foram coletados de uma população livre qualquer indício de imposex. Esses animais foram mantidos em 7 aquários, com aproximadamente 30 indivíduos cada

Speciation of organotin compounds in waters and marine sediments using purge-and-trap capillary gas chromatography with atomic emission detection

International Nuclear Information System (INIS)

Campillo, Natalia; Aguinaga, Nerea; Vin-tilde as, Pilar; Lopez-Garcia, Ignacio; Hernandez-Cordoba, Manuel

2004-01-01

A procedure for the simultaneous determination of six organotin compounds, including methyl-, butyl- and phenyltins, in waters and marine sediments is developed. The analytes were leached from the solid samples into an acetic acid:methanol mixture by using an ultrasonic probe. The organotins were derivatized with sodium tetraethylborate (NaBEt 4 ) in the aqueous phase, stripped by a flow of helium, pre-concentrated in a trap and thermally desorbed. This was followed by capillary gas chromatography with microwave-induced plasma atomic emission spectrometry as the detection system (GC-AED). Each chromatographic run took 22 min, including the purge time. Calibration curves were obtained by plotting peak area versus concentration and the correlation coefficients for linear calibration were at least 0.9991. Detection limits ranged from 11 to 50 ng Sn l -1 for tributyltin and tetramethyltin, respectively. The seawater samples analyzed contained variable concentrations of mono-, di- and tributyl- and monophenyltin, ranging from 0.05 to 0.48 μg Sn l -1 , depending on the compound. Some of the sediments analyzed contained concentrations of dibutyl- and tributyltin of between 6.0 and 13.0 ng Sn g -1 . Analysis of the certified reference material PACS-2, as well as of spiked water and sediment samples showed the accuracy of the method. The proposed method is selective and reproducible, and is considered suitable for monitoring organotin compounds in water and sediment samples

Speciation of organotin compounds in waters and marine sediments using purge-and-trap capillary gas chromatography with atomic emission detection

Energy Technology Data Exchange (ETDEWEB)

Campillo, Natalia [Department of Analytical Chemistry, Faculty of Chemistry, University of Murcia, E-30071 Murcia (Spain); Aguinaga, Nerea [Department of Analytical Chemistry, Faculty of Chemistry, University of Murcia, E-30071 Murcia (Spain); Vin-tilde as, Pilar [Department of Analytical Chemistry, Faculty of Chemistry, University of Murcia, E-30071 Murcia (Spain); Lopez-Garcia, Ignacio [Department of Analytical Chemistry, Faculty of Chemistry, University of Murcia, E-30071 Murcia (Spain); Hernandez-Cordoba, Manuel [Department of Analytical Chemistry, Faculty of Chemistry, University of Murcia, E-30071 Murcia (Spain)]. E-mail: hcordoba@um.es

2004-11-08

A procedure for the simultaneous determination of six organotin compounds, including methyl-, butyl- and phenyltins, in waters and marine sediments is developed. The analytes were leached from the solid samples into an acetic acid:methanol mixture by using an ultrasonic probe. The organotins were derivatized with sodium tetraethylborate (NaBEt{sub 4}) in the aqueous phase, stripped by a flow of helium, pre-concentrated in a trap and thermally desorbed. This was followed by capillary gas chromatography with microwave-induced plasma atomic emission spectrometry as the detection system (GC-AED). Each chromatographic run took 22 min, including the purge time. Calibration curves were obtained by plotting peak area versus concentration and the correlation coefficients for linear calibration were at least 0.9991. Detection limits ranged from 11 to 50 ng Sn l{sup -1} for tributyltin and tetramethyltin, respectively. The seawater samples analyzed contained variable concentrations of mono-, di- and tributyl- and monophenyltin, ranging from 0.05 to 0.48 {mu}g Sn l{sup -1}, depending on the compound. Some of the sediments analyzed contained concentrations of dibutyl- and tributyltin of between 6.0 and 13.0 ng Sn g{sup -1}. Analysis of the certified reference material PACS-2, as well as of spiked water and sediment samples showed the accuracy of the method. The proposed method is selective and reproducible, and is considered suitable for monitoring organotin compounds in water and sediment samples.

The organotin compounds trimethyltin (TMT) and triethyltin (TET) but not tributyltin (TBT) induce activation of microglia co-cultivated with astrocytes.

Science.gov (United States)

Röhl, C; Grell, M; Maser, E

2009-12-01

The organotin compounds trimethyltin (TMT), triethyltin (TET) and tributyltin (TBT) show different organotoxicities in vivo. While TMT and TET induce a strong neurotoxicity accompanied by microglial and astroglial activation, TBT rather effects the immune system. Previously, we have shown in an in vitro co-culture model that microglial cells can be activated by TMT in the presence of astrocytes. In this study, we wanted to investigate (a) if the neurotoxic organotin compound TET can also activate microglial cells in vitro similar to TMT and (b) if differences between the neurotoxicants TMT and TET on the one side and TBT on the other exist concerning microglial activation. Therefore, purified microglial and astroglial cell cultures from neonatal rat brains were treated either alone or in co-cultures for 24h with different concentrations of TMT, TET or TBT and the basal cytotoxicity and nitric oxide formation was determined. Furthermore, morphological changes of astrocytes were examined. Our results show that microglial activation can be increased in subcytolethal concentrations, but only in the presence of astrocytes and not in microglial cell cultures alone. This increase was induced by the neurotoxicants TMT and TET but not by TBT. Taken together, the differing microglia activating effect of the organotin compounds may contribute to the differing neurotoxic potential of this group of chemicals in vivo. In addition, our results emphasize the need for co-culture systems when studying interactions between different cell types for toxicity assessment.

Organotin contamination in fishes with different living patterns and its implications for human health risk in Taiwan

International Nuclear Information System (INIS)

Lee, C.-C.; Wang, T.; Hsieh, C.-Y.; Tien, C.-J.

2005-01-01

Contaminated levels of butyl- and phenyltin compounds, tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), triphenyltin (TPT), diphenlytin (DPT), and monophenyltin (MPT), were investigated in pelagic, demersal and cultured fish species from different seasons and locations in Taiwan. Seasonal variations were found in fishes from Wuchi and Hsingta fishing harbors for their butyltin levels (winter > summer) with the opposite trend for phenyltins in fishes from Patoutzu fishing harbor and demersal fishes from four fishing harbors (summer > winter). Fish liver contained the lowest percentage of TBT and the highest percentage of TPT among six organotin compounds. Consumption of contaminated pelagic species and fishes from Hsingta fishing harbor had the highest hazard index. However, the hazard quotients and hazard indices were all less than 1, suggesting a daily exposure at these levels of TBT, DBT and TPT may not be likely to cause any deleterious effects during lifetime in human population. - Spatial and seasonal variations in accumulation of organotins were showed by fishes with different living patterns and the potential health risk to ingest such fishes

Organotin contamination in fishes with different living patterns and its implications for human health risk in Taiwan

Energy Technology Data Exchange (ETDEWEB)

Lee, C.-C. [Department of Environmental and Occupational Health, Medical College, National Cheng Kung University, 138 Sheng Li Road, Tainan 704, Taiwan (China); Research Center of Environmental Trace Toxic Substances, National Cheng Kung University, 138 Sheng Li Road, Tainan 704, Taiwan (China); Wang, T. [Department of Environmental and Occupational Health, Medical College, National Cheng Kung University, 138 Sheng Li Road, Tainan 704, Taiwan (China); Hsieh, C.-Y. [Research Center of Environmental Trace Toxic Substances, National Cheng Kung University, 138 Sheng Li Road, Tainan 704, Taiwan (China); Tien, C.-J. [Department of Industrial Safety and Hygiene, Chung Hwa College of Medical Technology, 89 Wen-Hwa 1st Street, Jen-Te 717, Tainan, Taiwan (China)]. E-mail: cjtien@mail.hwai.edu.tw

2005-09-15

Contaminated levels of butyl- and phenyltin compounds, tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), triphenyltin (TPT), diphenlytin (DPT), and monophenyltin (MPT), were investigated in pelagic, demersal and cultured fish species from different seasons and locations in Taiwan. Seasonal variations were found in fishes from Wuchi and Hsingta fishing harbors for their butyltin levels (winter > summer) with the opposite trend for phenyltins in fishes from Patoutzu fishing harbor and demersal fishes from four fishing harbors (summer > winter). Fish liver contained the lowest percentage of TBT and the highest percentage of TPT among six organotin compounds. Consumption of contaminated pelagic species and fishes from Hsingta fishing harbor had the highest hazard index. However, the hazard quotients and hazard indices were all less than 1, suggesting a daily exposure at these levels of TBT, DBT and TPT may not be likely to cause any deleterious effects during lifetime in human population. - Spatial and seasonal variations in accumulation of organotins were showed by fishes with different living patterns and the potential health risk to ingest such fishes.

Ferrocene-quinoxaline Y-shaped chromophores as fascinating second-order NLO building blocks for long lasting highly active SHG polymeric films.

Science.gov (United States)

Senthilkumar, Kabali; Thirumoorthy, Krishnan; Dragonetti, Claudia; Marinotto, Daniele; Righetto, Stefania; Colombo, Alessia; Haukka, Matti; Palanisami, Nallasamy

2016-07-26

The first example of a Y-shaped ferrocene quinoxaline derivative with a surprisingly high and stable second harmonic generation (SHG) response in composite polymeric films is reported. The interesting quadratic hyperpolarizability values of different substituted Y-shaped chromophores are also investigated in solution by the EFISH technique.

Aerobic biodegradation of organotin compounds in activated sludge batch reactors

Energy Technology Data Exchange (ETDEWEB)

Stasinakis, Athanasios S. [Department of Environmental Studies, Water and Air Quality Laboratory, University of the Aegean, University Hill, Mytilene 81 100 (Greece)]. E-mail: astas@env.aegean.gr; Thomaidis, Nikolaos S. [Laboratory of Analytical Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, Zografou, Athens 157 71 (Greece); Nikolaou, Anastasia [Department of Environmental Studies, Water and Air Quality Laboratory, University of the Aegean, University Hill, Mytilene 81 100 (Greece); Kantifes, Andreas [Department of Environmental Studies, Water and Air Quality Laboratory, University of the Aegean, University Hill, Mytilene 81 100 (Greece)

2005-04-01

The biodegradation behavior of four organotin (OT) compounds, namely tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT) and triphenyltin (TPhT), was studied in lab-scale activated sludge batch reactors. The activated sludge was spiked with the OT compounds at a level of 100 {mu}g l{sup -1} as Sn. Determination of the OT compounds by GC-FPD after ethylation in the dissolved and particulate phase revealed that 24 h after the start of the experiments, almost the total of OT compounds has been removed from the dissolved phase and is associated with the suspended solids. Calculation of mass balance in batch reactors showed that OT compounds biodegradation was performed via a sequential dealkylation process. Removals due to biodegradation were differentiated according to the parent compound. In experiments with non-acclimatized biomass, a percentage of 27.1, 8.3, 73.8 and 51.3 was still present as TBT, DBT, MBT and TPhT, respectively, at the end of the experiment (18th day). Half-lives (t{sub 1/2}) of 10.2 and 5.1 days were calculated for TBT and DBT, respectively, whereas apparent t{sub 1/2} values could not be determined for MBT and TPhT (t{sub 1/2} > 18 days). The capacity of activated sludge to biodegrade OT compounds in the absence of supplemental substrate indicated that these compounds can be metabolized as single sources of carbon and energy in activated sludge systems. Excluding TBT, the presence of low concentrations of supplemental substrate did not affect the biodegradation potential of activated sludge. The acclimatization of biomass on OT compounds enhanced significantly biodegradation, resulting in significant decreases of half-lives of OT compounds. As a result in the presence of acclimatized biomass, half-lives of 1.4, 3.6, 9.8 and 5.0 days were calculated for TBT, DBT, MBT and TPhT, respectively. - The fate of organotins is assessed in activated sludge systems.

Aerobic biodegradation of organotin compounds in activated sludge batch reactors

International Nuclear Information System (INIS)

Stasinakis, Athanasios S.; Thomaidis, Nikolaos S.; Nikolaou, Anastasia; Kantifes, Andreas

2005-01-01

The biodegradation behavior of four organotin (OT) compounds, namely tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT) and triphenyltin (TPhT), was studied in lab-scale activated sludge batch reactors. The activated sludge was spiked with the OT compounds at a level of 100 μg l -1 as Sn. Determination of the OT compounds by GC-FPD after ethylation in the dissolved and particulate phase revealed that 24 h after the start of the experiments, almost the total of OT compounds has been removed from the dissolved phase and is associated with the suspended solids. Calculation of mass balance in batch reactors showed that OT compounds biodegradation was performed via a sequential dealkylation process. Removals due to biodegradation were differentiated according to the parent compound. In experiments with non-acclimatized biomass, a percentage of 27.1, 8.3, 73.8 and 51.3 was still present as TBT, DBT, MBT and TPhT, respectively, at the end of the experiment (18th day). Half-lives (t 1/2 ) of 10.2 and 5.1 days were calculated for TBT and DBT, respectively, whereas apparent t 1/2 values could not be determined for MBT and TPhT (t 1/2 > 18 days). The capacity of activated sludge to biodegrade OT compounds in the absence of supplemental substrate indicated that these compounds can be metabolized as single sources of carbon and energy in activated sludge systems. Excluding TBT, the presence of low concentrations of supplemental substrate did not affect the biodegradation potential of activated sludge. The acclimatization of biomass on OT compounds enhanced significantly biodegradation, resulting in significant decreases of half-lives of OT compounds. As a result in the presence of acclimatized biomass, half-lives of 1.4, 3.6, 9.8 and 5.0 days were calculated for TBT, DBT, MBT and TPhT, respectively. - The fate of organotins is assessed in activated sludge systems

Retrospective monitoring of organotin compounds in biological samples from North Sea and Baltic Sea. Are the use restrictions successful?; Retrospektives Monitoring von Organozinnverbindungen in biologischen Proben aus Nord- und Ostsee. Sind die Anwendungsbeschraenkungen erfolgreich?

Energy Technology Data Exchange (ETDEWEB)

Ruedel, Heinz; Steinhanses, Juergen; Mueller, Josef [Fraunhofer-Inst. fuer Molekularbiologie und Angewandte Oekologie (IME), Schmallenberg (Germany); Schroeter-Kermani, Christa [Umweltbundesamt, FG II 1.2, Berlin (Germany)

2009-06-15

Organotin compounds are used as biocides, plastic additives and catalysts. With respect to environmental effects, tributyltin (TBT) and triphenyltin (TPT) compounds are the most relevant, because of their high aquatic toxicity and endocrine effects on mussels and snails. TBT was mainly used as antifouling agents in coatings of ships and boats. In 1989, Germany banned the application to ships < 25 m length. Finally, in 2003, the use of organotin-based antifoulants within the European Union was completely banned. The results demonstrate the effectiveness of the legal measures undertaken to control organotin inputs into the aquatic environment. Nevertheless, organotin compounds are still relevant pollutants. Water concentrations calculated from the measured tissue concentrations by using the respective bioconcentration factors are still above the Environmental Quality Standards derived in the context of the Water Framework Directive (0.2ng/l) and the OSPAR mussel EAC (Environmental Assessment Criteria; 2.4ng/g ww), Thus adverse effects to marine organisms cannot be excluded. Further studies should be performed to verify the declining trends. More sensitive analytical methods, e.g. species-specific isotope dilution analysis, are recommended in order to detect lower environmental concentrations. (orig.)

Design, synthesis, biological assessment and molecular docking studies of new 2-aminoimidazole-quinoxaline hybrids as potential anticancer agents

Science.gov (United States)

Ghanbarimasir, Zahra; Bekhradnia, Ahmadreza; Morteza-Semnani, Katayoun; Rafiei, Alireza; Razzaghi-Asl, Nima; Kardan, Mostafa

2018-04-01

In a search for novel antiproliferative agents, a series of quinoxaline derivatives containing 2-aminoimidazole (8a-8x) were designed and synthesized. The structures of synthesized compounds were confirmed by IR, 1H NMR, 13C NMR, Mass Spectroscopy and analyzed using HSQC, COSY, ROESY, HMBC techniques. The anticancer activity of all derivatives were evaluated for colon cancer and breast cancer cell lines by the MTT assay and acridine orange/ethidium bromide double staining method. The anti-cancer effect in human colon cancer (HCT-116) and breast cancer (MCF-7) cell lines exhibited that compounds 8a, 8s, 8t, 8w, 8x appeared as potent antiproliferative agents and especially inhibited the human colon cancer cell proliferation with percentage of inhibition by over 50%. The most active compound was (E)-4-phenyl-1-((quinoxalin-2-ylmethylene)amino)-1H-imidazol-2-amine (8a) with the highest inhibition for MCF-7 (83.3%) and HCT-116 (70%) cell lines after 48 and 24 h, respectively. Molecular docking studies of these derivatives within c-kit active site as a validated target might be suggested them as appropriate candidates for further efforts toward more potent anticancer compounds.

Short-term exposure to the organotin compound triphenyltin modulates esterified steroid levels in females of Marisa cornuarietis.

Science.gov (United States)

Lyssimachou, Angeliki; Bachmann, J; Porte, C

2008-08-29

Long-term exposures to organotin compounds have shown alterations on endogenous steroid levels in gastropods together with the development of imposex. However, information regarding short-term effects of these compounds on the endocrine system of gastropods is lacking. This work aimed at investigating those responses in the ramshorn snail Marisa cornuarietis by looking at both endogenous levels of free and esterified steroids and the metabolism of the androgen precursor androstenedione by digestive gland/gonad microsomal fractions. One-week exposure to the organotin compound triphenyltin (TPT) led to a significant increase in esterified testosterone (60-85%) and a decrease in esterified estradiol (50-84%) in females, but had no effect on males. The observed alterations in esterified steroids were not directly related to changes in P450 aromatase activity that remained unchanged in exposed females. The enzymes involved in the metabolism of the androgen precursor androstenedione, namely 17beta-hydroxysteroid dehydrogenases and 5alpha-reductases, were not significantly altered by TPT exposure, suggesting that such enzymes are not primary targets of TPT in M. cornuarietis. Additional studies are needed to fully understand the significance of the observed alterations in females and their potential relationship with the development of imposex.

The Determination of Pesticidal and Non-Pesticidal Organotin Compounds by in situ Ethylation and Capillary Gas Chromatography with Pulsed Flame Photometric Detection

Science.gov (United States)

The concurrent determination of pesticidal and non-pesticidal organotin compounds in several water matrices, using a simultaneous in situ ethylation and liquid-liquid extraction followed by splitless injection mode capillary gas chromatography with pulsed flame photometric detect...

[Determination of organotin compounds in plastic products by GC/MS after ethyl derivatization with sodium tetraethylborate].

Science.gov (United States)

Ohno, Hiroyuki; Suzuki, Masako; Nakashima, Shigehito; Aoyama, Taiki; Mitani, Kazunori

2002-08-01

A simultaneous determination method for 9 organotin compounds in polyvinyl chloride (PVC) and silicone products used as kitchen utensils and food packages was developed using ethyl derivatization with sodium tetraethylborate (NaBEt4). Organotin compounds were extracted with acetone-hexane (3:7) from the samples after acidification and the extract was filtered and concentrated at under 40 degrees C. After centrifugal separation, these compounds were derivatized with 2% NaBEt4 solution and determined by GC/MS. This method was applicable for simple routine analysis. Recoveries of spiked compounds were 49.1-118.1% for 3 PVC products and 88.8-102.2% for a siliconized paper. Monooctyltin, dioctyltin and trioctyltin compounds were found in all PVC food containers at the levels of 123-1,380 micrograms/g, 1,770-13,200 micrograms/g and 6.6-139 micrograms/g, respectively. They also were found in 3 gloves, 5 spouts, 1 hose and 5 pipes. Some PVC products contained monomethyltin, dimethyltin, trimethyltin, monobutyltin and dibutyltin compounds at the levels of 97.3-433 micrograms/g, 96.5-5,120 micrograms/g, 8.5-24.9 micrograms/g, 1.2-852 micrograms/g and 1.2-29.4 micrograms/g, respectively.

Organotin compounds in surface sediments of the Southern Baltic coastal zone: a study on the main factors for their accumulation and degradation.

Science.gov (United States)

Filipkowska, Anna; Kowalewska, Grażyna; Pavoni, Bruno

2014-02-01

Sediment samples were collected in the Gulf of Gdańsk, and the Vistula and Szczecin Lagoons-all located in the coastal zone of the Southern Baltic Sea-just after the total ban on using harmful organotins in antifouling paints on ships came into force, to assess their butyltin and phenyltin contamination extent. Altogether, 26 sampling stations were chosen to account for different potential exposure to organotin pollution and environmental conditions: from shallow and well-oxygenated waters, shipping routes and river mouths, to deep and anoxic sites. Additionally, the organic carbon content, pigment content, and grain size of all the sediment samples were determined, and some parameters of the near-bottom water (oxygen content, salinity, temperature) were measured as well. Total concentrations of butyltin compounds ranged between 2 and 182 ng Sn g(-1) d.w., whereas phenyltins were below the detection limit. Sediments from the Gulf of Gdańsk and Vistula Lagoon were found moderately contaminated with tributyltin, whereas those from the Szczecin Lagoon were ranked as highly contaminated. Butyltin degradation indices prove a recent tributyltin input into the sediments adjacent to sites used for dumping for dredged harbor materials and for anchorage in the Gulf of Gdańsk (where two big international ports are located), and into those collected in the Szczecin Lagoon. Essential factors affecting the degradation and distribution of organotins, based on significant correlations between butyltins and environmental variables, were found in the study area.

A facile synthesis of phenazine and quinoxaline derivatives using magnesium sulfate heptahydrate as a catalyst

Directory of Open Access Journals (Sweden)

BAHADOR KARAMI

2011-09-01

Full Text Available Convenient and simple procedures for the synthesis of phenazine and quinoxaline derivatives were developed via a reaction of o-phenylenediamines and 1,2-dicarbonyl compounds. In addition, the synthesis of two new 1,4-benzodiazine derivatives and the catalytic activity of magnesium sulfate heptahydrate (MgSO4·7H2O in the room temperature condensation of o-phenylenediamines and 1,2-dicarbonyl compounds in ethanol as solvent are reported. This method has many appealing attributes, such as excellent yields, short reaction times, and simple work-up procedures.

Synthesis and Neuropharmacological Evaluation of Some Novel Quinoxaline 2, 3-Dione Derivatives

Directory of Open Access Journals (Sweden)

Selvaraj Jubie

2012-01-01

Full Text Available Quinoxaline-2, 3-dione obtained from cyclocondensation reaction of o-phenylene diamine with oxalic acid was reacted with three different ketones and formaldehyde to give the corresponding Mannich bases in satisfactory yield. Their structures were confirmed by using 1H NMR, IR, and mass analysis. In pharmacological evaluation, the synthesized compounds showed its curative effect against ethidium-bromide-induced demyelination in rats. For the purpose, different screening methods such as open field exploratory behavior test, rota rod test, grip strength test, beam walk test, and photo actometer test were performed. Ethidium bromide induction showed muscle weakness; muscle discoordination; loss of locomotor activity, and so forth, the synthesized drugs reversed all the above-mentioned neuromuscular disorders caused by ethidium bromide administration.

A category approach to predicting the developmental (neuro) toxicity of organotin compounds: The value of the zebrafish (Danio rerio) embryotoxicity test (ZET)

NARCIS (Netherlands)

Beker van Woudenberg, A.; Wolterbeek, A.; Brake, L. te; Snel, C.; Menke, A.; Rubingh, C.; Groot, D. de; Kroese, D.

2013-01-01

Zebrafish embryos were exposed to different organotin compounds during very early development (<100. h post fertilization). Morphology, histopathology and swimming activity (in a motor activity test) were the endpoints analyzed. DBTC was, by far, the most embryotoxic compound at all time points and

Synthesis, spectral characterization and biological studies of some organotin(IV) complexes of L-proline, trans-hydroxy- L-proline and L-glutamine

Science.gov (United States)

Nath, Mala; Jairath, Ruchi; Eng, George; Song, Xueqing; Kumar, Ashok

2005-12-01

New organotin(IV) complexes of the general formula R 3Sn(L) (where R = Me, n-Bu and HL = L-proline; R = Me, Ph and HL = trans-hydroxy- L-proline and L-glutamine) and R 2Sn(L) 2 (where R = n-Bu, Ph and HL = L-proline; R = Ph, HL = trans-hydroxy- L-proline) have been synthesized by the reaction of R nSnCl 4- n (where n = 2 or 3) with sodium salt of the amino acid (HL). n-Bu 2Sn(Pro) 2 was synthesized by the reaction of n-Bu 2SnO with L-proline under azeotropic removal of water. The bonding and coordination behavior in these complexes have been discussed on the basis of IR and 119Sn Mössbauer spectroscopic studies in the solid-state. Their coordination behavior in solution has been discussed with the help of multinuclear ( 1H, 13C and 119Sn) NMR spectral studies. The 119Sn Mössbauer and IR studies indicate that L-proline and trans-hydroxy- L-proline show similar coordination behavior towards organotin(IV) compounds. Pentacoordinate trigonal-bipyramidal and hexacoordinate octahedral structures, respectively, have been proposed for the tri- and diorganotin(IV) complexes of L-proline and trans-hydroxy- L-proline, in which the carboxylate group acts as bidentate group. L-Glutamine shows different coordination behavior towards organotin(IV) compounds, it acts as monoanionic bidentate ligand coordinating through carboxylate and amino group. The triorganotin(IV) complexes of L-glutamine have been proposed to have trigonal-bipyramidal environment around tin. The newly synthesized complexes have been tested for their antiinflammatory and cardiovascular activities. Their LD 50 values are >1000 mg kg -1.

Esters of Quinoxaline 1ˏ4-Di-N-oxide with Cytotoxic Activity on Tumor Cell Lines Based on NCI-60 Panel

Science.gov (United States)

Rivera, Gildardo; Ahmad Shah, Syed Shoaib; Arrieta-Baez, Daniel; Palos, Isidro; Mongue, Antonio; Sánchez-Torres, Luvia Enid

2017-01-01

Quinoxalines display diverse and interesting pharmacological activities as antibacterial, antiviral, antiparasitic and anticancer agents. Particularly, their 1ˏ4-di-N-oxide derivatives have proved to be cytotoxic agents that are active under hypoxic conditions as that of solid tumours. A new series of quinoxaline 1ˏ4-di-N-oxide substitutes at 7-position with esters group were synthetized and characterized by infrared (IR), proton nuclear magnetic resonance (1H-NMR), spectroscopy, and elemental analysis. Seventeen derivatives (M1-M3, E1-E8, P1-P3 and DR1-DR3) were selected and evaluated for antitumor activities using the NCI-60 human tumor cell lines screen. Results showed that E7, P3 and E6 were the most active compounds against the cell lines tested. Substitutions at 7-position with esters group not necessarily affect the biological activity, but the nature of the esters group could exert an influence on the selectivity. Additionally, substitutions at 2-position influenced the cytotoxic activity of the compounds. PMID:29201086

Design, synthesis and antimalarial activity of novel bis{N-[(pyrrolo[1,2-a]quinoxalin-4-yl)benzyl]-3-aminopropyl}amine derivatives.

Science.gov (United States)

Guillon, Jean; Cohen, Anita; Gueddouda, Nassima Meriem; Das, Rabindra Nath; Moreau, Stéphane; Ronga, Luisa; Savrimoutou, Solène; Basmaciyan, Louise; Monnier, Alix; Monget, Myriam; Rubio, Sandra; Garnerin, Timothée; Azas, Nadine; Mergny, Jean-Louis; Mullié, Catherine; Sonnet, Pascal

2017-12-01

Novel series of bis- and tris-pyrrolo[1,2-a]quinoxaline derivatives 1 were synthesized and tested for in vitro activity upon the intraerythrocytic stage of W2 and 3D7 Plasmodium falciparum strains. Biological results showed good antimalarial activity with IC 50 in the μM range. In attempting to investigate the large broad-spectrum antiprotozoal activities of these new derivatives, their properties toward Leishmania donovani were also investigated and revealed their selective antiplasmodial profile. In parallel, the in vitro cytotoxicity of these molecules was assessed on the human HepG2 cell line. Structure-activity relationships of these new synthetic compounds are discussed here. The bis-pyrrolo[1,2-a]quinoxalines 1n and 1p were identified as the most potent antimalarial candidates with selectivity index (SI) of 40.6 on W2 strain, and 39.25 on 3D7 strain, respectively. As the telomeres of the parasite could constitute an attractive target, we investigated the possibility of targeting Plasmodium telomeres by stabilizing the Plasmodium telomeric G-quadruplexes through a FRET melting assay by our new compounds.

The Determination of Pesticidal and Non-Pesticidal Organotin Compounds in Water Matrices by in situ Ethylation and Gas Chromatography with Pulsed Flame Photometric Detection

Science.gov (United States)

The concurrent determination of pesticidal and non-pesticidal organotin compounds in several water matrices, using a simultaneous in situ ethylation and liquid-liquid extraction followed by splitless injection mode capillary gas chromatography with pulsed flame photometric detect...

Radioiodination and biodistribution of NBNPQD ( 2-benzyl-1-oxo-1-2-dihydropyrido (4,3-b) quinoxaline 5,10- dioxide) in tumor bearing mice

International Nuclear Information System (INIS)

Ibrahim, I. T.; Habib, S. A.; Wally, H. A.; El-Shishtawy, M. M.

2012-12-01

NBNPQD (2-benzyl-1-oxo-1,2 dihydropyrido (quinoxaline 5,10-dioxide) is a new synthesized quinoxaline derivative. It could be labeled with Auger emitter iodine-125 successfully with yield about 90%. The labeled product was evaluated by electrophoresis and studied. 1 23I - NBNPQD was stable up to 48 h post labeling. Biodistribution study of 1 23I - NBNPQD in normal and tumor bearing mice was also conducted. The biodistribution data revealed that 1 23I -NBNPQD diffused rapidly to tumor sites in to both ascites and solid tumor bearing mice. 1 23I -NBNPQD was decline rapidly from most of organs but slowly from tumor sites. In-vitro radiotoxicity of 1 23I - NBNPQD increased with the increase of its radioactivity. This study encourages the possible use of 1 23I - NBNPQD in tumor imaging and treatment. It also encourages further studies on the chemotherapeutic activity of NBNPQD hoping to get a new potent antitumor agent. (Author)

Experimental and theoretical characterization of organic salt: 2-((4-bromophenyl)amino) pyrido[1,2-a] quinoxalin-11-ium bromide monohydrate synthesized via oxidative cyclization

Science.gov (United States)

Faizi, Md. Serajul Haque; Alam, Mohammad Jane; Haque, Ashanul; Ahmad, Shabbir; Shahid, M.; Ahmad, Musheer

2018-03-01

Quinoxalines are nitrogen-embedded heterocyclic compounds that possess unique and versatile pharmacological applications. The present article describes synthesis and characterization of organic salt 2-((4-bromophenyl)amino)pyrido [1,2-a]quinoxalin-11-ium bromide (BAPQ), an oxidative cyclized product of N-phenyl-N-(pyridine-2-ylmethylene)benzene-1,4-diamine (PPMD). The structure of the synthesized product was extensively characterized by 1H NMR, 2D-COSY NMR, MS, IR, UV-vis, X-ray techniques and elemental analysis. The electronic and structural properties of BAPQ was well complemented by performing extensive computational studies (B3LYP/6-311G (d,p) basis sets). Metal-free, mild reaction condition, easy work-up and excellent yield with high purity are main features of this work and thus holds promise for the generation of new compounds of this class. Analytical results indicated ionic nature of the compound with bromide as counterion. DFT calculation showed low kinetic stability and high reactivity of the compound.

Association of placenta organotin concentrations with growth and ponderal index in 110 newborn boys from Finland during the first 18 months of life

DEFF Research Database (Denmark)

Rantakokko, Panu; Main, Katharina M; Wohlfart-Veje, Christine

2014-01-01

BACKGROUND: Humans are exposed to tributyltin (TBT), previously used as an antifouling paint in ships, mainly through fish consumption. As TBT is a known obesogen, we studied the association of placenta TBT and other organotin compounds (OTCs) with ponderal index (PI) and growth during the first 18...

Contaminação ambiental por compostos organoestânicos Environmental contamination for organotin compounds

Directory of Open Access Journals (Sweden)

Ana Flavia Locateli Godoi

2003-10-01

Full Text Available The occurrence and the effects of organotin compounds (OTs have been studied since a long time, due to their widespread use and deleterious effects. Some OTs are used as pesticides in crops, or as biocides in antifouling paints, applied in the ship hulls to avoid attachment and growth of tube worms, mussels and barnacles. However, "nontarget" organisms may be exposed, resulting in the poisoning of biological system, originating mutations and sentencing species to extinction. In this work we reported a revision study on the history of OTs and the techniques developed for its assessment and control.

Two-dimensional 1H and 31P NMR spectra of a decamer oligodeoxyribonucleotide duplex and a quinoxaline ([MeCys3, MeCys7]TANDEM) drug duplex complex

International Nuclear Information System (INIS)

Powers, R.; Olsen, R.K.; Gorenstein, D.G.

1989-01-01

Assignment of the 1H and 31P NMR spectra of a decamer oligodeoxyribonucleotide duplex, d(CCCGATCGGG), and its quinoxaline ([MeCys3, MeCys7]TANDEM) drug duplex complex has been made by two-dimensional 1H-1H and heteronuclear 31P-1H correlated spectroscopy. The 31P chemical shifts of this 10 base pair oligonucleotide follow the general observation that the more internal the phosphate is located within the oligonucleotide sequence, the more upfield the 31P resonance occurs. While the 31P chemical shifts show sequence-specific variations, they also do not generally follow the Calladine rules previously demonstrated. 31P NMR also provides a convenient monitor of the phosphate ester backbone conformational changes upon binding of the drug to the duplex. Although the quinoxaline drug, [MeCys3, MeCys7]TANDEM, is generally expected to bind to duplex DNA by bis-intercalation, only small 31P chemical shift changes are observed upon binding the drug to duplex d(CCCGATCGGG). Additionally, only small perturbations in the 1H NMR and UV spectra are observed upon binding the drug to the decamer, although association of the drug stabilizes the duplex form relative to the other states. These results are consistent with a non-intercalative mode of association of the drug. Modeling and molecular mechanics energy minimization demonstrate that a novel structure in which the two quinoxaline rings of the drug binds in the minor groove of the duplex is possible

Synthesis, Characterization and Epoxidation of cis-Enriched New Polycarbonates Catalyzed by Efficient Organotin Compound

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A. H. Massoudi

2011-01-01

Full Text Available Presence of active functional groups on polymer chain is a suitable aspect of polymer structure which allows performing next favourite reactions on polymer molecule. In this research a novel aromatic derivative of cis-but-2-endiol was synthesized as monomer. The synthesized monomer was polymerized using diphenyl carbonate and 1,4-butandiol as second and third monomer along with organotin catalyst. Polymerization reaction performed by using melt-phase transesterification process to produce a new terpolymer of polycarbonate. During the reaction the double bonds are preserved on polymer chain and epoxidized by m-chloroperbenzoic acid (MCBPA in good yield to demonstrate the reactivity and possibility of performing further reactions on double bonds of polymer.

A Ferrocene-Quinoxaline Derivative as a Highly Selective Probe for Colorimetric and Redox Sensing of Toxic Mercury(II Cations

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Antonio Caballero

2010-12-01

Full Text Available A new chemosensor molecule 3 based on a ferrocene-quinoxaline dyad recognizes mercury (II cations in acetonitrile solution. Upon recognition, an anodic shift of the ferrocene/ferrocenium oxidation peaks and a progressive red-shift (Δλ = 140 nm of the low-energy band, are observed in its absorption spectrum. This change in the absorption spectrum is accompanied by a colour change from orange to deep green, which can be used for a “naked-eye” detection of this metal cation.

Spectral and Kinetic Properties of Radicals Derived from Oxidation of Quinoxalin-2-One and Its Methyl Derivative

OpenAIRE

Konrad Skotnicki; Julio R. De la Fuente; Alvaro Cañete; Krzysztof Bobrowski

2014-01-01

The kinetics and spectral characteristics of the transients formed in the reactions of •OH and •N3 with quinoxalin-2(1H)-one (Q), its methyl derivative, 3-methylquinoxalin-2(1H)-one (3-MeQ) and pyrazin-2-one (Pyr) were studied by pulse radiolysis in aqueous solutions at pH 7. The transient absorption spectra recorded in the reactions of •OH with Q and 3-MeQ consisted of an absorption band with λmax = 470 nm assigned to the OH-adducts on the benzene ring, and a second band with λmax = 390 nm (...

Organotin Exposure and Vertebrate Reproduction: A Review

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Julia Fernandez Puñal de Araújo

2018-03-01

Full Text Available Organotin (OTs compounds are organometallic compounds that are widely used in industry, such as in the manufacture of plastics, pesticides, paints, and others. OTs are released into the environment by anthropogenic actions, leading to contact with aquatic and terrestrial organisms that occur in animal feeding. Although OTs are degraded environmentally, reports have shown the effects of this contamination over the years because it can affect organisms of different trophic levels. OTs act as endocrine-disrupting chemicals (EDCs, which can lead to several abnormalities in organisms. In male animals, OTs decrease the weights of the testis and epididymis and reduce the spermatid count, among other dysfunctions. In female animals, OTs alter the weights of the ovaries and uteri and induce damage to the ovaries. In addition, OTs prevent fetal implantation and reduce mammalian pregnancy rates. OTs cross the placental barrier and accumulate in the placental and fetal tissues. Exposure to OTs in utero leads to the accumulation of lipid droplets in the Sertoli cells and gonocytes of male offspring in addition to inducing early puberty in females. In both genders, this damage is associated with the imbalance of sex hormones and the modulation of the hypothalamic–pituitary–gonadal axis. Here, we report that OTs act as reproductive disruptors in vertebrate studies; among the compounds are tetrabutyltin, tributyltin chloride, tributyltin acetate, triphenyltin chloride, triphenyltin hydroxide, dibutyltin chloride, dibutyltin dichloride, diphenyltin dichloride, monobutyltin, and azocyclotin.

Synthesis, spectroscopic properties and biological activity of new mono organotin(IV complexes with 5-bromo-2-hydroxybenzaldehyde-4,4-dimethylthiosemicarbazone

Directory of Open Access Journals (Sweden)

Rosenani A. Haque

2015-12-01

Full Text Available The organotin(IV complexes [RSn(L] (where R = Me (2, R = n-Bu (3, R = Ph (4; H2L (1 = 5-bromo-2-hydroxybenzaldehyde-4,4-dimethylthiosemicarbazone have been synthesized by the reaction of organotin(IV chloride(s with H2L (1. All the compounds have been characterized by CHN analyses, UV–vis, FT-IR, 1H, 13C and 119Sn NMR spectral studies. The molecular structure of H2L (1 has been confirmed by X-ray crystallography. The infrared spectrum gives confirmation for the compound (H2L in the thione form, which is supported with the observed bond lengths from the crystal structure. Spectral studies revealed that the dinegative tridentate ligand is bonded to the tin(IV atom via phenolic-O, azomethine-N and thiolate-S atoms. 119Sn NMR data in DMSO-d6 suggested penta-coordinated Sn(IV atom in solutions for all complexes (2–4. The compound, H2L (1 crystallizes into a monoclinic lattice with the space group P21/c, Z = 4, V = 1,191.75(8Å3. The compounds were also tested for their antiproliferative activity against human colon cancer cell line (HCT 116 and displayed strong cytotoxic activities.

Conductometric and voltammetric studies on the bis(triphenyl phosphine) ruthenium(II) complex, cis-[RuCl2(L)(PPh3)2], where L: 2-(2'-pyridyl)quinoxaline

Czech Academy of Sciences Publication Activity Database

Tsierkezos, Nikos; Philippopoulos, A. I.

2009-01-01

Roč. 362, č. 4 (2009), s. 3079-3087 ISSN 0020-1693 Grant - others:Kapodistrias Program(GR) 70/4/9277 Institutional research plan: CEZ:AV0Z40550506 Keywords : assocition constant * conductivity * cyclic voltammetry * ruthenium * quinoxaline Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.322, year: 2009

Structure-based drug design of a highly potent CDK1,2,4,6 inhibitor with novel macrocyclic quinoxalin-2-one structure.

Science.gov (United States)

Kawanishi, Nobuhiko; Sugimoto, Tetsuya; Shibata, Jun; Nakamura, Kaori; Masutani, Kouta; Ikuta, Mari; Hirai, Hiroshi

2006-10-01

The design of a novel series of cyclin-dependent kinase (CDK) inhibitors containing a macrocyclic quinoxaline-2-one is reported. Structure-based drug design and optimization from the starting point of diarylurea 2, which we previously reported as a moderate CDK1,2,4,6 inhibitor [J. Biol.Chem.2001, 276, 27548], led to the discovery of potent CDK1,2,4,6 inhibitor that were suitable for iv administration for in vivo study.

Organotins in zebra mussels (Dreissena polymorpha) and sediments of the Quebec City Harbour area of the St. Lawrence River.

Science.gov (United States)

Regoli, L; Chan, H M; de Lafontaine, Y; Mikaelian, I

2001-07-01

Toxic antifouling agents such as tributyltin (TBT) and triphenyltin (TPT) have been released in aquatic ecosystems through the use of antifouling paint applied to ship hulls, pleasure crafts and fish nets and these compounds can bioaccumulate in aquatic organisms. The purpose of this study was 1) to assess the extent of the distribution of organotins from a contaminated marina to the St. Lawrence River system by measuring organotin concentrations in zebra mussels (Dreissena polymorpha) and in sediments collected from 9 sites along the St. Lawrence River near Quebec City in July 1998, and 2) to examine the histopathological condition of zebra mussel tissues from these sites. TBT concentrations in zebra mussels were between 37 and 1078 ng Sn g(-1) wet weight, with the highest value found in the Bassin Louise marina. Elevated concentrations were also found in two other marinas. The concentrations decreased sharply to background levels just outside the marinas. All butyltins were detected in all sediments analysed, with highest values found in the Bassin Louise marina. Phenyltins were detected in three of the nine sites in low concentrations (zebra mussels. There was a significant correlation between TBT in sediments and mussels. Gonadal development of zebra mussels varied largely between sites, and was negatively associated to TBT levels in mussel tissue. This study shows that TBT contamination remains a problem in localised freshwater sectors of the St. Lawrence River.

Flame retardants, surfactants and organotins in sediment and mysid shrimp of the Scheldt estuary (The Netherlands)

International Nuclear Information System (INIS)

Verslycke, Tim A.; Vethaak, A. Dick; Arijs, Katrien; Janssen, Colin R.

2005-01-01

Sediment and mysids from the Scheldt estuary, one of the largest and most polluted estuaries in Western Europe, were analyzed for a number of contaminants that have been shown to possess endocrine-disrupting activity, i.e. organotins, polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), tetrabromobisphenol A (TBBPA), nonylphenol ethoxylates (NPE) and transformation products, nonylphenol (NP) and nonylphenol ether carboxylates (NPEC). In addition, in vitro estrogenic and androgenic potencies of water and sediment extracts were determined. Total organotin concentrations ranged from 84 to 348 ng/g dw in sediment and 1110 to 1370 ng/g dw in mysid. Total PBDE (excluding BDE-209) concentrations ranged from 14 to 22 ng/g dw in sediment and from 1765 to 2962 ng/g lipid in mysid. High concentrations of BDE-209 (240-1650 ng/g dw) were detected in sediment and mysid (269-600 ng/g lipid). Total HBCD concentrations in sediment and mysid were 14-71 ng/g dw and 562-727 ng/g lipid, respectively. Total NPE concentrations in sediment were 1422 ng/g dw, 1222 ng/g dw for NP and 80 ng/g dw for NPEC and ranged from 430 to 1119 ng/g dw for total NPE and from 206 to 435 ng/g dw for NP in mysid. Significant estrogenic potency, as analyzed using the yeast estrogen assay, was detected in sediment and water samples from the Scheldt estuary, but no androgenic activity was found. This study is the first to report high levels of endocrine disruptors in estuarine mysids. - Field populations of mysid shrimp (Neomysis integer) of the Scheldt estuary (The Netherlands) are exposed to high concentrations of endocrine disruptors

Baseline of organotin pollution in fishes, clams, shrimps, squids and crabs collected from the west coast of India

Digital Repository Service at National Institute of Oceanography (India)

Jadhav, S.; Bhosale, D.; Bhosle, N.B.

is available. The present study was planned to assess organotin contamination levels in edible marine organisms collected from the fish markets of Goa, Karwar and Mumbai, the west coast of India. The sampling locations: Goa (15.5ºN, 73.9ºE), Karwar (14.8º... of Karwar is around 36,000 tonnes. Mumbai coast is about 140 km long. Mumbai is among busiest harbours on the west coast of India is known for industrial pollution. The fishes, clams, crabs and squids and shrimps were collected from local fish markets...

New mono-organotin (IV) dithiocarbamate complexes

International Nuclear Information System (INIS)

Muthalib, Amirah Faizah Abdul; Baba, Ibrahim

2014-01-01

Eighteen new mono-organotin dithiocarbamate compounds derived each nine from methyltin(IV) and phenyltin(IV) reacted using in-situ method with various type of N-dialkylamine together with carbon disulphide with the ratio of 1:3:3. Elemental and gravimetric analysis showed that the general formula of these compounds were RSnCl[S 2 CNR′R″] 2 (R= Ph, CH 3 , R′ = CH 3 , C 2 H 5 , C 7 H 7 and R″ = C 2 H 5 , C 6 H 11 , iC 3 H 7 , C 7 H 7 ). These compounds had been characterized by infrared spectroscopy, ultraviolet spectroscopy, 1 H, 13 C NMR spectroscopy and single crystal X-ray crystallography. The infrared spectra of these compounds showed three important peaks indicating the formation of dithiocarbamate compounds, ν(C N), ν(C S) and ν(Sn-S) band which present in the region of 1444–1519, 954–1098 and 318–349 cm −1 respectively. The ultraviolet-visible spectra showed an absorption band for the π - π* transition of N C S group in the range of 253 – 259 nm due to the intramolecular charge transfer of the ligand. The 13 C NMR spectra showed an important shift for δ(N 13 CS 2 ) in the range of 196.8 – 201.9 ppm.. Single crystal X-ray diffraction studies showed three new structures with the general formula of PhSnCl[S 2 CN(Et)(i−Pr)] 2 , MeSnCl[S 2 CN(Me)(Cy)] 2 and MeSnCl[S 2 CN(i−Pr)(CH 2 Ph)] 2 . All structures having a distorted octahedral geometry set by CClS 4 donor atom from the two chelating dithiocarbamate ligands

Organotin intake through fish consumption in Finland

Energy Technology Data Exchange (ETDEWEB)

Airaksinen, Riikka, E-mail: Riikka.Airaksinen@thl.fi [National Institute for Health and Welfare, Department of Environmental Health, P.O. Box 95, FI-70701 Kuopio (Finland); Rantakokko, Panu; Turunen, Anu W.; Vartiainen, Terttu [National Institute for Health and Welfare, Department of Environmental Health, P.O. Box 95, FI-70701 Kuopio (Finland); Vuorinen, Pekka J.; Lappalainen, Antti; Vihervuori, Aune [Finnish Game and Fisheries Research Institute, Helsinki (Finland); Mannio, Jaakko [Finnish Environment Institute, Helsinki (Finland); Hallikainen, Anja [Finnish Food Safety Authority Evira, Helsinki (Finland)

2010-08-15

Background: Organotin compounds (OTCs) are a large class of synthetic chemicals with widely varying properties. Due to their potential adverse health effects, their use has been restricted in many countries. Humans are exposed to OTCs mostly through fish consumption. Objectives: The aim of this study was to describe OTC exposure through fish consumption and to assess the associated potential health risks in a Finnish population. Methods: An extensive sampling of Finnish domestic fish was carried out in the Baltic Sea and freshwater areas in 2005-2007. In addition, samples of imported seafood were collected in 2008. The chemical analysis was performed in an accredited testing laboratory during 2005-2008. Average daily intake of the sum of dibutyltin (DBT), tributyltin (TBT), triphenyltin (TPhT) and dioctyltin (DOT) ({Sigma}OTCs) for the Finnish population was calculated on the basis of the measured concentrations and fish consumption rates. Results: The average daily intake of {Sigma}OTCs through fish consumption was 3.2 ng/kg bw day{sup -1}, which is 1.3% from the Tolerable Daily Intake (TDI) of 250 ng/kg bw day{sup -1} set by the European Food Safety Authority. In total, domestic wild fish accounted for 61% of the {Sigma}OTC intake, while the intake through domestic farmed fish was 4.0% and the intake through imported fish was 35%. The most important species were domestic perch and imported salmon and rainbow trout. Conclusions: The Finnish consumers are not likely to exceed the threshold level for adverse health effects due to OTC intake through fish consumption.

Organotin intake through fish consumption in Finland

International Nuclear Information System (INIS)

Airaksinen, Riikka; Rantakokko, Panu; Turunen, Anu W.; Vartiainen, Terttu; Vuorinen, Pekka J.; Lappalainen, Antti; Vihervuori, Aune; Mannio, Jaakko; Hallikainen, Anja

2010-01-01

Background: Organotin compounds (OTCs) are a large class of synthetic chemicals with widely varying properties. Due to their potential adverse health effects, their use has been restricted in many countries. Humans are exposed to OTCs mostly through fish consumption. Objectives: The aim of this study was to describe OTC exposure through fish consumption and to assess the associated potential health risks in a Finnish population. Methods: An extensive sampling of Finnish domestic fish was carried out in the Baltic Sea and freshwater areas in 2005-2007. In addition, samples of imported seafood were collected in 2008. The chemical analysis was performed in an accredited testing laboratory during 2005-2008. Average daily intake of the sum of dibutyltin (DBT), tributyltin (TBT), triphenyltin (TPhT) and dioctyltin (DOT) (ΣOTCs) for the Finnish population was calculated on the basis of the measured concentrations and fish consumption rates. Results: The average daily intake of ΣOTCs through fish consumption was 3.2 ng/kg bw day -1 , which is 1.3% from the Tolerable Daily Intake (TDI) of 250 ng/kg bw day -1 set by the European Food Safety Authority. In total, domestic wild fish accounted for 61% of the ΣOTC intake, while the intake through domestic farmed fish was 4.0% and the intake through imported fish was 35%. The most important species were domestic perch and imported salmon and rainbow trout. Conclusions: The Finnish consumers are not likely to exceed the threshold level for adverse health effects due to OTC intake through fish consumption.

Simple synthesis of new carbon-11-labeled 1,2,4-triazolo[4,3-a]quinoxalin-1-one derivatives for PET imaging of A3 adenosine receptor

International Nuclear Information System (INIS)

Gao, Mingzhang; Gao, Andy Chufan; Wang, Min; Zheng, Qi-Huang

2014-01-01

The reference standards 4a-b, 6a-b, 7a-c, and desmethylated precursors 9a-b, 10a-b, 8a-c were synthesized from 4-methoxyaniline, ethyl 2-chloro-acetoacetate and substituted benzene-1,2-diamines with 3, 5, 6 steps in 61–67%, 34–41%, 23–31%, and with 4, 6, 7 steps in 49–57%, 28–35%, 20–27% overall chemical yield, respectively. The target tracers [ 11 C]4a-b, [ 11 C]6a-b, [ 11 C]7a-c were synthesized from their corresponding precursors with [ 11 C]CH 3 OTf through O-[ 11 C]methylation and isolated by simplified SPE in 40–60% decay corrected radiochemical yields at EOB, with 185–370 GBq/μmol specific activity at EOS. - Highlights: • New 1,2,4-triazolo[4,3-a]quinoxalin-1-one derivatives were synthesized. • New 11 C-labeled 1,2,4-triazolo[4,3-a]quinoxalin-1-one derivatives were synthesized. • A simplified SPE technique was employed in radiosynthesis

Synthesis and structural studies of first row transition metal complexes of N-(2-nitro-benzilidine-3-hydrazino quinoxaline-2-one

Directory of Open Access Journals (Sweden)

P.V. Anantha Lakshmi

2008-12-01

Full Text Available Cr(III, Mn(II, Fe(III, Co(II, Ni(II and Cu(II complexes of N-(2-nitro-benzilidene-3-hydrazino quinoxaline-2-one (NBHQO have been synthesized and characterized by elemental analysis, conductance, thermal, spectral and magnetic data. NBHQO acts as a bidentate ON donor in all the complexes except in Ni(II complex in which it acts as a tridentate ONO donor. Octahedral geometries have been proposed for all the complexes except for Cu(II complex to which the square planar geometry is assigned.

Organotin persistence in contaminated marine sediments and porewaters: In situ degradation study using species-specific stable isotopic tracers

Energy Technology Data Exchange (ETDEWEB)

Furdek, Martina; Mikac, Nevenka [Division for Marine and Environmental Research, Rudjer Boskovic Institute, Bijenicka 54, Zagreb (Croatia); Bueno, Maite; Tessier, Emmanuel; Cavalheiro, Joana [Laboratoire de Chimie Analytique Bio-inorganique et Environnement, Institut Pluridisciplinaire de Recherche sur l’Environnement et les Matériaux, CNRS UMR 5254, Université de Pau et des Pays de l’Adour, Hélioparc Pau Pyrénées, 2, Av. P. Angot, 64053 Pau Cedex 9 (France); Monperrus, Mathilde, E-mail: mathilde.monperrus@univ-pau.fr [Laboratoire de Chimie Analytique Bio-inorganique et Environnement, Institut Pluridisciplinaire de Recherche sur l’Environnement et les Matériaux, CNRS UMR 5254, Université de Pau et des Pays de l’Adour, Hélioparc Pau Pyrénées, 2, Av. P. Angot, 64053 Pau Cedex 9 (France)

2016-04-15

Highlights: • Limiting step in OTC degradation in sediments is their desorption into porewater. • TBT persistence in contaminated sediments increases in sediments rich in organic matter. • DBT does not accumulate in sediments as degradation product of TBT. • TBT and DBT degradation in porewaters occurs with half-lives from 2.9 to 9.2 days. • PhTs degradation is slower than BuTs degradation in oxic porewaters. - Abstract: This paper provides a comprehensive study of the persistence of butyltins and phenyltins in contaminated marine sediments and presents the first data on their degradation potentials in porewaters. The study’s aim was to explain the different degradation efficiencies of organotin compounds (OTC) in contaminated sediments. The transformation processes of OTC in sediments and porewaters were investigated in a field experiment using species-specific, isotopically enriched organotin tracers. Sediment characteristics (organic carbon content and grain size) were determined to elucidate their influence on the degradation processes. The results of this study strongly suggest that a limiting step in OTC degradation in marine sediments is their desorption into porewaters because their degradation in porewaters occurs notably fast with half-lives of 9.2 days for tributyltin (TBT) in oxic porewaters and 2.9 ± 0.1 and 9.1 ± 0.9 days for dibutyltin (DBT) in oxic and anoxic porewaters, respectively. By controlling the desorption process, organic matter influences the TBT degradation efficiency and consequently defines its persistence in contaminated sediments, which thus increases in sediments rich in organic matter.

Organotin persistence in contaminated marine sediments and porewaters: In situ degradation study using species-specific stable isotopic tracers

International Nuclear Information System (INIS)

Furdek, Martina; Mikac, Nevenka; Bueno, Maite; Tessier, Emmanuel; Cavalheiro, Joana; Monperrus, Mathilde

2016-01-01

Highlights: • Limiting step in OTC degradation in sediments is their desorption into porewater. • TBT persistence in contaminated sediments increases in sediments rich in organic matter. • DBT does not accumulate in sediments as degradation product of TBT. • TBT and DBT degradation in porewaters occurs with half-lives from 2.9 to 9.2 days. • PhTs degradation is slower than BuTs degradation in oxic porewaters. - Abstract: This paper provides a comprehensive study of the persistence of butyltins and phenyltins in contaminated marine sediments and presents the first data on their degradation potentials in porewaters. The study’s aim was to explain the different degradation efficiencies of organotin compounds (OTC) in contaminated sediments. The transformation processes of OTC in sediments and porewaters were investigated in a field experiment using species-specific, isotopically enriched organotin tracers. Sediment characteristics (organic carbon content and grain size) were determined to elucidate their influence on the degradation processes. The results of this study strongly suggest that a limiting step in OTC degradation in marine sediments is their desorption into porewaters because their degradation in porewaters occurs notably fast with half-lives of 9.2 days for tributyltin (TBT) in oxic porewaters and 2.9 ± 0.1 and 9.1 ± 0.9 days for dibutyltin (DBT) in oxic and anoxic porewaters, respectively. By controlling the desorption process, organic matter influences the TBT degradation efficiency and consequently defines its persistence in contaminated sediments, which thus increases in sediments rich in organic matter.

Hantzsch reaction and quinoxaline synthesis using 1-methyl-3-(2-(sulfooxyethyl-1H-imidazol-3-ium chloride as a new, efficient and BrØnsted acidic ionic liquid catalyst

Directory of Open Access Journals (Sweden)

Sami Sajjadifar

2013-10-01

Full Text Available In this work, the efficiency, generality and applicability of new BrØnsted acidic ionic liquid (BAIL 1-methyl-3-(2-(sulfooxyethyl-1H-imidazol-3-ium chloride {[Msei]Cl} as heterogeneous and green catalyst for organic transformations are studied. Herein, the following one-pot multi-component reactions in the presence of [Msei]Cl are investigated: (i the synthesis of quinoxaline derivatives from the reaction of phenylenediamines and 1,2-diketones in EtOH under mild conditions (room temperature, (ii the preparation of 1,4-dihydropyridines from one-pot multi component condensation of 1,3-dicarbonyl compounds, NH4OAcand aldehydes under solvent-free conditions at moderate temperature (90 °C. High yields, relatively short reaction times, efficiency, generality, clean process, simple methodology, low cost, easy work-up, ease of preparation and regeneration of the catalyst and green conditions (in the synthesis of the quinoxaline derivatives are advantages of the application of [Mesi]Cl as catalyst in the above organic reactions.

Constructing organic D-A-π-A-featured sensitizers with a quinoxaline unit for high-efficiency solar cells: the effect of an auxiliary acceptor on the absorption and the energy level alignment.

Science.gov (United States)

Pei, Kai; Wu, Yongzhen; Wu, Wenjun; Zhang, Qiong; Chen, Baoqin; Tian, He; Zhu, Weihong

2012-06-25

Four organic D-A-π-A-featured sensitizers (TQ1, TQ2, IQ1, and IQ2) have been studied for high-efficiency dye-sensitized solar cells (DSSCs). We employed an indoline or a triphenylamine unit as the donor, cyanoacetic acid as the acceptor/anchor, and a thiophene moiety as the conjugation bridge. Additionally, an electron-withdrawing quinoxaline unit was incorporated between the donor and the π-conjugation unit. These sensitizers show an additional absorption band covering the broad visible range in solution. The contribution from the incorporated quinoxaline was investigated theoretically by using DFT and time-dependent DFT. The incorporated low-band-gap quinoxaline unit as an auxiliary acceptor has several merits, such as decreasing the band gap, optimizing the energy levels, and realizing a facile structural modification on several positions in the quinoxaline unit. As demonstrated, the observed additional absorption band is favorable to the photon-to-electron conversion because it corresponds to the efficient electron transitions to the LUMO orbital. Electrochemical impedance spectroscopy (EIS) Bode plots reveal that the replacement of a methoxy group with an octyloxy group can increase the injection electron lifetime by a factor of 2.4. IQ2 and TQ2 can perform well without any co-adsorbent, successfully suppress the charge recombination from TiO(2) conduction band to I(3)(-) in the electrolyte, and enhance the electron lifetime, resulting in a decreased dark current and enhanced open circuit voltage (V(oc)) values. By using a liquid electrolyte, DSSCs based on dye IQ2 exhibited a broad incident photon-to-current conversion efficiency (IPCE) action spectrum and high efficiency (η=8.50 %) with a short circuit current density (J(sc)) of 15.65 mA cm(-2), a V(oc) value of 776 mV, a fill factor (FF) of 0.70 under AM 1.5 illumination (100 mW cm(-2)). Moreover, the overall efficiency remained at 97% of the initial value after 1000 h of visible

Quinoxaline-, dopamine-, and amino acid-derived metabolites from the edible insect Protaetia brevitarsis seulensis.

Science.gov (United States)

Lee, JungIn; Hwang, In Hyun; Kim, Jang Hoon; Kim, Mi-Ae; Hwang, Jae Sam; Kim, Young Ho; Na, MinKyun

2017-09-01

Edible insects have been reported to produce metabolites showing various pharmacological activities, recently emerging as rich sources of health functional food. In particular, the larvae of Protaetia brevitarsis seulensis (Kolbe) have been used as traditional Korean medicines for treating diverse diseases, such as breast cancer, inflammatory disease, hepatic cancer, liver cirrhosis, and hepatitis. However, only few chemical investigations were reported on the insect larvae. Therefore, the aim of this study was to discover and identify biologically active chemical components of the larvae of P. brevitarsis seulensis. As a result, a quinoxaline-derived alkaloid (1) was isolated, which was not reported previously from natural sources. In addition, other related compounds (2, 4-10, 15, 16) were also encountered for the first time from the larvae. The structures of all the isolated compounds were established mainly by analysis of HRESIMS, NMR, and electronic circular dichroism data. Compound 5 exhibited inhibition of tyrosinase with IC 50 value of 44.8 µM.

Species analysis of organotin compounds to investigate their pathway in the aquatic environment; Speziesanalytik von zinnorganischen Verbindungen zur Aufklaerung ihrer Biopfade in der aquatischen Umwelt

Energy Technology Data Exchange (ETDEWEB)

Kuballa, J. [GKSS-Forschungszentrum Geesthacht GmbH (Germany). Inst. fuer Physikalische und Chemische Analytik

1997-12-31

In this thesis the sorption, transport and accumulation behaviour of organotin compounds in the aquatic environment was investigated in order to assess and evaluate the toxic potential. In situ derivatization with sodiumthetraethylborate and extraction with hexane were employed to isolate the tin species from the matrices. Separation and quantification were performed using on-line gas chromatorgraphy coupled with atomic absorption spectrometry. The main conclusion of this work is that organotin compounds show a characteristic bioaccumulation behaviour, which is influenced by the solubility of the species in combination with lipophily and sorption on particles, humic substances and biofilms. (orig.) [Deutsch] In der vorliegenden Arbeit wurden das Sorptions-, Transport- und Akkumulationsverhalten von Organozinnverbindungen in der aquatischen Umwelt untersucht mit dem Ziel einer Abschaetzung und Bewertung des oekologischen Schaedigungspotentials. Die Isolierung der Zinnspezies aus den Matrizes gelang mit der In-Situ-Derivatisierung mit Natriumtetraethylborat und Extraktion mit Hexan. Die Trennung und Quantifizierung erfolgte mittels Gaschromatographie on-line gekoppelt mit Atomabsorptionsspektrometrie. Die wichtigste Aussage dieser Arbeit ist, dass zinnorganische Verbindungen ein charakteristisches Bioakkumulationsverhalten aufweisen, das wesentlich von der Wasserloeslichkeit der Spezies in Verbindung mit der Lipophilie und der Bindung an Partikel, Huminstoffe und Biofilme beeinflusst wird. (orig.)

Species analysis of organotin compounds to investigate their pathway in the aquatic environment; Speziesanalytik von zinnorganischen Verbindungen zur Aufklaerung ihrer Biopfade in der aquatischen Umwelt

Energy Technology Data Exchange (ETDEWEB)

Kuballa, J [GKSS-Forschungszentrum Geesthacht GmbH (Germany). Inst. fuer Physikalische und Chemische Analytik

1998-12-31

In this thesis the sorption, transport and accumulation behaviour of organotin compounds in the aquatic environment was investigated in order to assess and evaluate the toxic potential. In situ derivatization with sodiumthetraethylborate and extraction with hexane were employed to isolate the tin species from the matrices. Separation and quantification were performed using on-line gas chromatorgraphy coupled with atomic absorption spectrometry. The main conclusion of this work is that organotin compounds show a characteristic bioaccumulation behaviour, which is influenced by the solubility of the species in combination with lipophily and sorption on particles, humic substances and biofilms. (orig.) [Deutsch] In der vorliegenden Arbeit wurden das Sorptions-, Transport- und Akkumulationsverhalten von Organozinnverbindungen in der aquatischen Umwelt untersucht mit dem Ziel einer Abschaetzung und Bewertung des oekologischen Schaedigungspotentials. Die Isolierung der Zinnspezies aus den Matrizes gelang mit der In-Situ-Derivatisierung mit Natriumtetraethylborat und Extraktion mit Hexan. Die Trennung und Quantifizierung erfolgte mittels Gaschromatographie on-line gekoppelt mit Atomabsorptionsspektrometrie. Die wichtigste Aussage dieser Arbeit ist, dass zinnorganische Verbindungen ein charakteristisches Bioakkumulationsverhalten aufweisen, das wesentlich von der Wasserloeslichkeit der Spezies in Verbindung mit der Lipophilie und der Bindung an Partikel, Huminstoffe und Biofilme beeinflusst wird. (orig.)

Effects of Organotins on Crustaceans: Update and Perspectives

Science.gov (United States)

Vogt, Éverton L.; Model, Jorge F. A.; Vinagre, Anapaula S.

2018-01-01

Organotins (OTs) are considered some of the most toxic chemicals introduced into aquatic environments by anthropogenic activities. They are widely used for agricultural and industrial purposes and as antifouling additives on boat hull’s paints. Even though the use of OTs was banned in 2008, elevated levels of OTs can still be detected in aquatic environments. OTs’ deleterious effects upon wildlife and experimental animals are well documented and include endocrine disruption, immunotoxicity, neurotoxicity, genotoxicity, and metabolic dysfunction. Crustaceans are key members of zooplankton and benthic communities and have vital roles in food chains, so the endocrine-disrupting effects of tributyltin (TBT) on crustaceans can affect other organisms. TBT can disrupt carbohydrate and lipid homeostasis of crustaceans by interacting with retinoid X receptor (RXR) and crustacean hyperglycemic hormone (CHH) signaling. Moreover, it can also interact with other nuclear receptors, disrupting methyl farnesoate and ecdysteroid signaling, thereby altering growth and sexual maturity, respectively. This compound also interferes in cytochrome P450 system disrupting steroid synthesis and reproduction. Crustaceans are also important fisheries worldwide, and its consumption can pose risks to human health. However, some questions remain unanswered. This mini review aims to update information about the effects of OTs on the metabolism, growth, and reproduction of crustaceans; to compare with known effects in mammals; and to point aspects that still needs to be addressed in future studies. Since both macrocrustaceans and microcrustaceans are good models to study the effects of sublethal TBT contamination, novel studies should be developed using multibiomarkers and omics technology. PMID:29535684

Effects of Organotins on Crustaceans: Update and Perspectives

Directory of Open Access Journals (Sweden)

Éverton L. Vogt

2018-02-01

Full Text Available Organotins (OTs are considered some of the most toxic chemicals introduced into aquatic environments by anthropogenic activities. They are widely used for agricultural and industrial purposes and as antifouling additives on boat hull’s paints. Even though the use of OTs was banned in 2008, elevated levels of OTs can still be detected in aquatic environments. OTs’ deleterious effects upon wildlife and experimental animals are well documented and include endocrine disruption, immunotoxicity, neurotoxicity, genotoxicity, and metabolic dysfunction. Crustaceans are key members of zooplankton and benthic communities and have vital roles in food chains, so the endocrine-disrupting effects of tributyltin (TBT on crustaceans can affect other organisms. TBT can disrupt carbohydrate and lipid homeostasis of crustaceans by interacting with retinoid X receptor (RXR and crustacean hyperglycemic hormone (CHH signaling. Moreover, it can also interact with other nuclear receptors, disrupting methyl farnesoate and ecdysteroid signaling, thereby altering growth and sexual maturity, respectively. This compound also interferes in cytochrome P450 system disrupting steroid synthesis and reproduction. Crustaceans are also important fisheries worldwide, and its consumption can pose risks to human health. However, some questions remain unanswered. This mini review aims to update information about the effects of OTs on the metabolism, growth, and reproduction of crustaceans; to compare with known effects in mammals; and to point aspects that still needs to be addressed in future studies. Since both macrocrustaceans and microcrustaceans are good models to study the effects of sublethal TBT contamination, novel studies should be developed using multibiomarkers and omics technology.

Quinoxaline 1, 4-di-N-oxides: Biological activities and mechanisms of actions

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Guyue eCheng

2016-03-01

Full Text Available Quinoxaline 1, 4-di-N-oxides (QdNOs have manifold biological properties, including antimicrobial, antitumoral, antitrypanosomal and antiinflammatory/antioxidant activities. These diverse activities endow them broad applications and prospects in human and veterinary medicines. As QdNOs arouse widespread interest, the evaluation of their medicinal chemistry is still in progress. In the meantime, adverse effects have been reported in some of the QdNO derivatives. For example, genotoxicity and bacterial resistance have been found in QdNO antibacterial growth promoters, conferring urgent need for discovery of new QdNO drugs. However, the modes of actions of QdNOs are not fully understood, hindering the development and innovation of these promising compounds. Here, QdNOs are categorized based on the activities and usages, among which the antimicrobial activities are consist of antibacterial, antimycobacterial and anticandida activities, and the antiprotozoal activities include antitrypanosomal, antimalarial, antitrichomonas and antiamoebic activities. The structure-activity relationship and the mode of actions of each type of activity of QdNOs are summarized, and the toxicity and the underlying mechanisms are also discussed, providing insight for the future research and development of these fascinating compounds.

Cleavage of Sn-C and S-C(alkyl) bonds on an organotin scaffold: synthesis and characterization of a novel organotin-sulfite cluster bearing methyltin- and dimethyltin fragments.

Science.gov (United States)

Shankar, Ravi; Jain, Archana; Kociok-Köhn, Gabriele; Mahon, Mary F; Molloy, Kieran C

2010-05-17

Hydrolysis of the mixed-ligand dimethyltin(ethoxy)ethanesulfonate, [Me(2)Sn(OEt)(OSO(2)Et)](n) (1a) in moist hexane proceeds via disproportionation and partial cleavage of Sn-C and S-C bonds to afford a novel oxo-/hydroxo- organotin cluster of the composition [(Me(2)Sn)(MeSn)(4)(OSO(2)Et)(2)(OH)(4)(O)(2)(SO(3))(2)] (1) bearing both mono- and dimethyltin fragments and in situ generated sulfite (SO(3)(2-)) anion in the structural framework. On the other hand, similar reactions with analogous mixed ligand diorganotin precursors, [R(2)Sn(OR(1))(OSO(2)R(1))](n) (R = n-Bu, R(1) = Et (2a); R = Et, R(1) = Me (3a)), result in the formation of tetranuclear diorganotin clusters, [{(n-Bu(2)Sn)(2)(OH)(OSO(2)Et)}O](2) (2) and [(Et(2)Sn)(4)(OH)(O)(2)(OSO(2)Me)(3)] (3), respectively. The activation of the Sn-C or S-C bond is not observed in these cases. These findings provide a preliminary insight into the unusual reactivity of 1a under hydrolytic conditions.

Les peintures marines antisalissures à base de polymères organostanniques Antifouling Marine Paints Containing Organo-Tin Polymers

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Dawans F.

2006-11-01

Full Text Available Le dépôt des salissures marines sur les ouvrages immergés est influencé par plusieurs facteurs et il entraîne des conséquences néfastes, en particulier pour la maintenance des supports de plates-formes de production du pétrole en mer et pour la consommation d'énergie requise pour la propulsion des navires. Divers moyens de lutte antisalissure ont été envisagés parmi lesquels les peintures marines antisalissures occupent une place de choix. Ces peintures contiennent, en général, un composé métallique toxique envers les organismes marins d'origine animale ou végétale et différents mécanismes d'action ont été proposés. Les dérivés organostanniques sont des agents biocides très efficaces et lorsqu'ils sont liés chimiquement sur un polymère, en particulier sous forme de greffons, on obtient un contrôle amélioré de leur lixiviation dans la phase aqueuse et par conséquent la durée de vie du revêtement antisalissure est prolongée. La synthèse de polymères comportant un cation organostannique toxique peut être effectuée, soit par la polymérisation ou la copolymérisation de monomères insaturés organostanniques, soit par la réaction chimique de composés organostanniques avec un substrat polymère comportant des groupes fonctionnels appropriés. Les avantages et les inconvénients de diverses formulations de peintures à base de dérivés organostanniques sont discutés. Marine fouling deposits on submerged structures are influenced by several factors and bring about harmful consequences, especially with regard to offshore oil-production platform structures and for the energy consumption required for ship propulsion. Various antifouling methods have been considered, including antifouling marine coatings in particular. Such paints generally contain a metallic compound which is toxic with regard to marine organisms of animal or vegetable origin, and various action mechanisms have been proposed. Organo-tin

A novel UV-photolysis approach with acetone and isopropyl alcohol for the rapid determination of fluoride in organofluorine-containing drugs by spectrophotometry.

Science.gov (United States)

Mullapudi, Venkata Balarama Krishna; Dheram, Karunasagar

2018-01-01

A UV photolysis decomposition (UVPD) method for the determination of fluoride in fluorine containing pharmaceuticals by spectrophotometry is reported. It is based on the use of high intensity UV-irradiation in the presence of a digesting solution comprising a mixture of acetone and isopropanol. For the optimization of the UVPD procedure, three bulk drugs (levofloxacin, nebivolol and efavirenz) were chosen as representatives of three diverse compounds containing a single fluorine atom, two fluorine atoms, and trifluoromethyl groups respectively. Operational conditions of the UVPD method, such as concentration and volume of reagents (acetone and isopropyl alcohol), and UV irradiation time (1-6 minutes) were optimized. The efficiency of digestion was evaluated by the determination of fluoride in sample digests. Using the developed method, it was possible for complete conversion of the organofluoride to free fluoride ion for its subsequent determination by spectrophotometry based on bleaching of Zr-xylenol orange-color complex. Quantitative recovery (>98%) of the fluorine in the drug samples could be achieved using a mixture of 2% acetone + 2% isopropyl alcohol + 0.003% Na 2 CO 3 in just 5 minutes of UV irradiation, which can be considered an important aspect considering the difficulties involved in the cleavage of the CF bond. Accuracy was evaluated by comparison of results obtained by the UVPD method with the values estimated using formula weight of the compound and no statistical difference was observed between the results. Therefore, the proposed method is suitable for application in routine analysis of fluoride in organofluorine-containing drugs. Copyright © 2016. Published by Elsevier B.V.

Potential of Nassarius nitidus for monitoring organotin pollution in the lagoon of Bizerta (northern Tunisia)

Institute of Scientific and Technical Information of China (English)

Youssef Lahbib; Sami Abidli; Pablo Rodrfguez González; José Ignacio Garcfa Alonso; Najoua Trigui-El Menif

2011-01-01

Imposex and butyltin burden were assessed in Nassarius nitidus,Bolinus brandaris and Hexaplex trunculus collected at five stations in the Bizerta lagoon.Biological analysis showed that imposex followed type (a) in N.nitidus (distal evolution),against type (d) in the two muricids (proximal evolution).Imposex indices were higher in sites located nearby sources of tributyltin and N.nitidus was the least affected species of the five sites,followed by B.brandaris and H.trunculus.Butyltin analysis showed lower accumulation in N.nitidus followed by H.trunculus and B.brandaris.This study has allowed the gathering of data on imposex in a snail studied for the first time in Tunisia (N.nitidus).It suggests the possibility of using such snail as a complementary species for organotin monitoring programs in the Mediterranean and further confirmed that H.trunculus is the most suitable species for such investigations.

Donor-acceptor-donor thienyl/bithienyl-benzothiadiazole/quinoxaline model oligomers: experimental and theoretical studies.

Science.gov (United States)

Pina, João; de Melo, J Seixas; Breusov, D; Scherf, Ullrich

2013-09-28

A comprehensive spectral and photophysical investigation of four donor-acceptor-donor (DAD) oligomers consisting of electron-deficient 2,1,3-benzothiadiazole or quinoxaline moieties linked to electron-rich thienyl or bithienyl units has been undertaken. Additionally, a bis(dithienyl) substituted naphthalene was also investigated. The D-A-D nature of these oligomers resulted in the presence of an intramolecular charge transfer (ICT) state, which was further substantiated by solvatochromism studies (analysis with the Lippert-Mataga formalism). Hereby, significant differences have been obtained for the fluorescence quantum yields of the oligomers in the non-polar solvent methylcyclohexane vs. the polar ethanol. The study was further complemented with the determination of the optimized ground-state molecular geometries for the oligomers together with the prediction of the lowest vertical one-electron excitation energy and the relevant molecular orbital contours using DFT calculations. The electronic transitions show a clear HOMO to LUMO charge-transfer character. In contrast to the thiophene oligomers (the oligothiophenes with n = 1-7), where the intersystem crossing (ISC) yield decreases with n, the studied DAD oligomers were found to show an increase in the ISC efficiency with the number of (donor) thienyl units.

Synthesis and Positive Inotropic Activity of [1,2,4]Triazolo[4,3-a] Quinoxaline Derivatives Bearing Substituted Benzylpiperazine and Benzoylpiperazine Moieties

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Xue-Kun Liu

2017-02-01

Full Text Available In an attempt to search for more potent positive inotropic agents, two series of [1,2,4]triazolo[4,3-a] quinoxaline derivatives bearing substituted benzylpiperazine and benzoylpiperazine moieties were synthesized and their positive inotropic activities evaluated by measuring left atrial stroke volume in isolated rabbit heart preparations. Several compounds showed favorable activities compared with the standard drug, milrinone. Compound 6c was the most potent agent, with an increased stroke volume of 12.53% ± 0.30% (milrinone: 2.46% ± 0.07% at 3 × 10−5 M. The chronotropic effects of compounds having considerable inotropic effects were also evaluated.

Synthesis of 9H-indeno [1, 2-b] pyrazine and 11H-indeno [1, 2-b] quinoxaline derivatives in one-step reaction from 2-bromo-4-chloro-1-indanone

OpenAIRE

Jasouri, S.; Khalafy, J.; Badali, M.; Prager, R.H.

2011-01-01

The reaction of 2-bromo-4-chloro-1-indanone with 2,3-diaminomaleonitrile, benzene-1,2-diamine and 4-methylbenzene-1,2-diamine in glacial acetic acid gave 8-chloro-9H-indeno[1,2-b]pyrazine-2,3-dicarbonitrile, 1-chloro-11H-indeno[1,2-b]quinoxa-line and 1-chloro-7-methyl-11H-indeno[1,2-b]quinoxaline, respectively, in good yield.

Synthesis and anticonvulsant activity of Schiff’s bases of 3-{[2-({(E-[(substituted phenyl] methylidene} amino ethyl] amino} quinoxalin-2(1H-one

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Ratnadeep V. Ghadage

2011-06-01

Full Text Available In an effort to develop potent anticonvulsant agents, we have synthesized some novel schiff’s bases of 3-{[2-({(E-[substituted phenyl] methylidene} amino ethyl] amino} quinoxalin-2(1H-one and evaluated for in vivo anticonvulsant activity. All the compounds were characterized by IR, 1H NMR data. This activity was carried out on pentylenetetrazole-induced seizure model. Compounds (IIIb and (IIIc Showed maximum time for straub tail and clonic convulsions. That means they possess good activity compared with standard. Animals treated with compounds (IIIb and (IIIe were recovered from this activity.

Organotins in Neuronal Damage, Brain Function, and Behavior: A Short Review

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Igor Ferraz da Silva

2018-01-01

Full Text Available The consequences of exposure to environmental contaminants have shown significant effects on brain function and behavior in different experimental models. The endocrine-disrupting chemicals (EDC present various classes of pollutants with potential neurotoxic actions, such as organotins (OTs. OTs have received special attention due to their toxic effects on the central nervous system, leading to abnormal mammalian neuroendocrine axis function. OTs are organometallic pollutants with a tin atom bound to one or more carbon atoms. OT exposure may occur through the food chain and/or contaminated water, since they have multiple applications in industry and agriculture. In addition, OTs have been used with few legal restrictions in the last decades, despite being highly toxic. In addition to their action as EDC, OTs can also cross the blood–brain barrier and show relevant neurotoxic effects, as observed in several animal model studies specifically involving the development of neurodegenerative processes, neuroinflammation, and oxidative stress. Thus, the aim of this short review is to summarize the toxic effects of the most common OT compounds, such as trimethyltin, tributyltin, triethyltin, and triphenyltin, on the brain with a focus on neuronal damage as a result of oxidative stress and neuroinflammation. We also aim to present evidence for the disruption of behavioral functions, neurotransmitters, and neuroendocrine pathways caused by OTs.

Overview of the Pathophysiological Implications of Organotins on the Endocrine System.

Science.gov (United States)

Marques, Vinicius Bermond; Faria, Rodrigo Alves; Dos Santos, Leonardo

2018-01-01

Organotins (OTs) are pollutants that are used widely by industry as disinfectants, pesticides, and most frequently as biocides in antifouling paints. This mini-review presents the main evidences from the literature about morphophysiological changes induced by OTs in the mammal endocrine system, focusing on the metabolism and reproductive control. Similar to other toxic compounds, the main effects with potential health risks to humans and experimental animals are not only related to dose and time of exposure but also to age, gender, and tissue/cell exposed. Regarding the underlying mechanisms, current literature indicates that OTs can directly damage endocrine glands, as well as interfere with neurohormonal control of endocrine function (i.e., in the hypothalamic-pituitary axis), altering hormone synthesis and/or bioavailability or activity of hormone receptors in the target cells. Importantly, OTs induces biochemical and morphological changes in gonads, abnormal steroidogenesis, both associated with reproductive dysfunctions such as irregular estrous cyclicity in female or spermatogenic disorders in male animals. Additionally, due to their role on endocrine systems predisposing to obesity, OTs are also included in the metabolism disrupting chemical hypothesis, either by central (e.g., accurate nucleus and lateral hypothalamus) or peripheral (e.g., adipose tissue) mechanisms. Thus, OTs should be indeed considered a major endocrine disruptor, being indispensable to understand the main toxic effects on the different tissues and its causative role for endocrine, metabolic, and reproductive dysfunctions observed.

Trypanocidal Activity of Quinoxaline 1,4 Di-N-oxide Derivatives as Trypanothione Reductase Inhibitors

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Karla Fabiola Chacón-Vargas

2017-02-01

Full Text Available Chagas disease or American trypanosomiasis is a worldwide public health problem. In this work, we evaluated 26 new propyl and isopropyl quinoxaline-7-carboxylate 1,4-di-N-oxide derivatives as potential trypanocidal agents. Additionally, molecular docking and enzymatic assays on trypanothione reductase (TR were performed to provide a basis for their potential mechanism of action. Seven compounds showed better trypanocidal activity on epimastigotes than the reference drugs, and only four displayed activity on trypomastigotes; T-085 was the lead compound with an IC50 = 59.9 and 73.02 µM on NINOA and INC-5 strain, respectively. An in silico analysis proposed compound T-085 as a potential TR inhibitor with better affinity than the natural substrate. Enzymatic analysis revealed that T-085 inhibits parasite TR non-competitively. Compound T-085 carries a carbonyl, a CF3, and an isopropyl carboxylate group at 2-, 3- and 7-position, respectively. These results suggest the chemical structure of this compound as a good starting point for the design and synthesis of novel trypanocidal derivatives with higher TR inhibitory potency and lower toxicity.

New mono-organotin (IV) dithiocarbamate complexes

Energy Technology Data Exchange (ETDEWEB)

Muthalib, Amirah Faizah Abdul; Baba, Ibrahim [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi (Malaysia)

2014-09-03

Eighteen new mono-organotin dithiocarbamate compounds derived each nine from methyltin(IV) and phenyltin(IV) reacted using in-situ method with various type of N-dialkylamine together with carbon disulphide with the ratio of 1:3:3. Elemental and gravimetric analysis showed that the general formula of these compounds were RSnCl[S{sub 2}CNR′R″]{sub 2} (R= Ph, CH{sub 3}, R′ = CH{sub 3}, C{sub 2}H{sub 5}, C{sub 7}H{sub 7} and R″ = C{sub 2}H{sub 5}, C{sub 6}H{sub 11}, iC{sub 3}H{sub 7}, C{sub 7}H{sub 7}). These compounds had been characterized by infrared spectroscopy, ultraviolet spectroscopy, {sup 1}H, {sup 13}C NMR spectroscopy and single crystal X-ray crystallography. The infrared spectra of these compounds showed three important peaks indicating the formation of dithiocarbamate compounds, ν(CN), ν(CS) and ν(Sn-S) band which present in the region of 1444–1519, 954–1098 and 318–349 cm{sup −1} respectively. The ultraviolet-visible spectra showed an absorption band for the π - π* transition of NCS group in the range of 253 – 259 nm due to the intramolecular charge transfer of the ligand. The {sup 13}C NMR spectra showed an important shift for δ(N{sup 13}CS{sub 2}) in the range of 196.8 – 201.9 ppm.. Single crystal X-ray diffraction studies showed three new structures with the general formula of PhSnCl[S{sub 2}CN(Et)(i−Pr)]{sub 2}, MeSnCl[S{sub 2}CN(Me)(Cy)]{sub 2} and MeSnCl[S{sub 2}CN(i−Pr)(CH{sub 2}Ph)]{sub 2}. All structures having a distorted octahedral geometry set by CClS{sub 4} donor atom from the two

Comparison of organotin accumulation on the white-spotted charr Salvelinus leucomaenis between sea-run and freshwater-resident types

Science.gov (United States)

Ohji, Madoka; Harino, Hiroya; Arai, Takaomi

2011-01-01

To examine the accumulation pattern of organotin compounds (OTs) in relation to the migration of diadromous fish, tributyltin (TBT) and triphenyltin (TPT) compounds and their derivatives were determined in the muscle tissue of both sea-run (anadromous) and freshwater-resident (nonanadromous) types of the white-spotted charr Salvelinus leucomaenis. There were generally no significant correlations between the TBT and TPT accumulation and various biological characteristics such as the total length (TL), body weight (BW), age and sex in S. leucomaenis. It is noteworthy that the TBT and TPT concentrations in sea-run white-spotted charr were significantly higher than in freshwater-resident individuals, although they are intraspecies. These results suggest that the sea-run S. leucomaenis has a higher ecological risk of TBT and TPT exposure than the freshwater-residents during their life history.

Overview of the Pathophysiological Implications of Organotins on the Endocrine System

Directory of Open Access Journals (Sweden)

Vinicius Bermond Marques

2018-03-01

Full Text Available Organotins (OTs are pollutants that are used widely by industry as disinfectants, pesticides, and most frequently as biocides in antifouling paints. This mini-review presents the main evidences from the literature about morphophysiological changes induced by OTs in the mammal endocrine system, focusing on the metabolism and reproductive control. Similar to other toxic compounds, the main effects with potential health risks to humans and experimental animals are not only related to dose and time of exposure but also to age, gender, and tissue/cell exposed. Regarding the underlying mechanisms, current literature indicates that OTs can directly damage endocrine glands, as well as interfere with neurohormonal control of endocrine function (i.e., in the hypothalamic–pituitary axis, altering hormone synthesis and/or bioavailability or activity of hormone receptors in the target cells. Importantly, OTs induces biochemical and morphological changes in gonads, abnormal steroidogenesis, both associated with reproductive dysfunctions such as irregular estrous cyclicity in female or spermatogenic disorders in male animals. Additionally, due to their role on endocrine systems predisposing to obesity, OTs are also included in the metabolism disrupting chemical hypothesis, either by central (e.g., accurate nucleus and lateral hypothalamus or peripheral (e.g., adipose tissue mechanisms. Thus, OTs should be indeed considered a major endocrine disruptor, being indispensable to understand the main toxic effects on the different tissues and its causative role for endocrine, metabolic, and reproductive dysfunctions observed.

Overview of the Pathophysiological Implications of Organotins on the Endocrine System

Science.gov (United States)

Marques, Vinicius Bermond; Faria, Rodrigo Alves; Dos Santos, Leonardo

2018-01-01

Organotins (OTs) are pollutants that are used widely by industry as disinfectants, pesticides, and most frequently as biocides in antifouling paints. This mini-review presents the main evidences from the literature about morphophysiological changes induced by OTs in the mammal endocrine system, focusing on the metabolism and reproductive control. Similar to other toxic compounds, the main effects with potential health risks to humans and experimental animals are not only related to dose and time of exposure but also to age, gender, and tissue/cell exposed. Regarding the underlying mechanisms, current literature indicates that OTs can directly damage endocrine glands, as well as interfere with neurohormonal control of endocrine function (i.e., in the hypothalamic–pituitary axis), altering hormone synthesis and/or bioavailability or activity of hormone receptors in the target cells. Importantly, OTs induces biochemical and morphological changes in gonads, abnormal steroidogenesis, both associated with reproductive dysfunctions such as irregular estrous cyclicity in female or spermatogenic disorders in male animals. Additionally, due to their role on endocrine systems predisposing to obesity, OTs are also included in the metabolism disrupting chemical hypothesis, either by central (e.g., accurate nucleus and lateral hypothalamus) or peripheral (e.g., adipose tissue) mechanisms. Thus, OTs should be indeed considered a major endocrine disruptor, being indispensable to understand the main toxic effects on the different tissues and its causative role for endocrine, metabolic, and reproductive dysfunctions observed. PMID:29615977

Synthesis, crystal structure and biological activity of the Schiff base organotin(IV) complexes based on salicylaldehyde-o-aminophenol

Science.gov (United States)

Tan, Yu-Xing; Zhang, Zhi-Jian; Liu, Yang; Yu, Jiang-Xi; Zhu, Xiao-Ming; Kuang, Dai-Zhi; Jiang, Wu-Jiu

2017-12-01

Schiff base organotin(IV) complexes C1 ∼ C5b have been synthesized via the reaction of the substituted salicylaldehyde-o-aminophenol Schiff base ligands (L1 ∼ L3) with the dibenzyltin dichloride, n-butyltin trichloride or dibutyltin oxide, respectively. The complexes have been characterized by IR, UV-Vis, 1H NMR, 13C NMR spectra, elemental analysis and the crystal structures have been determined by X-ray diffraction. The anticancer activity of the Schiff base ligand and complexes C1 ∼ C5b against five species of cancer cell which are Hela, MCF7, HepG2, Colo205, NCIsbnd H460 were tested respectively, the tests showed that C1 ∼ C5b exhibited significant anticancer activity for the cancer cells in comparison with the ligand, and the activity was greater than carboplatin.

Synthesis, characterization and biocidal activity of new organotin complexes of 2-(3-oxocyclohex-1-enyl)benzoic acid.

Science.gov (United States)

Vieira, Flaviana T; de Lima, Geraldo M; Maia, José R da S; Speziali, Nivaldo L; Ardisson, José D; Rodrigues, Leonardo; Correa, Ary; Romero, Oscar B

2010-03-01

The reaction of 1,3-cyclohexadione with 2-aminobenzoic acid has produced the 2-(3-oxocyclohex-1-enyl)benzoic acid (HOBz). Subsequent reactions of the ligand with organotin chlorides led to [Me(2)Sn(OBz)O](2) (1), [Bu(2)Sn(OBz)O](2) (2), [Ph(2)Sn(OBz)O](2) (3), [Me(3)Sn(OBz)] (4), [Bu(3)Sn(OBz)] (5) and [Ph(3)Sn(OBz)] (6). All complexes have been fully characterized. In addition the structure of complexes (2) and (4) have been authenticated by X-ray crystallography. The biological activity of all derivatives has been screened against Cryptococcus neoformans and Candida albicans. In addition we have performed toxicological testes employing human kidney cell. The complexes (3), (5) and (6) displayed the best values of inhibition of the fungus growing, superior to ketoconazole. Compound (5) presented promising results in view of the antifungal and cytotoxicity assays. Copyright (c) 2009 Elsevier Masson SAS. All rights reserved.

Synthesis of quinoxaline derivatives via condensation of aryl-1,2-diamines with 1,2-diketones using (NH4)6 Mo7 O24 . 4 H2 O as an efficient, mild and reusable catalyst

International Nuclear Information System (INIS)

Hasaninejad, A.; Zare, A.; Mohammadizadeh, M. R.; Karami, Z.

2009-01-01

Ammonium heptamolybdate tetrahydrate [(NH 4 ) 6 Mo 7 O 24. 4H 2 O] efficiently catalyzes the condensation of aryl-1,2-diamines with l,2-diketones in EtOH/H 2 O as a green media at room temperature to afford quinoxaline derivatives as biologically interesting compounds. Ease of recycling of the catalyst is one of the most advantages of the proposed method

Synthetic biology approaches to fluorinated polyketides.

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Thuronyi, Benjamin W; Chang, Michelle C Y

2015-03-17

The catalytic diversity of living systems offers a broad range of opportunities for developing new methods to produce small molecule targets such as fuels, materials, and pharmaceuticals. In addition to providing cost-effective and renewable methods for large-scale commercial processes, the exploration of the unusual chemical phenotypes found in living organisms can also enable the expansion of chemical space for discovery of novel function by combining orthogonal attributes from both synthetic and biological chemistry. In this context, we have focused on the development of new fluorine chemistry using synthetic biology approaches. While fluorine has become an important feature in compounds of synthetic origin, the scope of biological fluorine chemistry in living systems is limited, with fewer than 20 organofluorine natural products identified to date. In order to expand the diversity of biosynthetically accessible organofluorines, we have begun to develop methods for the site-selective introduction of fluorine into complex natural products by engineering biosynthetic machinery to incorporate fluorinated building blocks. To gain insight into how both enzyme active sites and metabolic pathways can be evolved to manage and select for fluorinated compounds, we have studied one of the only characterized natural hosts for organofluorine biosynthesis, the soil microbe Streptomyces cattleya. This information provides a template for designing engineered organofluorine enzymes, pathways, and hosts and has allowed us to initiate construction of enzymatic and cellular pathways for the production of fluorinated polyketides.

Radical Ions of 3-Styryl-quinoxalin-2-one Derivatives Studied by Pulse Radiolysis in Organic Solvents.

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Skotnicki, Konrad; De la Fuente, Julio R; Cañete, Álvaro; Berrios, Eduardo; Bobrowski, Krzysztof

2018-04-12

The absorption-spectral and kinetic behaviors of radical ions and neutral hydrogenated radicals of seven 3-styryl-quinoxalin-2(1 H)-one (3-SQ) derivatives, one without substituents in the styryl moiety, four others with electron-donating (R = -CH 3 , -OCH 3 , and -N(CH 3 ) 2 ) or electron-withdrawing (R = -OCF 3 ) substituents in the para position in their benzene ring, and remaining two with double methoxy substituents (-OCH 3 ), however, at different positions (meta/para and ortho/meta) have been studied by UV-vis spectrophotometric pulse radiolysis in neat acetonitrile saturated with argon (Ar) and oxygen (O 2 ) and in 2-propanol saturated with Ar, at room temperature. In acetonitrile solutions, the radical anions (4R-SQ •- ) are characterized by two absorption maxima located at λ max = 470-490 nm and λ max = 510-540 nm, with the respective molar absorption coefficients ε 470-490 = 8500-13 100 M -1 cm -1 and ε 510-540 = 6100-10 300 M -1 cm -1 , depending on the substituent (R). All 4R-SQ •- decay in acetonitrile via first-order kinetics, with the rate constants in the range (1.2-1.5) × 10 6 s -1 . In 2-propanol solutions, they decay predominantly through protonation by the solvent, forming neutral hydrogenated radicals (4R-SQH • ), which are characterized by weak absorption bands with λ max = 480-490 nm. Being oxygen-insensitive, the radical cations (4R-SQ •+ ) are characterized by a strong absorption with λ max = 450-630 nm, depending on the substituent (R). They are formed in a charge-transfer reaction between a radical cation derived from acetonitrile (ACN •+ ) and substituted 3-styryl-quinoxalin-2-one derivatives (4R-SQ) with a pseudo-first-order rate constant k = (2.7-4.7) × 10 5 s -1 measured in solutions containing 0.1 mM 4R-3-SQ. The Hammett equation plot gave a very small negative slope (ρ = -0.08), indicating a very weak influence of the substituents in the benzene ring on the rate of charge-transfer reaction. The decay of 4R

RESSONÂNCIA MAGNÉTICA NUCLEAR DE SUBSTÂNCIAS ORGANOFLUORADAS: UM DESAFIO NO ENSINO DE ESPECTROSCOPIA

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Frederico Silva Castelo Branco

2015-11-01

Full Text Available Nuclear magnetic resonance is a technique that is widely used for elucidating and characterizing organic substances. Organofluorine substances have applications in many areas from drugs to liquid crystals, but their NMR spectra are often challenging due to fluoride coupling with other nuclei. For this reason, NMR spectra of this class of substances are not commonly covered in undergraduate and graduate chemistry courses and related fields. Thus, the aim of this work was the presentation and discussion of 1H, 13C, and 19F NMR spectra of eleven organofluorine substances which, in the case of 1H and 13C nuclei, showed classic patterns of first-order coupling and the effects of the fluorine nucleus in different chemical and magnetic environments. In addition, the observation of long distance coupling constants was possible through the use of apodization functions in the processing of the spectra. It is expected that the examples presented herein can be utilized and discussed in undergraduate and graduate NMR spectroscopy disciplines and thus improve the teaching and future research of organofluorine compounds.

Occurrence of imposex in Thais haemastoma: possible evidence of environmental contamination derived from organotin compounds in Rio de Janeiro and Fortaleza, Brazil

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Fernandez Marcos Antonio

2002-01-01

Full Text Available There are indications that the widespread use of organotin compounds (TBT and TPT as antifoulings, as stabilizers in plastic and as pesticides, has severely affected several species of marine organisms. The most striking effect of TBT and TPT as hormonal disruptors is the development of male organs in females of gastropods, currently denominated imposex. This syndrome can lead to the sterilization and death of affected organisms. The present work gives an overview of the present state of knowledge on imposex occurrence and reports results of a survey conducted in Guanabara Bay, Rio de Janeiro and in several sites along the coast of Fortaleza, Ceará State. Different stages of imposex development were verified in this survey, however, the most prominent levels appeared associated to known spot sources of TBT and TPT.

Synthesis, Characterization, and Thermal and Antimicrobial Activities of Some Novel Organotin(IV: Purine Base Complexes

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Reena Jain

2013-01-01

Full Text Available A new series of organotin(IV complexes with purine bases theophylline (HL1 and theobromine (L2 of the types R3Sn(L1, R2Sn(L1Cl, R3Sn(L2Cl, and R2Sn(L2Cl2 (R = C6H5CH2–; p-ClC6H4CH2– have been synthesized in anhydrous THF. The complexes were characterized by elemental analysis, conductance measurements, molecular weight determinations, UV-vis, IR, 1H, 13C NMR, and mass spectral studies. Various kinetic and thermodynamic parameters of these complexes have also been determined using TG/DTA technique. The thermal decomposition techniques indicate the formation of SnO2 as a residue. The results show that the ligands act as bidentate, forming a five-member chelate ring. All the complexes are 1 : 1 metal-ligand complexes. In order to assess their antimicrobial activity, the ligands and their corresponding complexes have also been tested in vitro against bacteria (E. coli, S. aureus, and P. pyocyanea and fungi (Rhizopus oryzae and Aspergillus flavus. All the complexes exhibit remarkable activity, and the results provide evidence that the studied complexes might indeed be a potential source of antimicrobial agents.

Organotin compounds in Brachidontes rodriguezii mussels from the Bahía Blanca Estuary, Argentina.

Science.gov (United States)

Quintas, Pamela Y; Arias, Andrés H; Oliva, Ana L; Domini, Claudia E; Alvarez, Mónica B; Garrido, Mariano; Marcovecchio, Jorge E

2017-11-01

Levels of tributyltin and its breakdown compounds, including the first record of monobutyltin (MBT) in history for Latin America, were determined in native mussels (Brachidontes rodriguezii) by means of CG-MS, after extraction/derivatization assisted by ultrasound. The samples were collected in 2013 in Bahía Blanca Estuary (Argentina) at 6 sites, which reflect different levels of maritime activities. Total butyltins (TBts = TBT+ DBT+ MBT) levels ranged from 19.64 to 180.57ng Sn g -1 dry weight. According to the Oslo-Paris commission, the results indicated that 73.9% of mussels could be under biological effects risks associated with TBT pollution. In accordance with the calculated bioaccumulation factors, approximately 56% of samples appeared to have accumulated TBT through the sediments. All sampling sites were shown to be impacted by organotin compounds (OTCs) showing variable levels through seasons, which could be related with the variation of the water temperature. Degradation index analyses suggested aged inputs of TBT possibly under a general degradation process at the area of study. In addition, the occurrence of DBT and MBT could not be uniquely attributed to the degradation pathway of the TBT; in fact, results outlined the possible contribution of some punctual and diffuse sources at the area such as proximity to plastic industries, industrial effluents, sewage outlets and domestic wastewaters. Copyright © 2017 Elsevier Inc. All rights reserved.

Spatio-temporal variation of organotin compounds in seawater and sediments from Cape Town harbour, South Africa using gas chromatography with flame photometric detector (GC-FPD

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Hussein K. Okoro

2016-01-01

Full Text Available The spatio-temporal variation of two organotin compounds (OTCs of tributyltin and triphenyltin in the seawater and sediment of Cape Town harbour was investigated. The organotin compounds were determined by GC-FPD following prior extraction with 0.02% tropolone. The concentration of OTCs varies for locations in Cape Town harbour. The concentration of OTCs in seawater ranges from 0.067 ± 0.01 to 111.290 ± 32.20 × 10−3 μg/l for TBT while that of TPT ranges between between ND ± SD and 23008.0 ± 0.03 × 10−3 μg/l respectively between locations. Relatively higher concentrations were measured for TBT and TPT during summer than in winter and spring seasons (p ⩽ 0.05. Apparently, the observed high or low values recorded for TBT in Cape Town harbour could be the result of an increase or decrease in the traffic of ships and boats. TBT was detected in all the sediment samples analysed except for location 9 (entrance to harbour, the two control sites (which are located far away from the inner harbour where boating activities are taking place, and location 12 (Robinson dry dock 2 where the samples were not at all found. For the control sites, antifouling compounds TBT and TPT were not detected throughout except for TBT that was found in control A during summer. The seasonal variation of OTC abundance in sediment was also investigated. The results indicated that TBT is present throughout the seasons but is predominantly present in this order summer > winter > spring.

MÉTODOS SELETIVOS DE FLUORAÇÃO DE MOLÉCULAS ORGÂNICAS

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Núbia Boechat

2015-12-01

Full Text Available Presently, the world depends on a wide variety of new materials based on organofluorine compounds. These compounds can be used as surfactants, high resistance polymers, liquid crystals, agrochemicals, radiopharmaceuticals for positron emission tomography, and drugs. However, the selective formation of C–F bonds remains a challenge. This study reviews our knowledge of organofluorine compounds and describes conventional and modern selective fluorination methods for obtaining these compounds. Here, we highlight the most common fluorination reagents and describe the fluorination reactions. This review is organized by the type of fluorine transfer: nucleophilic, electrophilic, and enzymatic

Action of tributyltin (TBT) on the lipid content and potassium retention in the organotins degradating fungus Cunninghamella elegans.

Science.gov (United States)

Bernat, Przemysław; Słaba, Mirosława; Długoński, Jerzy

2009-09-01

The purpose of the presented paper was to study the effect of high concentrations of tributyltin (TBT) on the potassium retention and fatty acid (FA) composition of the fungus Cunninghamella elegans recognized as a very efficient TBT degrader. An increase in TBT had a strong influence on the potassium concentration in the fungus. In growth medium without TBT, the potassium content of the fungal cells was 5.8 mg K(+) g dry weight(-1). The maximum concentration of K(+) was 15.06 mg g(-1) dry weight at 30 mg l(-1) of TBT. The major FAs that characterized the tested strain were C16:0, C18:1, C18:2, C18:3 and C18:0. TBT in the concentration range 5-30 mg l(-1) strongly influenced the FA composition. In the presence of the organotin, the degree of saturation increased. It suggests that the observed changes promote an increase in the lipid ordering of the membrane by reducing its permeability and inhibiting potassium ion efflux.

In vitro approaches to evaluate toxicity induced by organotin compounds tributyltin (TBT), dibutyltin (DBT), and monobutyltin (MBT) in neuroblastoma cells.

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Ferreira, Martiña; Blanco, Lucía; Garrido, Alejandro; Vieites, Juan M; Cabado, Ana G

2013-05-01

The toxic effects of the organotin compounds (OTCs) monobutyltin (MBT), dibutyltin (DBT), and tributyltin (TBT) were evaluated in vitro in a neuroblastoma human cell line. Mechanisms of cell death, apoptosis versus necrosis, were studied by using several markers: inhibition of cell viability and proliferation, F-actin, and mitochondrial membrane potential changes as well as reactive oxygen species (ROS) production and DNA fragmentation. The most toxic effects were detected with DBT and TBT even at very low concentrations (0.1-1 μM). In contrast, MBT induced lighter cytotoxic changes at the higher doses tested. None of the studied compounds stimulated propidium iodide uptake, although the most toxic chemical, TBT, caused lactate dehydrogenase release at the higher concentrations tested. These findings suggest that in neuroblastoma, OTC-induced cytotoxicity involves different pathways depending on the compound, concentration, and incubation time. A screening method for DBT and TBT quantification based on cell viability loss was developed, allowing a fast detection alternative to complex methodology.

Differences in organotin accumulation in relation to life history in the white-spotted charr Salvelinus leucomaenis

International Nuclear Information System (INIS)

Ohji, Madoka; Harino, Hiroya; Arai, Takaomi

2011-01-01

Research highlights: → Otolith Sr:Ca ratios in sea-run type were higher than those in freshwater-residents. → TBT and TPT concentrations in sea-run type were higher than those in freshwater-residents. → Sea-run type have higher risk of TBT and TPT than freshwater-residents in white-spotted charr. - Abstract: To examine the accumulation pattern of organotins (OTs) in relation to the migration of diadromous fish, tributyltin (TBT) and triphenyltin (TPT) and their derivatives were determined in the muscle tissue of both sea-run (anadromous) and freshwater-resident (nonanadromous) types of the white-spotted charr Salvelinus leucomaenis. Ontogenic changes in otolith strontium (Sr) and calcium (Ca) concentrations were examined along life history transect to discriminate migration type. Mean Sr:Ca ratio from the core to the edge of the otolith in sea-run individuals was significantly higher than those in freshwater-resident one. There were no significant correlations in S. leucomaenis between OT accumulation and various biological characteristics. It is noteworthy that TBT and TPT concentrations in sea-run type were significantly higher than those in freshwater-resident individuals, although they are both of the same species. These results suggest that sea-run S. leucomaenis have a higher ecological risk of OT exposure than freshwater-residents during their life histories.

Comparison of GC/MSD and GC/AED for the determination of organotin compounds in the environment

Energy Technology Data Exchange (ETDEWEB)

Staeb, J.A. (Inst. of Environmental Studies, Free Univ., Amsterdam (Netherlands)); Cofino, W.P. (Inst. of Environmental Studies, Free Univ., Amsterdam (Netherlands)); Hattum, B. van (Inst. of Environmental Studies, Free Univ., Amsterdam (Netherlands)); Brinkman, U.A.T. (Dept. of Analytical Chemistry, Free Univ., Amsterdam (Netherlands))

Methods are described for the analysis of environmental samples like water, sediment and suspended matter for the determination of all organotin compounds (OTs) that are currently used as biocides: Tributyltin (TBT) triphenyltin (TPT), tricyclohexyltin (TCT) and fenbutatin oxide (FBTO). In water also five degradation products (di and mono substituted analogs) can be determined. Alkylation using a Grignard reagent was used to obtain OT derivatives amenable to gas chromatography (GC). Both methylation and pentylation have been employed for derivatization prior to GC analysis. The present results show that derivatization efficiencies for TPT, TCT and FBTO at trace levels are higher using methylation than pentylation. Detection limits for each type of sample matrix were determined using GC/Mass Selective Detection (GC/MSD) and GC/Atomic Emission Detection (AED). In sediment and suspended matter only tri-substituted OTs (i.e. the parent compounds) could be determined. Detection limits ranged from 0.2 to 10 ng/g dry weight. FBTO, not previously detected in environmental samples, was found at levels of 4 and 11 ng/g in a suspended matter sample and a sediment sample, respectively. In water the OTs and their degradation products were determined at levels of 1-10 ng/l (as tin) using 200 ml water samples. (orig.)

Stereochemistry of quinoxaline antagonist binding to a glutamate receptor investigated by Fourier transform infrared spectroscopy.

Science.gov (United States)

Madden, D R; Thiran, S; Zimmermann, H; Romm, J; Jayaraman, V

2001-10-12

The stereochemistry of the interactions between quinoxaline antagonists and the ligand-binding domain of the glutamate receptor 4 (GluR4) have been investigated by probing their vibrational modes using Fourier transform infrared spectroscopy. In solution, the electron-withdrawing nitro groups of both compounds establish a resonance equilibrium that appears to stabilize the keto form of one of the cyclic amide carbonyl bonds. Changes in the 6,7-dinitro-2,3-dihydroxyquinoxaline vibrational spectra on binding to the glutamate receptor, interpreted within the framework of a published crystal structure, illuminate the stereochemistry of the interaction and suggest that the binding site imposes a more polarized electronic bonding configuration on this antagonist. Similar spectral changes are observed for 6-cyano-7-dinitro-2,3-dihydroxyquinoxaline, confirming that its interactions with the binding site are highly similar to those of 6,7-dinitro-2,3-dihydroxyquinoxaline and leading to a model of the 6-cyano-7-dinitro-2,3-dihydroxyquinoxaline-S1S2 complex, for which no crystal structure is available. Conformational changes within the GluR ligand binding domain were also monitored. Compared with the previously reported spectral changes seen on binding of the agonist glutamate, only a relatively small change is detected on antagonist binding. This correlation between the functional effects of different classes of ligand and the magnitude of the spectroscopic changes they induce suggests that the spectral data reflect physiologically relevant conformational processes.

Certification of butyltins and phenyltins in marine sediment certified reference material by species-specific isotope-dilution mass spectrometric analysis using synthesized {sup 118}Sn-enriched organotin compounds

Energy Technology Data Exchange (ETDEWEB)

Inagaki, Kazumi; Takatsu, Akiko; Watanabe, Takuro; Aoyagi, Yoshie; Yarita, Takashi; Okamoto, Kensaku; Chiba, Koichi [National Institute of Advanced Industrial Science and Technology (AIST), Environmental Standard Section, National Metrology Institute of Japan (NMIJ), Tsukuba, Ibaraki (Japan)

2007-04-15

A new marine sediment certified reference material, NMIJ CRM 7306-a, for butyltin and phenyltin analysis has been prepared and certified by the National Metrological Institute of Japan at the National Institute of Advanced Industrial Science and Technology (NMIJ/AIST). Candidate sediment material was collected at a bay near industrial activity in Japan. After air-drying, sieving, and mixing the material was sterilized with {gamma}-ray irradiation. The material was re-mixed and packaged into 250 glass bottles (15 g each) and these were stored in a freezer at -30 C. Certification was performed by use of three different types of species-specific isotope-dilution mass spectrometry (SSID-MS) - SSID-GC-ICP-MS, SSID-GC-MS, and SSID-LC-ICP-MS, with {sup 118}Sn-enriched organotin compounds synthesized from {sup 118}Sn-enriched metal used as a spike. The {sup 118}Sn-enriched mono-butyltin (MBT), dibutyltin (DBT), and tributyltin (TBT) were synthesized as a mixture whereas the {sup 118}Sn-enriched di-phenyltin (DPhT) and triphenyltin (TPhT) were synthesized individually. Four different extraction methods, mechanical shaking, ultrasonic, microwave-assisted, and pressurized liquid extraction, were adopted to avoid possible analytical bias caused by non-quantitative extraction and degradation or inter-conversion of analytes in sample preparations. Tropolone was used as chelating agent in all the extraction methods. Certified values are given for TBT 44{+-}3 {mu}g kg{sup -1} as Sn, DBT 51 {+-} 2 {mu}g kg{sup -1} as Sn, MBT 67 {+-} 3 {mu}g kg{sup -1} as Sn, TPhT 6.9 {+-} 1.2 {mu}g kg{sup -1} as Sn, and DPhT 3.4 {+-} 1.2 {mu}g kg{sup -1} as Sn. These levels are lower than in other sediment CRMs currently available for analysis of organotin compounds. (orig.)

Structural and Biochemical Characterization of Organotin and Organolead Compounds Binding to the Organomercurial Lyase MerB Provide New Insights into Its Mechanism of Carbon–Metal Bond Cleavage

Energy Technology Data Exchange (ETDEWEB)

Wahba, Haytham M. [Département; Faculty; Stevenson, Michael J. [Department; Mansour, Ahmed [Département; Sygusch, Jurgen [Département; Wilcox, Dean E. [Department; Omichinski, James G. [Département

2017-01-03

The organomercurial lyase MerB has the unique ability to cleave carbon–Hg bonds, and structural studies indicate that three residues in the active site (C96, D99, and C159 in E. coli MerB) play important roles in the carbon–Hg bond cleavage. However, the role of each residue in carbon–metal bond cleavage has not been well-defined. To do so, we have structurally and biophysically characterized the interaction of MerB with a series of organotin and organolead compounds. Studies with two known inhibitors of MerB, dimethyltin (DMT) and triethyltin (TET), reveal that they inhibit by different mechanisms. In both cases the initial binding is to D99, but DMT subsequently binds to C96, which induces a conformation change in the active site. In contrast, diethyltin (DET) is a substrate for MerB and the SnIV product remains bound in the active site in a coordination similar to that of HgII following cleavage of organomercurial compounds. The results with analogous organolead compounds are similar in that trimethyllead (TML) is not cleaved and binds only to D99, whereas diethyllead (DEL) is a substrate and the PbIV product remains bound in the active site. Binding and cleavage is an exothermic reaction, while binding to D99 has negligible net heat flow. These results show that initial binding of organometallic compounds to MerB occurs at D99 followed, in some cases, by cleavage and loss of the organic moieties and binding of the metal ion product to C96, D99, and C159. The N-terminus of MerA is able to extract the bound PbVI but not the bound SnIV. These results suggest that MerB could be utilized for bioremediation applications, but certain organolead and organotin compounds may present an obstacle by inhibiting the enzyme.

The Pollutant Organotins Leads to Respiratory Disease by Inflammation: A Mini-Review

Science.gov (United States)

Nunes-Silva, Albená; Dittz, Dalton; Santana, Higor Scardini; Faria, Rodrigo Alves; Freitas, Katia Michelle; Coutinho, Christiane Rabelo; de Melo Rodrigues, Livia Carla; Miranda-Alves, Leandro; Silva, Ian Victor; Graceli, Jones Bernardes; Freitas Lima, Leandro Ceotto

2018-01-01

Organotins (OTs) are organometallic pollutants. The OTs are organometallic pollutants that are used in many industrial, agricultural, and domestic products, and it works as powerful biocidal compound against large types of microorganisms such as fungi and bacteria. In addition, OTs are well known to be endocrine-disrupting chemicals, leading abnormalities an “imposex” phenomenon in the female mollusks. There are some studies showing that OTs’ exposure is responsible for neural, endocrine, and reproductive dysfunctions in vitro and in vivo models. However, OTs’ effects over the mammalian immune system are poorly understood, particularly in respiratory diseases. The immune system, as well as their cellular components, performs a pivotal role in the control of the several physiologic functions, and in the maintenance and recovery of homeostasis. Thus, it is becoming important to better understand the association between environmental contaminants, as OTs, and the physiological function of immune system. There are no many scientific works studying the relationship between OTs and respiratory disease, especially about immune system activation. Herein, we reported studies in animal, humans, and in vitro models. We searched studies in PUBMED, LILACS, and Scielo platforms. Studies have reported that OTs exposure was able to suppress T helper 1 (Th1) and exacerbate T helper 2 (Th2) response in the immune system. In addition, OTs’ contact could elevate in the airway inflammatory response, throughout a mechanism associated with the apoptosis of T-regulatory cells and increased oxidative stress response. In addition, OTs induce macrophage recruitment to the tissue, leading to the increased necrosis, which stimulates an inflammatory cytokines secretion exacerbating the local inflammation and tissue function loss. Thus, the main intention of this mini-review is to up to date the main findings involving the inflammatory profile (especially Th1 and Th2 response) in the

Occurrence of PCDD/F, PCB, PBDE, PFAS, and organotin compounds in fish meal, fish oil and fish feed.

Science.gov (United States)

Suominen, K; Hallikainen, A; Ruokojärvi, P; Airaksinen, R; Koponen, J; Rannikko, R; Kiviranta, H

2011-10-01

We analysed polychlorinated dibenzo-p-dioxins and furans (PCDD/F, dioxins), and polychlorinated biphenyls (PCB) in 13 fish meal, five fish oil, and seven fish feed samples. Polybrominated diphenyl ethers (PBDE), organotin compounds (OTC), and perfluoroalkylated substances (PFAS) were analysed in ten fish meal, two fish oil, and two fish feed samples. All measured TEQ concentrations of PCDD/F and PCB were below the maximum levels set by Directive 2002/32/EC. There was no correlation between concentrations of WHOPCDD/F-TEQ and indicator PCB in our samples. The most common congeners among PBDEs were BDE-47 and BDE-100. BDE-209 was present in five fish meals of the ten analysed. Tributyltin (TBT) was the predominant congener in all samples except in three fish meals, where monobutyltin (MBT) was the major congener. Perfluorooctane sulphonate (PFOS) was the predominant congener in six fish meals of the ten analysed. There was large variation in concentrations and congener distributions of the studied compounds between our samples. Our results underline a need to pay special attention to the origin and purity of feed raw material of marine origin. Copyright © 2011 Elsevier Ltd. All rights reserved.

Crystal structure of 2-amino-1,3-dibromo-6-oxo-5,6-dihydropyrido[1,2-a]quinoxalin-11-ium bromide monohydrate

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Md. Serajul Haque Faizi

2015-11-01

Full Text Available In the title hydrated salt, C12H8Br2N3O+·Br−·H2O, which was synthesized by the reaction of the pyridine derivative Schiff base N1,N4-bis(pyridine-2-ylmethylenebenzene-1,4-diamine with bromine, the asymmetric unit contains a 2-amino-1,3-dibromo-6-oxo-5,6-dihydropyrido[1,2-a]quinoxalin-11-ium cation, with a protonated pyridine moiety, a bromide anion and a water molecule of solvation. The cation is non-planar with the dibromo-substituted benzene ring, forming dihedral angles of 24.3 (4 and 11.5 (4° with the fused pyridine and pyrazine ring moieties, respectively. In the crystal, the cations are linked through a centrosymmetric hydrogen-bonded cyclic R42(8 Br2(H2O2 unit by N—H...Br, N—H...O and O—H...Br hydrogen bonds, forming one-dimensional ribbons extending along b, with the planes of the cations lying parallel to (100.

Excited-state inter- and intramolecular proton transfer in methyl 3-hydroxy-2-quinoxalinate: effects of solvent and acid or base concentrations

International Nuclear Information System (INIS)

Dogra, S.K.

2005-01-01

Absorption, fluorescence excitation and fluorescence spectroscopy, combined with time-dependent spectroscopy and semi-empirical (AM1) and density functional theory using Gaussian 98 program calculations have been used to study the effects of solvent and acid or base concentration on the spectral characteristics of methyl 3-hydroxy-2-quinoxalinate (M3HQ). M3HQ is present as enol in less polar solvents and as keto in polar media. In non-polar solvents, large Stokes shifted fluorescence band is assigned to the phototautomer, formed by the excited-state intramolecular proton transfer, whereas fluorescence is only observed from keto in the polar solvents. In aqueous and polar solvents the monocation (MC5/MC6) is formed by protonating the carbonyl oxygen atom in the ground (S 0 ) and the first excited singlet states (S 1 ). Dication is formed by protonating one of ?N- atom of MC5/MC6. Monoanion is formed by deprotonating the phenolic proton of enol in the basic solution. pK a values for different prototropic equilibriums were determined in S 0 and S 1 states and discussed

Synthesis, crystal structures, and optical properties of the π-π interacting pyrrolo[2,3-b]quinoxaline derivatives containing 2-thienyl substituent

Science.gov (United States)

Goszczycki, Piotr; Stadnicka, Katarzyna; Brela, Mateusz Z.; Grolik, Jarosław; Ostrowska, Katarzyna

2017-10-01

Three (E/Z)-diastereoisomers, based on pyrrolo[2,3-b]quinoxaline system as fluorophore and containing: 2-thienylmethyl (1), bis(2-thienylmethyl)-2-aminoethyl (3a), bis(2-thienylmethyl)-3-aminopropyl (3b) groups as substituents, were synthesized and characterized by X-ray structural analysis, PXRD, NMR, UV-Vis as well as fluorescence. These compounds are non-fluorescent in acetonitrile solution, however, they exhibit aggregation induced emission enhancement (AIEE) upon water addition and in solid state. X-ray structural analysis revealed that molecules with 2-thienylmethyl and bis(2-thienylmethyl)-2-aminoethyl groups form dimers and π-stacks through π-π interactions between anitiparallel oriented pyrroloquinoxaline cores with interplanar distances 3.45 Å and 3.20 Å, respectively. Conformation of bis(2-thienylmethyl)-3-aminopropyl group is imposed by incorporated DMSO-d6 solvent molecule and weak intermolecular S-π and CH-π interactions, that prevents π-π interaction between fluorophore cores. The correlation between crystal structure and fluorescent properties of synthesized molecules was discussed. The DFT calculations were performed to rationalize the differences between considered systems.

Near-infrared-emitting heteroleptic cationic iridium complexes derived from 2,3-diphenylbenzo[g]quinoxaline as in vitro theranostic photodynamic therapy agents

Energy Technology Data Exchange (ETDEWEB)

Wang, Li; Yin, Huimin; Cui, Peng; Hetu, Marc; Wang, Chengzhe; Monro, Susan; Schaller, Richard D.; Cameron, Colin G.; Liu, Bingqing; Kilina, Svetlana; McFarland, Sherri A.; Sun, Wenfang

2017-05-19

Five heteroleptic cationic iridium complexes with a π-expansive cyclometalating 2,3-diphenylbenzo[g] quinoxaline (dpbq) ligand (C^N ligand) and different diimine ligands (N^N ligands) (i.e. 2,2’-bipyridine (bpy, 1), phenanthroline (phen, 2), 2-(2-pyridinyl)quinoline (pqu, 3), 2,2’-bisquinoline (bqu, 4), and 2-(quinolin-2-yl)quinoxaline (quqo, 5)) were synthesized and characterized. The lowest-energy singlet electronic transitions (S1 states) were mainly dpbq ligand-centred 1ILCT (intraligand charge transfer)/1MLCT (metal to ligand charge transfer) transitions mixed with some 1π,π* transitions for complexes 1–4 with increased contributions from 1LLCT (ligand to ligand charge transfer) in 3 and 4. For complex 5, the S1 state was switched to the 1LLCT/1MLCT transitions. All five complexes displayed weak near-infrared (NIR) phosphorescence, with maximal emission output spanning 700–1400 nm and quantum yields being on the order of 10-3. The triplet state absorptions of 1–4 all resembled that of the [Ir(dpbq)2Cl]2 dimer with lifetimes of ca. 400 ns, while the TA spectrum of 5 possessed the characteristics of both the quqo ligand and the [Ir(dpbq)2Cl]2 dimer with a bi-exponential decay of ca. 5 μs and 400 ns. While the photophysics of these complexes differ slightly, their theranostic photodynamic therapy (PDT) effects varied drastically. All of the complexes were biologically active toward melanoma cells. Complexes 2 and 3 were the most cytotoxic, with 230–340 nM activity and selectivity factors for melanoma cells over normal skin fibroblasts of 34 to 40 fold. Complexes 2, 3, and 5 became very potent cytotoxins with light activation, with EC50 values as low as 12–18 nM. This potent nanomolar light-triggered activity combined with a lower dark toxicity resulted in 5 having a phototherapeutic index (PI) margin of almost 275. The bpy coligand led to the least amount of dark toxicity of 1, while phen and pqu produced cytotoxic but selective complexes 2 and

Influence of the substituents on the electronic and electrochemical properties of a new square-planar nickel-bis(quinoxaline-6,7-dithiolate) system: synthesis, spectroscopy, electrochemistry, crystallography, and theoretical investigation.

Science.gov (United States)

Bolligarla, Ramababu; Reddy, Samala Nagaprasad; Durgaprasad, Gummadi; Sreenivasulu, Vudagandla; Das, Samar K

2013-01-07

We describe the synthesis, crystal structures, electronic absorption spectra, and electrochemistry of a series of square-planar nickel-bis(quinoxaline-6,7-dithiolate) complexes with the general formula [Bu(4)N](2)[Ni(X(2)6,7-qdt)(2)], where X = H (1a), Ph (2a), Cl (3), and Me (4). The solution and solid-state electronic absorption spectral behavior and electrochemical properties of these compounds are strongly dependent on the electron donating/accepting nature of the substituent X, attached to the quinoxaline-6,7-dithiolate ring in the system [Bu(4)N](2)[Ni(X(2)6,7-qdt)(2)]. Particularly, the charge transfer (CT) transition bands observed in the visible region are greatly affected by the electronic nature of the substituent. A possible explanation for this influence of the substituents on electronic absorption and electrochemistry is described based on highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO) gaps, which is further supported by ground-state electronic structure calculations. In addition to this, the observed CT bands in all the complexes are sensitive to the solvent polarity. Interestingly, compounds 1a, 2a, 3, and 4 undergo reversible oxidation at very low oxidation potentials appearing at E(1/2) = +0.12 V, 0.033 V, 0.18 V, and 0.044 V vs Ag/AgCl, respectively, in MeOH solutions, corresponding to the respective couples [Ni(X(2)6,7-qdt)(2)](-)/[Ni(X(2)6,7-qdt)(2)](2-). Compounds 1a, 3, and 4 have been characterized unambiguously by single crystal X-ray structural analysis; compound 2a could not be characterized by single crystal X-ray structure determination because of the poor quality of the concerned crystals. Thus, we have synthesized the tetraphenyl phosphonium salt of the complex anion of 2a, [PPh(4)](2)[Ni(Ph(2)6,7-qdt)(2)]·3DMF (2b) for its structural characterization.

In vitro screening of organotin compounds and sediment extracts for cytotoxicity to fish cells.

Science.gov (United States)

Giltrap, Michelle; Macken, Ailbhe; McHugh, Brendan; McGovern, Evin; Foley, Barry; Davoren, Maria

2011-01-01

The present study reports an in vitro screening method for contaminants in sediment samples utilizing an RTG-2 cell line. This technique integrates cytotoxicity testing with analytical chemistry with the aim of achieving a toxicity evaluation of the sediment sample. The toxic effect of individual organotin (OT) compounds and their presence in the sediment sample is the focus of the present study; however, other contaminants are also discussed. The following OT compounds: tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), triphenyltin (TPT), diphenyltin (DPT), and a sediment solvent extract are exposed to the RTG-2 fish cell line. Both the alamar blue (AB) and neutral red (NR) assays are used to assess cytotoxicity after 24-h and 96-h exposure. Methodology for preparation of a sediment solvent extract suitable for biological testing and analytical determination is also described. With the RTG-2 cells, the AB and NR assays had comparable sensitivity for each individual OT compound exposure after 24 h, with TPT being the most toxic compound tested. The individual OT compound concentrations required to induce a 50% toxic effect on the cells (369 ng ml⁻¹ TBT, 1,905 ng ml⁻¹ DBT) did not equate to the concentrations of these contaminants present in the sediment extract that induced a 50% effect on the cells (294 ng ml⁻¹ TBT, 109 ng ml⁻¹ DBT). The solvent extract therefore exhibited a greater toxicity, and this suggests that the toxic effects observed were not due to OT compounds alone. The presence of other contaminants in the solvent extract is confirmed with chemical analysis, warranting further toxicity testing of contaminant mixtures and exposure to the cell line to further elucidate a complete toxicity evaluation. © 2010 SETAC.

Indeno-1-one [2,3-b]quinoxaline as an effective inhibitor for the corrosion of mild steel in 0.5 M H2SO4 solution

International Nuclear Information System (INIS)

Obot, I.B.; Obi-Egbedi, N.O.

2010-01-01

Indeno-1-one [2,3-b] quinoxaline (INQUI), synthesized in our laboratory, was tested as inhibitor for the corrosion of mild steel in 0.5 M H 2 SO 4 using gravimetric method at 30 o C. The inhibitor (INQUI) showed about 81% inhibition efficiency (E (%)) at an optimum concentration of 10 x 10 -6 M. The inhibition efficiency increases with increase in inhibitor concentration but decreases with increase in immersion time. The adsorption of the inhibitor on the mild steel in the acid solution was found to accord with Temkin's adsorption isotherm. The calculated value of the free energy for the adsorption process, ΔG ads , reveals a strong chemisorbed bond between the inhibitor and mild steel surface and a spontaneous adsorption of the inhibitor on the mild steel surface. Density functional theory (DFT) proves that INQUI molecule is adsorbed on the mild steel surface by the most negatively charged nitrogen and oxygen atoms.

Roles of ROS mediated oxidative stress and DNA damage in 3-methyl-2-quinoxalin benzenevinylketo-1, 4-dioxide-induced immunotoxicity of Sprague-Dawley rats.

Science.gov (United States)

Gao, Hui; Wang, Di; Zhang, Shun; Xu, Mengjing; Yang, Wei; Yan, Peipei; Liu, Yang; Luo, Xiao; Wu, Hailei; Yao, Ping; Yan, Hong; Liu, Liegang

2015-11-01

3-methyl-2-quinoxalin benzenevinylketo-1, 4-dioxide (Quinocetone, QCT) has been broadly used to treat dysentery and promote animal growth in food producing animals. However, its potential toxicity could not been neglected as parts of safety assessment according to the acceptable guidelines for QCT administration. In this study, the immunotoxicity of QCT was investigated in male Sprague-Dawley (SD) rats following a 28-day oral exposure at doses of 0, 50, 800, and 2400 mg/kg/day. The food consumption, body weight gain and relative spleen weight were significantly decreased by QCT in a dose-dependent manner. Treatment of rats with QCT also notably suppressed the T-cell proliferation and natural killer (NK) cell activity, accompanied by intracellular reactive oxygen species (ROS) accumulation, antioxidant system inhibition and DNA damage enhancement. Thus, the primary finding of this study is that QCT exposure (2400 mg/kg/day) could cause immunotoxicity in SD rats due to ROS mediated oxidative stress and DNA damage. Copyright © 2015 Elsevier Inc. All rights reserved.

The synthesis of 5'-[14C1] and 3a, 4-[13C2] labelled panadiplon (U-78875; 3-(5'-cyclopropyl-1,2,4-oxadiazol-3-yl)-5-(1-methylethyl)-imidazo-[1,5a]-quinoxalin-4(5H)-one)

International Nuclear Information System (INIS)

Ackland, M.J.; Howard, M.R.; Dring, L.G.

1993-01-01

5'-[ 14 C 1 ]Panadiplon was prepared in 3 steps starting from [ 14 C 1 ]cyclopropane carboxylic acid and 3-(5'-cyano-1,2,4-oxadiazol-3-yl)-5-(1-methylethyl)-imidazo-[1,5a] -quinoxalin-4(5H)-one. 3a, 4-[ 13 C 2 ]Panadiplon was prepared in two steps from 13 C 2 -oxalic acid and N-1-(1-methylethyl)-o-phenylenediamine. The position of labelling was confirmed by the appearance of two coupled resonances (J C-C =80.59 Hz) at 121.95 and 154.39 ppm in the assigned 13 C-NMR spectrum. (Author)

Speciation of selenium in environmental samples by solid-phase spectrophotometry using 2,3-dichloro-6-(2,7-dihydroxy-naphthylazo)quinoxaline.

Science.gov (United States)

Amin, Alaa S

2014-01-01

Solid-phase spectrophotometry was applied to determination of trace amounts of selenium (Se) in water, soil, plant materials, human hair, and a cosmetic preparation (lipstick). Se(IV) was sorbed in a dextran type lipophilic gel as a complex with 2,3-dichloro-6-(2,7-dihydroxy-naphthylazo)quinoxaline (DCDHNAQ), whereas Se(VI) was determined after boiling in HCI for 10 min to convert Se(VI) to Se(IV). Resin phase absorbances at 588 and 800 nm were measured directly, which allowed the determination of Se in the range of 0.2-3.3 microg/L with an RSD of 1.22%. The influences of analytical parameters including pH of the aqueous solution, amounts of DCDHNAQ, and sample volume were investigated. The molar absorptivities were found to be 1.09 x 10(6), 4.60 x 10(6), and 1.23 x 10(7) L/mol cm for 100, 500, and 1000 mL, respectively. The LOD and LOQ of the 500 mL sample method were 110 and 360 ng/L, respectively, when using 50 mg dextran type lipophilic gel. For a 1000 mL sample, the LOD and LOQ were 60 and 200 ng/L, respectively, using 50 mg of the exchanger. Increasing the sample volume enhanced the sensitivity. No considerable interferences were observed from other investigated anions and cations on the Se determination.

Fulltext PDF

Indian Academy of Sciences (India)

Email: gu.chaturbhuj@gmail.com ... bear quinoxaline nucleus.11 Quinoxaline moiety is also .... 143 stretching of the SO3H group. Powder XRD pattern showed significant peaks positioned at ..... Brown D J 2004 In Quinoxalines: Supplement II.

Extraction processes and solvents for recovery of cesium, strontium, rare earth elements, technetium and actinides from liquid radioactive waste

Science.gov (United States)

Zaitsev, Boris N.; Esimantovskiy, Vyacheslav M.; Lazarev, Leonard N.; Dzekun, Evgeniy G.; Romanovskiy, Valeriy N.; Todd, Terry A.; Brewer, Ken N.; Herbst, Ronald S.; Law, Jack D.

2001-01-01

Cesium and strontium are extracted from aqueous acidic radioactive waste containing rare earth elements, technetium and actinides, by contacting the waste with a composition of a complex organoboron compound and polyethylene glycol in an organofluorine diluent mixture. In a preferred embodiment the complex organoboron compound is chlorinated cobalt dicarbollide, the polyethylene glycol has the formula RC.sub.6 H.sub.4 (OCH.sub.2 CH.sub.2).sub.n OH, and the organofluorine diluent is a mixture of bis-tetrafluoropropyl ether of diethylene glycol with at least one of bis-tetrafluoropropyl ether of ethylene glycol and bis-tetrafluoropropyl formal. The rare earths, technetium and the actinides (especially uranium, plutonium and americium), are extracted from the aqueous phase using a phosphine oxide in a hydrocarbon diluent, and reextracted from the resulting organic phase into an aqueous phase by using a suitable strip reagent.

TBT and its metabolites in sediments: Survey at a German coastal site and the central Baltic Sea.

Science.gov (United States)

Abraham, Marion; Westphal, Lina; Hand, Ines; Lerz, Astrid; Jeschek, Jenny; Bunke, Dennis; Leipe, Thomas; Schulz-Bull, Detlef

2017-08-15

Since the 1950s the organotin compound tributyltin (TBT) was intensively used in antifouling paints for marine vessels and it became of concern for the marine environment. Herein, we report on a study from 2015 on TBT and its metabolites monobutyltin (MBT) and dibutyltin (DBT) in sediments from the central Baltic Sea and a Baltic Sea coastal site with strong harbor activities (Warnemünde). Sublayers from a sediment core from the Arkona Basin were analyzed to investigate the long term organotin pressure for the Baltic Sea. For the central Baltic Sea total organotin (MBT+DBT+TBT) ranged from 100 to 500ng/g TOC with distinct areas of high organotin content probably due to historical inputs. For the coastal site total organotin ranged from 10,000 to 60,000ng/g TOC. MBT and DBT were the predominant organotin species detected. Overall, the data obtained indicate the progress of TBT degradation at the investigated sites. Copyright © 2017 Elsevier Ltd. All rights reserved.

Organotins and new antifouling biocides in water and sediments from three Korean Special Management Sea Areas following ten years of tributyltin regulation: Contamination profiles and risk assessment.

Science.gov (United States)

Lam, Nguyen Hoang; Jeong, Hui-Ho; Kang, Su-Dong; Kim, Dae-Jin; Ju, Mi-Jo; Horiguchi, Toshihiro; Cho, Hyeon-Seo

2017-08-15

A simultaneous monitoring study on organotins (butyltins and phenyltins) and most frequently used alternative antifouling biocides (Irgarol 1051, Diuron, Sea-Nine 211 and M1) in water and sediments (n=44) collected from three Special Management Sea Areas operated by Korean government. The lower concentration of butyltins (BTs) than that of new antifouling biocides (NEW) was found in water but the significant greater concentration of BTs than that of NEW was still found in sediments. The tributyltin (TBT) levels in water exceeded the chronic criterion to protect seawater aquatic life at several sites. Even ten years after the ban of the use of TBT-based antifouling paint, the concentrations of TBT, Diuron and Irgarol 1051 in sediments from shipyards exceeded global sediment quality guidelines and potentially poses adverse risks on marine organisms and extremely high concentration of TBT up to 2304ng/g was found for a sediment collected at a shipyard. Copyright © 2017 Elsevier Ltd. All rights reserved.

Mechanisms of antibacterial action of Quinoxaline 1,4-di-N-oxides against Clostridium perfringens and Brachyspira hyodysenteriae

Directory of Open Access Journals (Sweden)

Fanfan Xu

2016-12-01

Full Text Available Quinoxaline 1,4-di-N-oxides (QdNOs are a class of bioreductive compounds, however their antibacterial mechanisms are still unclarified. The aim of this study was to assess the ability of two representative QdNO drugs, cyadox (CYA and olaquindox (OLA, to produce reactive oxide species (ROS in Gram-positive anaerobe Clostridium perfringens CVCC1125 and Gram-negative anaerobe Brachyspira hyodysenteriae B204. In addition, the effects of QdNOs on the integrity of bacterial cell walls and membranes as well as the morphological alterations and DNA oxidative damage in C. perfringens and B. hyodysenteriae were analyzed. It was demonstrated that under anaerobic conditions, QdNOs were metabolized into the reduced products which did not show any antibacterial activity. A significant dose-related increase of intracellular ROS level and intracellular hydroxyl radicals were evident in bacteria exposed to QdNOs. The result of biochemical assay showed that the cell walls and membranes of the bacteria treated with QdNOs were damaged. After exposure to 1/2MIC to 4MIC of CYA and OLA, C. perfringens and B. hyodysenteriae became elongated and filamentous. Morphological observation with scanning and transmission electron microscopes revealed rupture, loss of cytoplasmic material and cell lysis in QdNO-treated bacteria, indicating serious damage of cells. There was an increase of 8-OHdG in the two strains treated by QdNOs, but it was lower in Gram-positive than in Gram-negative bacteria. Agarose gel electrophoresis showed the degradation of chromosomal DNA in both of the two anaerobes treated by QdNOs. The results suggest that QdNOs may kill C. perfringens and B. hyodysenteriae via the generation of ROS and hydroxyl radicals from the bacterial metabolism of QdNOs, which cause oxidative damage in bacteria under anaerobic conditions.

Untitled

African Journals Online (AJOL)

organotin halides form 1:2 (Lewis acid: Lewis base) adducts whereas the lower trialkyltin halides form 1:1 adducts. However, it appears that the ability of organotin-pseudohalides to complex with common Lewis bases such as the pyridines has been little reported. The ability of organotin halides to complex with Lewis bases.

Determination of organotin compounds in waters by headspace solid phase microextraction gas chromatography triple quadrupole tandem mass spectrometry under the European Water Framework Directive.

Science.gov (United States)

Moscoso-Pérez, C; Fernández-González, V; Moreda-Piñeiro, J; López-Mahía, P; Muniategui-Lorenzo, S; Prada-Rodríguez, D

2015-03-13

The European Union Water Framework Directive (2013/39/EU) sets very restrictive environmental quality standards for 45 priority substances and other pollutants, including organotin compounds (OTCs). Therefore, it is necessary to develop analytical methods in compliance with the environmental quality standard (EQSs) proposed to protect the aquatic environment and humans. The proposed method (HS-SPME-GC-QqQ-MS/MS) allows the determination of OTCs, i.e. monobutyltin (MBT), dibutyltin (DBT) and TBT in water in the range of few ng L(-1). The method is nearly full automated, sensitive and simple; it involves less reagents, reduces waste, and is less-time consuming than traditional methods for OTCs. As such, the procedure connects with the principles of green analytical chemistry. Additionally, good precision (RSD<20%), a very low method quantification limit (MQL) (0.76 ng L(-1) for TBT by using only 10 mL of sample) and excellent linearity (range MQL-20 ng L(-1)) are achieved. Under these conditions, the very restrictive limits for the environmental quality standards (EQS) fixed by the 2013/39/EU Directive are achieved. Copyright © 2015 Elsevier B.V. All rights reserved.

Anticonvulsant, anxiolytic and discriminative effects of the AMPA antagonist 2,3-dihydroxy-6-nitro-7-sulfamoyl-benzo(f)quinoxaline (NBQX).

Science.gov (United States)

Swedberg, M D; Jacobsen, P; Honoré, T

1995-09-01

The anticonvulsant effects of 2,3-dihydroxy-6-nitro-7-sulfamoyl-benzo(f)quinoxaline (NBQX), phencyclidine (PCP) and diazepam against audiogenic seizures in DBA/2 mice and against seizures induced by methyl-6,7-dimethoxy-4-ethyl-beta-carboline-3-carboxylate (DMCM) in NMRI mice were compared. Motor impairment was assessed in a rotarod apparatus in DBA/2 as well as NMRI mice. At 30 min after i.p. administration, NBQX was as effective as PCP and diazepam in protecting against audiogenic seizures and had a therapeutic ratio slightly higher than diazepam's and 7-fold higher than PCP's. Whereas diazepam was fully effective, NBQX and PCP were both ineffective against seizures induced by DMCM 30 min after i.p. administration. The anticonvulsant potential and motor-impairing effects of NBQX were evaluated further by the i.p. and the i.v. routes at different time points after administration. At all pretreatment intervals, NBQX protected against audiogenic seizures more potently than it produced motor impairment. NBQX administered i.p. protected against DMCM-induced seizures when given 15 min but not 5 min before testing, whereas after i.v. administration NBQX produced anticonvulsant and motor-impairing effects in the same dose range. NBQX only slightly and non-dose-dependently attenuated the discriminative effects of pentylenetetrazole in rats, showing a limited anxiolytic potential. NBQX produced no PCP-like or morphine-like discriminative effects in rats, suggesting lack of PCP or opiate-like subjective effects. These data demonstrate that NBQX has anticonvulsant effects, has limited anxiolytic effects, and does not produce subjective effects of PCP or opiate type.

Occurrence of organotin compounds in river sediments under the dynamic water level conditions in the Three Gorges Reservoir Area, China.

Science.gov (United States)

Gao, Jun-Min; Zhang, Ke; Chen, You-Peng; Guo, Jin-Song; Wei, Yun-Mei; Jiang, Wen-Chao; Zhou, Bin; Qiu, Hui

2015-06-01

The Three Gorges Project is the largest hydro project in the world, and the water level of the Three Gorges Reservoir (TGR) is dynamic and adjustable with the aim of flood control and electrical power generation. It is necessary to investigate the pollutants and their underlying contamination processes under dynamic water levels to determine their environmental behaviors in the Three Gorges Reservoir Area (TGRA). Here, we report the assessment of organotin compounds (OTs) pollution in the river sediments of the TGRA. Surface sediment samples were collected in the TGRA at low and high water levels. Tributyltin (TBT), triphenyltin (TPhT), and their degradation products in sediments were quantified by gas chromatography-mass spectrometry. Butyltins (BTs) and phenyltins (PhTs) were detected in sediments, and BTs predominated over PhTs in the whole study area under dynamic water level conditions. The concentrations of OTs in sediments varied markedly among locations, and significant concentrations were found in river areas with high levels of boat traffic and wastewater discharge. Sediments at all stations except Cuntan were lightly contaminated with TBT, and total organic carbon (TOC) was a significant factor affecting the fate of TBT in the TGRA. The butyltin and phenyltin degradation indices showed no recent inputs of TBT or TPhT into this region, with the exception of fresh TPhT input at Xiakou Town. Shipping activity, wastewater discharge, and agriculture are the most likely sources of OTs in the TGRA.

Spectral and kinetic properties of radicals derived from oxidation of quinoxalin-2-one and its methyl derivative.

Science.gov (United States)

Skotnicki, Konrad; De la Fuente, Julio R; Cañete, Alvaro; Bobrowski, Krzysztof

2014-11-19

The kinetics and spectral characteristics of the transients formed in the reactions of •OH and •N3 with quinoxalin-2(1H)-one (Q), its methyl derivative, 3-methylquinoxalin-2(1H)-one (3-MeQ) and pyrazin-2-one (Pyr) were studied by pulse radiolysis in aqueous solutions at pH 7. The transient absorption spectra recorded in the reactions of •OH with Q and 3-MeQ consisted of an absorption band with λmax = 470 nm assigned to the OH-adducts on the benzene ring, and a second band with λmax = 390 nm (for Q) and 370 nm (for 3-MeQ) assigned, inter alia, to the N-centered radicals on a pyrazin-2-one ring. The rate constants of the reactions of •OH with Q and 3-MeQ were found to be in the interval (5.9-9.7) × 109 M-1·s-1 and were assigned to their addition to benzene and pyrazin-2-one rings and H-abstraction from the pyrazin-2-one nitrogen. In turn, the transient absorption spectrum observed in the reaction of •N3 exhibits an absorption band with λmax = 350 nm. This absorption was assigned to the N-centered radical on the Pyr ring formed after deprotonation of the respective radical cation resulting from one-electron oxidation of 3-MeQ. The rate constant of the reaction of •N3 with 3 MeQ was found to be (6.0 ± 0.5) × 109 M-1·s-1. Oxidation of 3-MeQ by •N3 and Pyr by •OH and •N3 confirms earlier spectral assignments. With the rate constant of the •OH radical with Pyr (k = 9.2 ± 0.2) × 109 M-1·s‒1, a primary distribution of the •OH attack was estimated nearly equal between benzene and pyrazin-2-one rings.

Spectral and Kinetic Properties of Radicals Derived from Oxidation of Quinoxalin-2-One and Its Methyl Derivative

Directory of Open Access Journals (Sweden)

Konrad Skotnicki

2014-11-01

Full Text Available The kinetics and spectral characteristics of the transients formed in the reactions of •OH and •N3 with quinoxalin-2(1H-one (Q, its methyl derivative, 3-methylquinoxalin-2(1H-one (3-MeQ and pyrazin-2-one (Pyr were studied by pulse radiolysis in aqueous solutions at pH 7. The transient absorption spectra recorded in the reactions of •OH with Q and 3-MeQ consisted of an absorption band with λmax = 470 nm assigned to the OH-adducts on the benzene ring, and a second band with λmax = 390 nm (for Q and 370 nm (for 3-MeQ assigned, inter alia, to the N-centered radicals on a pyrazin-2-one ring. The rate constants of the reactions of •OH with Q and 3-MeQ were found to be in the interval (5.9–9.7 × 109 M–1·s–1 and were assigned to their addition to benzene and pyrazin-2-one rings and H-abstraction from the pyrazin-2-one nitrogen. In turn, the transient absorption spectrum observed in the reaction of •N3 exhibits an absorption band with λmax = 350 nm. This absorption was assigned to the N-centered radical on the Pyr ring formed after deprotonation of the respective radical cation resulting from one-electron oxidation of 3-MeQ. The rate constant of the reaction of •N3 with 3 MeQ was found to be (6.0 ± 0.5 × 109 M–1·s–1. Oxidation of 3-MeQ by •N3 and Pyr by •OH and •N3 confirms earlier spectral assignments. With the rate constant of the •OH radical with Pyr (k = 9.2 ± 0.2 × 109 M–1·s‒1, a primary distribution of the •OH attack was estimated nearly equal between benzene and pyrazin-2-one rings.

Variation in organotin accumulation in relation to the life history in the Japanese eel Anguilla japonica

Science.gov (United States)

Ohji, Madoka; Harino, Hiroya; Arai, Takaomi

2009-08-01

In order to examine the ecological risks caused by organotin compounds (OTs) in diadromous fish migrating between sea and freshwaters, tributyltin (TBT) and triphenyltin (TPT) compounds and their breakdown products were determined in the catadromous eel Anguilla japonica, which has sea, estuarine and river life histories, collected in Japanese sea, brackish and freshwaters within the same region. Ontogenic changes in otolith strontium (Sr) and calcium (Ca) concentrations were examined along the life history transect to discriminate the migration type. There were generally three different patterns, which were categorized as 'sea eels', 'estuarine eels' and 'river eels' according to the otolith Sr:Ca ratio. The concentrations of TBT in silver eels (mature eels) were significantly higher than that in yellow eels (immature eels), and the percentages of TBT were also higher in silver eels than in yellow eels. A positive correlation was found between TBT concentration and the gonad-somatic index (GSI). It is thus considered that silver eels have a higher risk of contamination by TBT than yellow eels. TBT and TPT concentrations in sea eels were significantly higher than those in river eels, while no significant differences were observed in TBT and TPT concentrations in estuarine eels compared to sea and river eels. These results suggest that sea eels have a higher ecological risk of OT contamination than river eels during their life history, and the risk of OTs in estuarine eels is considered to be intermediate between that of sea and river eels. Positive linear relationships were found between Sr:Ca ratios and the concentrations of TBT and TPT. Therefore, these results suggest that the ecological risk of OTs increase as the sea residence period in the eel becomes longer. TBT and TPT concentrations in sea eels were significantly higher than those in river eels even at the same growth stage. Thus, it is clear that migratory type is the most important factor for OT

3-Methyl-1-(prop-2-en-1-ylquinoxalin-2(1H-one

Directory of Open Access Journals (Sweden)

Youssef Ramli

2010-07-01

Full Text Available In the molecule of the title compound, C12H12N2O, the quinoxaline ring is planar with an r.m.s. deviation of 0.007 (15 Å. The dihedral angle between the quinoxaline and propenyl planes is 82.1 (2°. The crystal packing is stabilized by offset π–π stacking between the quinoxaline rings [centroid–centroid distance = 3.8832 (9 Å].

Organofluorine chemistry : applications, sources and sustainability.

OpenAIRE

Harsanyi, A.; Sandford, G.

2015-01-01

Fluorine is an essential element for life in the developed world that impacts hugely on the general public because many pharmaceuticals, agrochemicals, anaesthetics, materials and air conditioning materials owe their important properties to the presence of fluorine atoms within their structures. All fluorine atoms used in organic chemistry are ultimately sourced from a mined raw material, fluorspar (CaF2), but, given current usage and global reserve estimates, there is only sufficient fluorsp...

Exerting control over the helical chirality in the main chain of sergeants-and-soldiers-type poly(quinoxaline-2,3-diyl)s by changing from random to block copolymerization protocols.

Science.gov (United States)

Nagata, Yuuya; Nishikawa, Tsuyoshi; Suginome, Michinori

2015-04-01

Chiral random poly(quinoxaline-2,3-diyl) polymers of the sergeants-and-soldiers-type (sergeant units bearing (S)-3-octyloxymethyl groups) adopt an M- or P-helical conformation in the presence of achiral units bearing propoxymethyl or butoxy groups (soldier units), respectively. Unusual bidirectional induction of the helical sense can be observed for a copolymer with butoxy soldier units upon changing the mole fraction of the sergeant units. In the presence of 16-20% of sergeant units, the selective induction of a P-helix was observed, while the selective induction of an M-helix was observed for a mole fraction of sergeant units of more than 60%. This phenomenon could be successfully employed to control the helical chirality of copolymers by applying either random or block copolymerization protocols. Random or block copolymerization of sergeant and soldier monomers in a 18:82 ratio resulted in the formation of 250mers with almost absolute P- or M-helical conformation, respectively (>99% ee). Incorporation of a small amount of coordination sites into the random and block copolymers resulted in chiral macromolecular ligands, which allowed the enantioselective synthesis of both enantiomers in the Pd-catalyzed asymmetric hydrosilylation of β-methylstyrene.

Evaluation of the ex vivo antimalarial activity of organotin (IV) ethylphenyldithiocarbamate on erythrocytes infected with Plasmodium berghei NK 65.

Science.gov (United States)

Awang, Normah; Jumat, Hafizah; Ishak, Shafariatul Akmar; Kamaludin, Nurul Farahana

2014-06-01

Malaria is the most destructive and dangerous parasitic disease. The commonness of this disease is getting worse mainly due to the increasing resistance of Plasmodium falciparum against antimalarial drugs. Therefore, the search for new antimalarial drug is urgently needed. This study was carried out to evaluate the effects of dibutyltin (IV) ethylphenyldithiocarbamate (DBEP), diphenyltin (IV) ethylphenyldithiocarbamate (DPEP) and triphenyltin (IV) ethylphenyldithiocarbamate (TPEP) compounds as antimalarial agents. These compounds were evaluated against erythrocytes infected with Plasmodium berghei NK65 via ex vivo. Organotin (IV) ethylphenyldithiocarbamate, [R(n)Sn(C9H10NS2)(4-n)] with R = C4H9 and C6H5 for n = 2; R = C6H5 for n = 3 is chemically synthesised for its potential activities. pLDH assay was employed for determination of the concentration that inhibited 50% of the Plasmodium's activity (IC50) after 24 h treatment at concentration range of 10-0.0000001 mg mL(-1). Plasmodium berghei NK65 was cultured in vitro to determine the different morphology of trophozoite and schizont. Only DPEP and TPEP compounds have antimalarial activity towards P. berghei NK65 at IC50 0.094±0.011 and 0.892±0.088 mg mL(-1), respectively. The IC50 of DPEP and TPEP were lowest at 30% parasitemia with IC50 0.001±0.00009 and 0.0009±0.0001 mg mL(-1), respectively. In vitro culture showed that TPEP was effective towards P. berghei NK65 in trophozoite and schizont morphology with IC50 0.0001±0.00005 and 0.00009±0.00003 μg mL(-1), respectively. In conclusion, DPEP and TPEP have antimalarial effect on erythrocytes infected with P. berghei NK65 and have potential as antimalarial and schizonticidal agents.

Distribution of tributyltin (TBT) in the Mandovi estuary

Digital Repository Service at National Institute of Oceanography (India)

Bhosle, N.B.

. Their use as components of antifouling paints has increased several folds for the last few decades. The ship hulls coated with organotin such as tributyltin (TBT) reduce the attachment of marine organisms onto the ship hulls. Although organotins serve...

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.

Metabolism, Distribution, and Elimination of Mequindox in Pigs, Chickens, and Rats.

Science.gov (United States)

Huang, Lingli; Yin, Fujun; Pan, Yuanhu; Chen, Dongmei; Li, Juan; Wan, Dan; Liu, Zhenli; Yuan, Zonghui

2015-11-11

Mequindox (MEQ), a quinoxaline-N,N-dioxide antibacterial agent used to control bacterial enteritis in various food-producing animals, is a potential violative residue in food animal-derived products. The disposition and elimination of MEQ in rats, pigs, and chickens was comprehensively investigated to identify the marker residue and target tissue of MEQ in food animals for residue monitoring. Following a single oral administration, 62-71% of MEQ was rapidly excreted via urine and feces in all species within 24 h. Urinary excretion of radioactivity was 84 and 83.5% of the administered dose in rats and pigs, respectively. More than 92% of the administered dose was excreted in all species within 15 days. Radioactivity was found in nearly all tissues at the first 6 h after dosing, with the majority of radioactivity cleared within 4-6 days. The highest radioactivity and longest persisting time were found to be in the liver and kidney. Totals of 11, 12, and 7 metabolites were identified in rats, chickens, and pigs, respectively. No parent drug could be detected in any of the tissues of pigs and chickens. 3-Methyl-2-acetyl quinoxaline (M1), 3-methyl-2-(1-hydroxyethyl) quinoxaline-N4-monoxide (M4), and 3-methyl-2-(1-hydroxyethyl) quinoxaline-1,4-dioxide (M6) were the common and major metabolites of MEQ in all three species. Additionally, 3-methyl-2-(1-hydroxyethyl) quinoxaline (M5), 3-hydroxymethyl-2-ethanol quinoxaline-1,4-dioxide (M7), and 3-methyl-2-(1-hydroxyethyl) quinoxaline-N1-monoxide (M8) were the major metabolites of MEQ in rats, pigs, and chickens, respectively. M1 was designated to be the marker residue of MEQ in pigs and chickens. These results provide scientific data for the determination of marker residues and withdrawal time of MEQ in food animals and improve the understanding of the toxicity and disposition of MEQ in animals.

Biocidal synthetic coatings based on high-molecular metaloorganic compounds. [Aspergillus flavus; Aspergillus niger; Aspergillus terreus; Penicillium funiculosum; penicillium cyclopium; Penicillium chrysogenum; Paecilomyces varioti; Chaetomium globosum; trichoderma viride

Energy Technology Data Exchange (ETDEWEB)

Mishchenko, V.F.; Zubov, V.A.; Eremenko, Yu.G.

Long-term stays of man and animals in closed life-support systems lead to contamination of the space-craft by various microorganisms. Organotin compounds are considered promising biocidal agents for paints and varnishes with a broad spectrum of action against a variety of microorganisms. Several organotin polymers of the acrylate type were prepared and were found to be effective fungicides.

A new bioassay for the inspection and identification of TBT-containing antifouling paint.

Science.gov (United States)

Gueuné, Hervé; Thouand, Gérald; Durand, Marie-José

2009-11-01

Since the 1960s tributyl (TBT)-based antifouling paints are widely applied to protect ship's hulls from biofouling. Due to its high toxicity to aquatic ecosystem most of the countries (28 nations in 2008) signed the AFS convention to control the use of harmful antifouling systems on ships. Nevertheless there is currently no simple method to control the presence of organotin in paint. In this study, we propose a bioassay based on the use of a recombinant bioluminescent bacteria to detect directly in paint the presence of TBT. We also propose a simple device as an inspection system to control the absence of organotin in the ship's hull paint. The presence of organotin could be revealed in less than three hours.

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

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Bruno Commare

2017-06-01

Full Text Available 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 (heteroaromatic derivatives.

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.

6a-Nitro-6-(2,2,7,7-tetramethyltetrahydro-3aH-bis[1,3]dioxolo[4,5-b:4′,5′-d]pyran-5-yl-6a,6b,7,8,9,11a-hexahydro-6H-spiro[chromeno[3,4-a]pyrrolizine-11,11′-indeno[1,2-b]quinoxaline

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T. Anuradha

2014-01-01

Full Text Available In the title compound, C39H38N4O8, the quinoxaline and indene subunits are essentially planar, with maximum deviations of 0.071 (2 and 0.009 (2 Å, respectively. The indenoquinoxaline system forms a dihedral angle of 72.81 (3° with the chromenopyrrolizine system. The two dioxolane rings, as well as the pyran ring of the chromeno group and the terminal pyrrolizine, each adopt an envelope conformation with O and C as flap atoms. The central pyrrolizine ring adopts a twisted conformation. Intramolecular C—H...O and C—H...N hydrogen bonds occur. The crystal structure exhibits C—H...O hydrogen bonds, and is further stablized by C—H...π interactions, forming a two-dimensional network along the bc plane.

Dibutyltin disrupts glucocorticoid receptor function and impairs glucocorticoid-induced suppression of cytokine production.

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Christel Gumy

Full Text Available BACKGROUND: Organotins are highly toxic and widely distributed environmental chemicals. Dibutyltin (DBT is used as stabilizer in the production of polyvinyl chloride plastics, and it is also the major metabolite formed from tributyltin (TBT in vivo. DBT is immunotoxic, however, the responsible targets remain to be defined. Due to the importance of glucocorticoids in immune-modulation, we investigated whether DBT could interfere with glucocorticoid receptor (GR function. METHODOLOGY: We used HEK-293 cells transiently transfected with human GR as well as rat H4IIE hepatoma cells and native human macrophages and human THP-1 macrophages expressing endogenous receptor to study organotin effects on GR function. Docking of organotins was used to investigate the binding mechanism. PRINCIPAL FINDINGS: We found that nanomolar concentrations of DBT, but not other organotins tested, inhibit ligand binding to GR and its transcriptional activity. Docking analysis indicated that DBT inhibits GR activation allosterically by inserting into a site close to the steroid-binding pocket, which disrupts a key interaction between the A-ring of the glucocorticoid and the GR. DBT inhibited glucocorticoid-induced expression of phosphoenolpyruvate carboxykinase (PEPCK and tyrosine-aminotransferase (TAT and abolished the glucocorticoid-mediated transrepression of TNF-alpha-induced NF-kappaB activity. Moreover, DBT abrogated the glucocorticoid-mediated suppression of interleukin-6 (IL-6 and TNF-alpha production in lipopolysaccharide (LPS-stimulated native human macrophages and human THP-1 macrophages. CONCLUSIONS: DBT inhibits ligand binding to GR and subsequent activation of the receptor. By blocking GR activation, DBT may disturb metabolic functions and modulation of the immune system, providing an explanation for some of the toxic effects of this organotin.

A survey of antifoulants in sediments from Ports and Marinas along the French Mediterranean coast.

Science.gov (United States)

Cassi, Roberto; Tolosa, Imma; de Mora, Stephen

2008-11-01

Due to deleterious effects on non-target organisms, the use of organotin compounds on boat hulls of small vessels (ports and marinas along the France Mediterranean coastline (Cote d'Azur) and analysed for organotin compounds, Irgarol 1051, Sea-nine 211, Chlorothalonil, Dichlofluanid and Folpet. Every port and marina exhibited high levels of organotin compounds, with concentrations in sediments ranging from 37 ng Sn g(-1) dry wt in Menton Garavan to over 4000 ng Sn g(-1) dry wt close to the ship chandler within the port of Villefranche-sur-Mer. TBT degradation indexes suggested that fresh inputs are still made. Among the other antifoulants monitored, only Irgarol 1051 exhibited measurable concentrations in almost every port, with concentrations ranging from 40 ng g(-1) dry wt (Cannes) to almost 700 ng g(-1) dry wt (Villefranche-sur-Mer, ship chandler).

Electrochemical sensor based on molecularly imprinted polymer film via sol-gel technology and multi-walled carbon nanotubes-chitosan functional layer for sensitive determination of quinoxaline-2-carboxylic acid.

Science.gov (United States)

Yang, Yukun; Fang, Guozhen; Liu, Guiyang; Pan, Mingfei; Wang, Xiaomin; Kong, Lingjie; He, Xinlei; Wang, Shuo

2013-09-15

Quinoxaline-2-carboxylic acid (QCA) is difficult to measure since only trace levels are present in commercial meat products. In this study, a rapid, sensitive and selective molecularly imprinted electrochemical sensor for QCA determination was successfully constructed by combination of a novel modified glassy carbon electrode (GCE) and differential pulse voltammetry (DPV). The GCE was fabricated via stepwise modification of multi-walled carbon nanotubes (MWNTs)-chitosan (CS) functional composite and a sol-gel molecularly imprinted polymer (MIP) film on the surface. MWNTs-CS composite was used to enhance the electron transfer rate and expand electrode surface area, and consequently amplify QCA reduction electrochemical response. The imprinted mechanism and experimental parameters affecting the performance of MIP film were discussed in detail. The resulting MIP/sol-gel/MWNTs-CS/GCE was characterized using various electrochemical methods involving cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and DPV. The sensor using MIP/sol-gel/MWNTs-CS/GCE as working electrode showed a linear current response to the target QCA concentration in the wide range from 2.0×10(-6) to 1.0×10(-3)molL(-1) with a low detection limit of 4.4×10(-7)molL(-1) (S/N=3). The established sensor with excellent reproductivity and stability was applied to evaluate commercial pork products. At five concentration levels, the recoveries and standard deviations were calculated as 93.5-98.6% and 1.7-3.3%, respectively, suggesting the proposed sensor is promising for the accurate quantification of QCA at trace levels in meat samples. Copyright © 2013 Elsevier B.V. All rights reserved.

Organotin pollution at Arraial do Cabo, Rio de Janeiro State, Brazil: increasing levels after the TBT ban

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Raquel Toste

2011-03-01

Full Text Available Imposex, an endocrine disruption phenomenon, is a biomarker of tributyltin (TBT exposure in marine gastropod populations. The occurrence and intensity of the syndrome in populations of the neogastropod Stramonita haemastoma were ascertained at nine sampling stations in October 2008 at Arraial do Cabo, a very important tourist resort in Rio de Janeiro state (Brazil and part of the Marine Extractive Reserve of Arraial do Cabo. The results obtained made it possible to evaluate the changes which had occurred since the last biomonitoring campaign, undertaken in 2001, at these same stations. Despite the ban on the use of TBT imposed by the Brazilian Navy in 2003, the controls on the use of this agent in Brazil resulting from the establishment of NORMAM 23 by the Navy in 2007 and the complete ban of organotin compounds in antifouling paint formulae by the IMO on a global scale in 2008, imposex was still detected. Instead of the expected reduction, an increase was observed in the areas affected by imposex. Furthermore, populations in the areas seriously affected by imposex in 2001 were absent in the 2008 sampling campaign. These results suggest an increase in TBT pollution in the study area, indicating the inefficacy of legislative measures.O imposex, um fenômeno de desregulação endócrina, é um biomarcador da exposição ao tributilestanho (TBT em populações de gastrópodes marinhos. A ocorrência e intensidade dessa síndrome nas populações do neogastrópode Stramonita haemastoma foram verificadas em nove estações amostrais em outubro de 2008 em Arraial do Cabo, uma área de grande importância turística no Rio de Janeiro (Brasil e integrante da Reserva Extrativista Marinha de Arraial do Cabo. Com os resultados obtidos foi possível avaliar as alterações ocorridas desde o último biomonitoramento realizado em 2001, nessas mesmas estações. Mesmo após o banimento do TBT pela Marinha do Brasil em 2003, a entrada em vigor dos controles ao

Lewis Acid Catalyzed Asymmetric Three-Component Coupling Reaction: Facile Synthesis of α-Fluoromethylated Tertiary Alcohols.

Science.gov (United States)

Aikawa, Kohsuke; Kondo, Daisuke; Honda, Kazuya; Mikami, Koichi

2015-12-01

A chiral dicationic palladium complex is found to be an efficient Lewis acid catalyst for the synthesis of α-fluoromethyl-substituted tertiary alcohols using a three-component coupling reaction. The reaction transforms three simple and readily available components (terminal alkyne, arene, and fluoromethylpyruvate) to valuable chiral organofluorine compounds. This strategy is completely atom-economical and results in perfect regioselectivities and high enantioselectivities of the corresponding tertiary allylic alcohols in good to excellent yields. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tidstrend av oidentifierade poly- och perfluorerade alkylämnen i slam från reningsverk i Sverige

OpenAIRE

Yeung, Leo W. Y.; Eriksson, Ulrika

2017-01-01

The aims of this investigation are 1) to study spatial variation in PFAS discharge by measuring PFAS in sludge samples collected from four wastewater treatment plants (WWTPs: Öhn - Umeå, Bergkvara - Torsås, Henriksdal – Stockholm, and Gässlösa - Borås); 2) to evaluate the amount of unidentified PFAS, if any, in the sludge samples by measuring total organofluorine (TOF) in the samples; 3) to study the temporal discharge and pattern of PFASs by measuring different PFASs in archived sludge sampl...

Crystal Engineering: Synthesis and Structural Analysis of Coordination Polymers with Wavelike Properties

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Matasebia T. Munie

2011-10-01

Full Text Available Supramolecular coordination polymers with wavelike structures have been synthesized by self-assembly and their structures analyzed using the sine trigonometric function. Slow evaporation of a methylene chloride-methanol solution of a 1:1 molar mixture of [M(tmhd2], where M = Co or Ni, and quinoxaline; a 1:2:1 molar mixture of [M(acac2], where M = Co or Ni, 2,2,6,6-tetramethyl-3,5-heptadione and quinoxaline; or a 1:2:1 molar mixture of [Co(acac2], dibenzoylmethane, and quinoxaline, yielded the crystalline coordination polymers. In the presence of the nitrogenous base, ligand scrambling occurs yielding the most insoluble product. The synthesis and structures of the following wavelike polymers are reported: trans-[Co(DBM2(qox]n·nH2O (2, trans-[Co(tmhd2(qox]n (3, trans-[Ni(tmhd2(qox]n (4, where DBM− = dibenzoylmethanate, tmhd− = 2,2,6,6-tetramethyl-3,5-heptadionate, and qox = quinoxaline. The wavelike structures are generated by intramolecular steric interactions and crystal packing forces between the chains. Some of the tert-butyl groups show a two-fold disorder. The sine function, φ = A sin 2πx/λ, where φ = distance (Ǻ along the polymer backbone, λ = wavelength (Ǻ, A = amplitude (Ǻ, x = distance (Ǻ along the polymer axis, provides a method to approximate and visualize the polymer structures.

Development and application of an ultratrace method for speciation of organotin compounds in cryogenically archived and homogenized biological materials

Energy Technology Data Exchange (ETDEWEB)

Point, David; Davis, W.C.; Christopher, Steven J.; Ellisor, Michael B.; Pugh, Rebecca S.; Becker, Paul R. [Hollings Marine Laboratory, National Institute of Standards and Technology, Analytical Chemistry Division, Charleston, SC (United States); Donard, Olivier F.X. [Laboratoire de Chimie Analytique BioInorganique et Environnement UMR 5034 du CNRS, Pau (France); Porter, Barbara J.; Wise, Stephen A. [National Institute of Standards and Technology, Analytical Chemistry Division, Gaithersburg, MD (United States)

2007-04-15

a promising alternative to conventional freeze-dried materials for organotin speciation analysis, because these are, at present, the best conditions for minimizing degradation of thermolabile species and for long-term archival. Finally, the potential of the analytical method was illustrated by analysis of polar bear (Ursus maritimus) and beluga whale (Delphinapterus leuca) liver samples that had been collected in the Arctic and archived at the Marine Environmental Specimen Bank. Significant concentrations of butyltin compounds were found in the samples and provide the first evidence of the presence of this class of contaminant in the Arctic marine ecosystem. (orig.)

Organofluorine chemistry: synthesis and conformation of vicinal fluoromethylene motifs.

Science.gov (United States)

O'Hagan, David

2012-04-20

The C-F bond is the most polar bond in organic chemistry, and thus the bond has a relatively large dipole moment with a significant -ve charge density on the fluorine atom and correspondingly a +ve charge density on carbon. The electrostatic nature of the bond renders it the strongest one in organic chemistry. However, the fluorine atom itself is nonpolarizable, and thus, despite the charge localization on fluorine, it is a poor hydrogen-bonding acceptor. These properties of the C-F bond make it attractive in the design of nonviscous but polar organic compounds, with a polarity limited to influencing the intramolecular nature of the molecule and less so intermolecular interactions with the immediate environment. In this Perspective, the synthesis of aliphatic chains carrying multivicinal fluoromethylene motifs is described. It emerges that the dipoles of adjacent C-F bonds orientate relative to each other, and thus, individual diastereoisomers display different backbone carbon chain conformations. These conformational preferences recognize the influence of the well-known gauche effect associated with 1,2-difluoroethane but extend to considering 1,3-fluorine-fluorine dipolar repulsions. The synthesis of carbon chains carrying two, three, four, five, and six vicinal fluoromethylene motifs is described, with an emphasis on our own research contributions. These motifs obey almost predictable conformational behavior, and they emerge as candidates for inclusion in the design of performance organic molecules. © 2012 American Chemical Society

Formation of new heterocyclic amine mutagens by heating creatinine, alanine, threonine and glucose.

Science.gov (United States)

Skog, K; Knize, M G; Felton, J S; Jägerstad, M

1992-08-01

A mixture of alanine, threonine, creatinine and glucose was heated in diethylene glycol and water (5:1, v/v) for 15 min at 200 degrees C. The mutagens formed were purified by high-performance liquid chromatography using the Ames/Salmonella mutagenic activity to guide the purification. The structures of the purified mutagens were determined using UV absorption, mass and NMR spectrometry. A new mutagenic compound with a mass number of 217 was found and its mass spectrum did not correspond to any known mutagen derived from food. This new compound accounted for 4% of the total mutagenic activity. Other mutagenic compounds were identified as MeIQx (2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline), 4,8-DiMeIQx (2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline), and a new mutagen 4,7,8-TriMeIQx (2-amino-3,4,7,8-tetramethylimidazo[4,5-f]quinoxaline) with a mutagenic activity of 73,000 TA98 revertants per microgram. The percentage of the mutagenic activity attributable to MeIQx, 4,8-DiMeIQx and 4,7,8-TriMeIQx was 10%, 70% and 3%, respectively. The yield of MeIQx, 4,8-DiMeIQx and 4,7,8-TriMeIQx was 10, 36 and 6 nmole/mmole creatinine. The formation of TriMeIQx from natural meat components suggests that this new quinoxaline mutagen may be present in cooked foods.

Imposex in Thais rustica (Mollusca: Neogastropoda (Lamark, 1822 as an indicator of organotin compounds pollution at Maceio coast (Northeastern Brazil

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Edmundo Camillo

2004-06-01

Full Text Available The use of OTC (organotin compounds as biocides in naval antifouling paints causes impacts on non-target organisms. One of these impacts is a syndrome called imposex in gastropod molluscs. Imposex is the imposition of male secondary sexual characteristics in female gastropods as result of endocrine disruption. In this preliminary study, imposex was observed in four out of ten sampled stations in Maceió: the city Port (100% females exhibited imposex, the Marine Emissary (23% females exhibited imposex, the Marine Terminal (35% females exhibited imposex and Saco da Pedra beach (12% females exhibited imposex. These stations were distributed in a NE-SW orientation from the Port southwards along the coastline, following the general circulation pattern of the area. The low values of VDSI, RPSI and RPLI indicate that Maceió Coast is a less contaminated area, probably because of low shipping activities together with the fact that the sampling zone is an open coastal system and not an enclosed bay. These results suggest that the imposex development in Thais rustica may be used as a biological indicator of OTC pollution.O uso de COE (compostos orgânicos de estanho como biocida em tintas antiincrustantes para embarcações causa impactos em organismos não-alvos. Um destes impactos é a síndrome chamada imposex, em moluscos gastrópodos. Imposex é a imposição de caracteres sexuais secundários masculinos em fêmeas de gastrópodos como resultado de desregulação endócrina. Neste estudo preliminar, o imposex foi observado em quatro de dez estações de amostragem em Maceió: o Porto de Maceió (100% de fêmeas imposexadas, o Emissário Submarino (23% de fêmeas imposexadas, o Terminal Marítimo (35% de fêmeas imposexadas e a praia do Saco da Pedra (12% de fêmeas imposexadas. Estas estações estão distribuídas no litoral no sentido NE/SW a partir do Porto, seguindo o padrão de circulação local. Os valores relativamente baixos dos �

Experimental and theoretical studies of the thermal behavior of titanium dioxide-SnO2 based composites.

Science.gov (United States)

Voga, G P; Coelho, M G; de Lima, G M; Belchior, J C

2011-04-07

In this paper we report experimental and theoretical studies concerning the thermal behavior of some organotin-Ti(IV) oxides employed as precursors for TiO(2)/SnO(2) semiconducting based composites, with photocatalytic properties. The organotin-TiO(2) supported materials were obtained by chemical reactions of SnBu(3)Cl (Bu = butyl), TiCl(4) with NH(4)OH in ethanol, in order to impregnate organotin oxide in a TiO(2) matrix. A theoretical model was developed to support experimental procedures. The kinetics parameters: frequency factor (A), activation energy, and reaction order (n) can be estimated through artificial intelligence methods. Genetic algorithm, fuzzy logic, and Petri neural nets were used in order to determine the kinetic parameters as a function of temperature. With this in mind, three precursors were prepared in order to obtain composites with Sn/TiO(2) ratios of 0% (1), 15% (2), and 30% (3) in weight, respectively. The thermal behavior of products (1-3) was studied by thermogravimetric experiments in oxygen.

Time trend of butyl- and phenyl-tin contamination in organisms of the Lagoon of Venice (1999-2003).

Science.gov (United States)

Zanon, F; Rado, N; Centanni, E; Zharova, N; Pavoni, B

2009-05-01

In the period 1999-2003 a monitoring study on the accumulation of organotin compounds in edible organisms in the Lagoon of Venice was conducted. Butyl and Phenyl derivatives were determined in pooled samples of Mytilus galloprovincialis and Tapes spp. with the aims of assessing organotin contamination in the Lagoon of Venice in the period just preceding their ban in Europe, monitoring the concentrations in organisms with a high commercial use, evaluating a potential hazard for human health due to seafood and identifying the possible contamination sources. Sampling stations (up to 20) were distributed around the Lagoon and particularly concentrated in the area close to the town of Chioggia. Significantly higher (analysis of variance (ANOVA), p 0.05) in either species. Furthermore, by analyzing the entire data set, it is evident that most stations show analogous concentrations in the 3 years for both species, whereas few have anomalously higher concentrations. If organotin concentrations in specimens from some sites are compared with the Tolerable Average Residue Level, a possible risk for human health must be considered.

The effect of tributyltin on human eosinophilic [correction of eosinophylic] leukemia EoL-1 cells.

Science.gov (United States)

Sroka, Jolanta; Włosiak, Przemysław; Wilk, Anna; Antonik, Justyna; Czyz, Jarosław; Madeja, Zbigniew

2008-01-01

Organotin compounds are chemicals that are widely used in industry and agriculture as plastic stabilizers, catalysts and biocides. Many of them, including tributyltin (TBT), have been detected in human food and, as a consequence, detectable levels have been found in human blood. As organotin compounds were shown to possess immunotoxic activity, we focused our attention on the effect of TBT on the basic determinants of the function of eosinophils, i.e. cell adhesiveness and motility. We used human eosinophylic leukemia EoL-1 cells, a common in vitro cellular model of human eosinophils. Here, we demonstrate that TBT causes a dose-dependent decrease in the viability of EoL-1 cells. When administered at sub-lethal concentrations, TBT significantly decreases the adhesion of EoL-1 cells to human fibroblasts (HSFs) and inhibits their migration on fibroblast surfaces. Since the basic function of eosinophils is to invade inflamed tissues, our results indicate that TBT, and possibly other organotin compounds, may affect major cellular properties involved in the determination of in vivo eosinophil function.

Study of the catalytic selectivity of an aqueous two-component polyurethane system by ftir spectroscopy

Directory of Open Access Journals (Sweden)

Stamenković Jakov V.

2003-01-01

Full Text Available The difficulty in formulating a two component waterborne polyurethane, is the isocyanate-water side reaction, which can lead to gassing/foaming, loss of isocyanate functionality, low gloss and a reduced pot life. To compensate for this side reaction, these formulations usually contain a large excess of isocyanate. Tin compounds, especially dibutyltin dilaurate, are widely used in coatings as catalysts for the isocyanate/hydroxyl reaction. Because of the high aquatic toxicity of some organotin compounds, there has been an attempt to ban organotin compounds from all coating applications. As a general rule, organotin catalysts are not selective, they catalyze the reaction of isocyanates with both hydroxyl groups and water and also catalyze the hydrolysis of ester groups. One novel approach to control the water side reaction is the use of catalysts which selectively catalyze the isocyanate-polyol reaction and not the isocyanate-water reaction. The selectivity of a variety of metal catalysts (metal octoates, metal acetylacetonates and mangan chelates with mixed ligands to catalyze the preferred reaction was measured using the FTIR method.

Organotin(IV Derivatives of 2-Acetylpyridine-N(4-Phenylthiosemicarbazone, HAP4P, and 2-Hydroxyacetophenone-N(4-Phenylthiosemicarbazone, H2DAP4P: Crystal and Molecular Structure of [SnMe2(DAP4P] and [SnBu2(DAP4P

Directory of Open Access Journals (Sweden)

Sousa Gerimário F. de

2001-01-01

Full Text Available The reactions of 2-acetylpyridine-N(4-phenylthiosemicarbazone, HAP4P, and 2-hydroxyacetophenone-N(4-phenylthiosemicarbazone, H2DAP4P, with R4-mSnXm (m = 2, 3; R = Me, nBu, Ph and X = Cl, Br led to the formation of hexa- and penta-coordinated organotin(IV complexes, which were studied by microanalysis, IR, ¹H-NMR and Mössbauer spectroscopies. The molecular structures of [SnMe2(DAP4P] and [Sn nBu2(DAP4P] were determined by single-crystal X-ray diffraction studies. In the compounds [SnClMe2(AP4P] and [SnBrMe2(AP4P], the deprotonated ligand AP4P- is N,N,S-bonded to the Sn(IV atoms, which exhibit strongly distorted octahedral coordination. The structures of [SnMe2(DAP4P] and [Sn nBu2(DAP4P] revealed that the DAP4P2- anion acts as a O,N,S-tridentate ligand. In these cases, the Sn(IV atoms adopt a strongly distorted trigonal bipyramidal configuration where the azomethine N and the two C atoms are on the equatorial plane while the O and the S atoms occupy the axial positions.

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.

Spatial variation of butyltins in an intermittent French River

Science.gov (United States)

Chahinian, N.; Bancon-Montigny, C.; Brunel, V.; Tournoud, M. G.

2009-04-01

Organotins (OTs) have been increasingly used in industrial applications because of their thermoresistant and biocidal properties: in the 1970s and 1980s Tributyltin (TBT) based anti-fouling paints were used on ships and vessels of all kinds. However, studies pointed out the highly toxic nature of these compounds and their active role as an endoctrine perturbator. This lead the EU to ban the use of TBT paints in 2003. The toxicity of OTs combined to their widespread use has lead then to be included in the priority list of the EU water framework directive. Organotins are prone to adsorption, can bond easily to particulate matter and "migrate" from the water column unto the sediments where their half-life can extend to a few decades. Consequently sediments can become important organotin stores and release OT compounds during dredging operations, storms, tides or floods. The main objective of this work was to investigate the presence of organotin compounds in the sediments and water column of an intermittent river reach i.e. to establish the presence of organotins in regular flow conditions and assess their spatial variability. The study zone is a reach of the Vène River located in southern France. The Vène is a major tributary of the Thau lagoon which is an important shellfish farming site and thus very vulnerable to OT contamination. Butyltin, trace metal and dissolved organic carbon (DOC) concentrations were measured on water and sediment samples collected over a 3 month period stretching from March to May 2008. The results revealed the presence of butyltins at concentrations exceeding the EU and French pollution limits. In terms of spatial variability, by combining the butyltin and the trace metal results at 16 locations along the reach, two point pollutions spots were identified, namely a sewage treatment plant and a drainage ditch. However, the later are not the only OT input sources, the results of the sediment analysis pointed out to a diffuse pollution

Erythrocyte hemolysis by organic tin and lead compounds

Energy Technology Data Exchange (ETDEWEB)

Kleszcynska, H. [Agricultural Univ., Wroclaw (Poland). Dept. of Physics and Biophysics; Hladyszowski, J. [Agricultural Univ., Wroclaw (Poland). Dept. of Physics and Biophysics; Pruchnik, H. [Agricultural Univ., Wroclaw (Poland). Dept. of Physics and Biophysics; Przestalski, S. [Agricultural Univ., Wroclaw (Poland). Dept. of Physics and Biophysics

1997-01-01

The effect of trialkyllead and trialkyltin on pig erythrocyte hemolysis has been studied and compared. The results of experiments showed that the hemolytic activity of organoleads increases with their hydrophobicity and follows the sequence: triethyllead chloride < tri-n-propyllead chloride < tributyllead chloride. And similarly in the case of organotins: triethyltin chloride < tri-n-propyltin chloride < tributyltin chloride. Comparison of the hemolytic activity of organoleads and organotins indicates that the lead compounds exhibit higher hemolytic activity. The methods of quantum chemistry allowed to determine the maximum electric potential of the ions R{sub 3}Pb{sup +} and R{sub 3}Sn{sup +}, and suggest a relationship between the potential and toxicity. (orig.)

Formation of 4-hydroxy-2,5-dimethyl-3[2H]-furanone by Zygosaccharomyces rouxii: identification of an intermediate.

Science.gov (United States)

Hauck, Tobias; Brühlmann, Fredi; Schwab, Wilfried

2003-07-01

The formation of the important flavor compound 4-hydroxy-2,5-dimethyl-3[2H]-furanone (HDMF; Furaneol) from D-fructose-1,6-bisphosphate by the yeast Zygosaccharomyces rouxii was studied with regard to the identification of intermediates present in the culture medium. Addition of o-phenylenediamine, a trapping reagent for alpha-dicarbonyls, to the culture medium and subsequent analysis by high-pressure liquid chromatography with diode array detection revealed the formation of three quinoxaline derivatives derived from D-fructose-1,6-bisphosphate under the applied growth conditions (30 degrees C; pH 4 to 5). Isolation and characterization of these compounds by tandem mass spectrometry and nuclear magnetic resonance spectroscopy led to the identification of phosphoric acid mono-(2,3,4-trihydroxy-4-quinoxaline-2-yl-butyl) ester (Q1), phosphoric acid mono-[2,3-dihydroxy-3-(3-methyl-quinoxaline-2-yl)-propyl] ester (Q2), and phosphoric acid mono-[2-hydroxy-3-(3-methyl-quinoxaline-2-yl)-propyl] ester (Q3). Q1 and Q2 were formed independently of Z. rouxii cells, whereas Q3 was detected only in incubation systems containing the yeast. Identification of Q2 demonstrated for the first time the chemical formation of 1-deoxy-2,3-hexodiulose-6-phosphate in the culture medium, a generally expected but never identified intermediate in the formation pathway of HDMF. Since HDMF was detected only in the presence of Z. rouxii cells, additional enzymatic steps were presumed. Incubation of periplasmic and cytosolic protein extracts obtained from yeast cells with D-fructose-1,6-bisphosphate led to the formation of HDMF, implying the presence of the required enzymes in both extracts.

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.

Organotin levels in seafood

NARCIS (Netherlands)

Belfroid, A.C.; Purperhart, M.; Ariese, F.

2000-01-01

Tolerable average residue levels (TARL) for tributylin (TBT) in seafood products were calculated based on the tolerable daily intake (TDI) of TBT and the seafood consumption of the average consumer in various countries. Data from the literature show that these TARLs in seafood are exceeded in one or

Development of new organometallic species for the labelling of radiotracers with short half-lives radioisotopes

International Nuclear Information System (INIS)

Huet-Dales, A.

2003-11-01

The reactivity of clean organotins have been studied in the Stille coupling reaction in fast conditions, witch can be used with short half-life radioisotope. In a first part, development of the reaction conditions have been studied for the transfer of a methyl group by the Stille coupling reaction, via the synthesis of the correspond mono-organotin. The reaction time was optimized onto model compounds in 12-carbon and 11-carbon chemistry. In a second part, this methodology was applied to the synthesis of NK3 receptors radioligands, in 12-carbon and 11-carbon chemistry. Biological studies showed that these ligands have a good affinity with NK3 receptors, and are potential positron emission tomography tracers. (author)

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.

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.

Synthesis, Characterization and catalytic activity of triorganotin(IV) carboxylates for the production of biodiesel from rocket seed oil

International Nuclear Information System (INIS)

Tariq, M.; Ali, S.

2013-01-01

Organotin(IV) carboxylates have a wide range of industrial applications such as antifouling paints, PVC stabilization, ion carries in electrochemical membranes and homogeneous catalysts. The catalytic application of organotin carboxylates are in the field of silicone curing, polyurethane formation and esterification. Only a limited literature is available regarding the use of organotin carboxylates in the transesterification of vegetable oil to produce biodiesel . The present study deals with the synthesis of some new triorganotin(IV) carboxylates for their subsequent use as catalyst for transesterification of rocket seed oil to produce biodiesel. The three new triorganotin(IV) i.e. (Me/sub 3/SnL) (1),(Bu/sub 3/Snl) (2) and (Ph/sub 3/SnL) (3), were synthesized by refluxing sodium salt of ligand (NaL), where L=O/sub 2/C(CH/sub 3/)C=CHC/sub 6/H/sub 4/F with trimethyl, tributyl and triphenyl tin(IV) chlorides, respectively for 10 hrs. The synthesized compounds were characterized by instrumental techniques like FT-IR and NMR (1H, 13C). The catalytic activity of these compounds was assessed for transesterification of triglycerides in rocket seed oil to produce biodiesel. All the tested compounds showed good catalytic activity in the order 1> 2 > 3. (author)

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.

Presidential Green Chemistry Challenge: 1996 Designing Greener Chemicals Award

Science.gov (United States)

Presidential Green Chemistry Challenge 1996 award winner, Rohm and Haas, developed Sea-Nine, a marine antifoulant to control plants and animals on ship hulls. Sea-Nine replaces persistent, toxic organotin antifoulants.

IJS v10 n1.cdr

African Journals Online (AJOL)

De Don

2-dicarbonyl derivatives under different reaction conditions) have been reported to show various biological properties. The quinoxaline ring system has been described as bioisoster of aromatic rings, including quinoline, naphthalene,.

Green oxidations: Titanium dioxide induced tandem oxidation coupling reactions

OpenAIRE

Jeena, Vineet; Robinson, Ross S

2009-01-01

Summary The application of titanium dioxide as an oxidant in tandem oxidation type processes is described. Under microwave irradiation, quinoxalines have been synthesized in good yields from the corresponding ?-hydroxyketones.

Miljøfarlige stoffer i ålekvabbe - Delrapport I

DEFF Research Database (Denmark)

Dahllöf, Ingela; Strand, Jakob

Miljøfarlige stoffer i ålekvabbe blev analyseret og sammenholdt med forekomst af misdannede ålekvabbeunger. Kobber, organotin, dioxiner, furaner, dioxin-lignende PCB’er samt bromerede flammehæmmere blev vurderet....

Sensitive and selective electrochemical determination of quinoxaline-2-carboxylic acid based on bilayer of novel poly(pyrrole) functional composite using one-step electro-polymerization and molecularly imprinted poly(o-phenylenediamine)

Energy Technology Data Exchange (ETDEWEB)

Yang, Yukun; Fang, Guozhen; Wang, Xiaomin; Pan, Mingfei; Qian, Hailong; Liu, Huilin; Wang, Shuo, E-mail: s.wang@tust.edu.cn

2014-01-02

Graphical abstract: -- Highlights: •PPY-GO-BiCoPc composite was formed using a simple electrochemical method for the first time. •A novel PoPD-MIP sensor based on PPY-GO-BiCoPc composite had been fabricated. •The PPY-GO-BiCoPc functional composite was introduced to improve performance of the sensor. •Highly sensitive, selective and stable sensor had been achieved. •The established MIP sensor could be promising in food safety analysis. -- Abstract: A facile and efficient molecularly imprinted polymer (MIP) recognition element of electrochemical sensor was fabricated by directly electro-polymerizing monomer o-phenylenediamine (oPD) in the presence of template quinoxaline-2-carboxylic acid (QCA), based on one-step controllable electrochemical modification of poly(pyrrole)-graphene oxide-binuclear phthalocyanine cobalt (II) sulphonate (PPY-GO-BiCoPc) functional composite on glassy carbon electrode (GCE). The MIP film coated on PPY-GO-BiCoPc functional composite decorated GCE (MIP/PPY-GO-BiCoPc/GCE) was presented for the first time. The synergistic effect and electro-catalytic activity toward QCA redox of PPY-GO-BiCoPc functional composite were discussed using various contrast tests. Also, the effect of experimental variables on the current response such as, electro-polymerization cycles, template/monomer ratio, elution condition for template removal, pH of the supporting electrolyte and accumulation time, were investigated in detail. Under the optimized conditions, the proposed MIP sensor possessed a fast rebinding dynamics and an excellent recognition capacity to QCA, while the anodic current response of square wave voltammetry (SWV) was well-proportional to the concentration of QCA in the range of 1.0 × 10{sup −8}–1.0 × 10{sup −4} and 1.0 × 10{sup −4}–5.0 × 10{sup −4} mol L{sup −1} with a low detection limit of 2.1 nmol L{sup −1}. The established sensor was applied successfully to determine QCA in commercial pork and chicken muscle

Sensitive and selective electrochemical determination of quinoxaline-2-carboxylic acid based on bilayer of novel poly(pyrrole) functional composite using one-step electro-polymerization and molecularly imprinted poly(o-phenylenediamine)

International Nuclear Information System (INIS)

Yang, Yukun; Fang, Guozhen; Wang, Xiaomin; Pan, Mingfei; Qian, Hailong; Liu, Huilin; Wang, Shuo

2014-01-01

Graphical abstract: -- Highlights: •PPY-GO-BiCoPc composite was formed using a simple electrochemical method for the first time. •A novel PoPD-MIP sensor based on PPY-GO-BiCoPc composite had been fabricated. •The PPY-GO-BiCoPc functional composite was introduced to improve performance of the sensor. •Highly sensitive, selective and stable sensor had been achieved. •The established MIP sensor could be promising in food safety analysis. -- Abstract: A facile and efficient molecularly imprinted polymer (MIP) recognition element of electrochemical sensor was fabricated by directly electro-polymerizing monomer o-phenylenediamine (oPD) in the presence of template quinoxaline-2-carboxylic acid (QCA), based on one-step controllable electrochemical modification of poly(pyrrole)-graphene oxide-binuclear phthalocyanine cobalt (II) sulphonate (PPY-GO-BiCoPc) functional composite on glassy carbon electrode (GCE). The MIP film coated on PPY-GO-BiCoPc functional composite decorated GCE (MIP/PPY-GO-BiCoPc/GCE) was presented for the first time. The synergistic effect and electro-catalytic activity toward QCA redox of PPY-GO-BiCoPc functional composite were discussed using various contrast tests. Also, the effect of experimental variables on the current response such as, electro-polymerization cycles, template/monomer ratio, elution condition for template removal, pH of the supporting electrolyte and accumulation time, were investigated in detail. Under the optimized conditions, the proposed MIP sensor possessed a fast rebinding dynamics and an excellent recognition capacity to QCA, while the anodic current response of square wave voltammetry (SWV) was well-proportional to the concentration of QCA in the range of 1.0 × 10 −8 –1.0 × 10 −4 and 1.0 × 10 −4 –5.0 × 10 −4 mol L −1 with a low detection limit of 2.1 nmol L −1 . The established sensor was applied successfully to determine QCA in commercial pork and chicken muscle samples with acceptable

Reaction kinetics and transformation of carbadox and structurally related compounds with aqueous chlorine.

Science.gov (United States)

Shah, Amisha D; Kim, Jae-Hong; Huang, Ching-Hua

2006-12-01

The potential release of carbadox (CDX), a commonly used antibacterial agent in swine husbandry, into water systems is of a concern due to its carcinogenic and genotoxic effects. Until this study, the reactivity of carbadox (possessing quinoxaline N,N'-dioxide and hydrazone moieties) toward aqueous chlorine has yetto be investigated in depth. Chemical reactivity, reaction kinetics, and transformation pathways of carbadox and structurally related compounds with free chlorine under typical water treatment conditions were determined. This study found that only CDX and desoxycarbadox (DCDX), a main metabolite of CDX with no ring N-oxide groups, react rapidly with free chlorine while other structurally related compounds including olaquindox, quindoxin, quinoxaline N-oxide, quinoxaline, and quinoline N-oxide do not. The reaction kinetics of CDX and DCDX with chlorine are highly pH dependent (e.g., the apparent second-order rate constant, kapp, for CDX ranges from 51.8 to 3.15 x 10(4) M(-1)s(-1) at pH 4-11). The high reactivity of CDX and DCDX to chlorine involves deprotonation of their hydrazone N-H moieties where initial chlorine attack results in a reactive intermediate that is further attacked by nucleophiles in the matrix to yield non-chlorinated, hydroxylated, and larger molecular weight byproducts. All of the CDX's byproducts retain their biologically active N-oxide groups, suggesting that they may remain as active antibacterial agents.

THE NEUROTOXICANT TRIMETHYLTIN STIMULATES APOPTOSIS VIA OXIDATIVE STRESS, CASPASE ACTIVATION AND P38 PROTEIN KINASE.

Science.gov (United States)

Acute exposure to the tri-substituted organotin trimethyltin (TMT) causes neuronal degeneration in the hippocampus, amygdala, pyriform cortex, and neocortex. Developmental exposure to TMT impairs later learning and memory. Despite extensive efforts elucidating neuropathological...

Imposex occurrence in marine whelks at a military facility in the high Arctic

Energy Technology Data Exchange (ETDEWEB)

Strand, Jakob [Department of Marine Ecology, National Environmental Research Institute, Frederiksborgvej 399, P.O. Box 358, 4000 Roskilde (Denmark)]. E-mail: jak@dmu.dk; Glahder, Christian M. [Department of Arctic Environment, National Environmental Research Institute, Frederiksborgvej 399, 4000 Roskilde (Denmark); Asmund, Gert [Department of Arctic Environment, National Environmental Research Institute, Frederiksborgvej 399, 4000 Roskilde (Denmark)

2006-07-15

Imposex was found in the Arctic whelk Buccinum finmarkianum at several marine stations off Thule Air Base, an US military facility in Northwest Greenland. This indicates a widespread contamination with the antifouling agents, tributyltin (TBT) or triphenyltin (TPhT) in the area, but such contamination was not supported by the organotin analyses in sediments, whelks and clams, which in general was below the analytical detection limit. Organotin concentrations above the detection limit were found only at one station close to a quay, where the highest frequency of imposex also occurred. This suggests that imposex in B. finmarkianum is a biomarker of TBT more sensitive than the detection limits, which the analytical chemistry could achieve in this study. - Imposex as a biomarker was more sensitive for TBT than analytical chemical methods.

Imposex occurrence in marine whelks at a military facility in the high Arctic

International Nuclear Information System (INIS)

Strand, Jakob; Glahder, Christian M.; Asmund, Gert

2006-01-01

Imposex was found in the Arctic whelk Buccinum finmarkianum at several marine stations off Thule Air Base, an US military facility in Northwest Greenland. This indicates a widespread contamination with the antifouling agents, tributyltin (TBT) or triphenyltin (TPhT) in the area, but such contamination was not supported by the organotin analyses in sediments, whelks and clams, which in general was below the analytical detection limit. Organotin concentrations above the detection limit were found only at one station close to a quay, where the highest frequency of imposex also occurred. This suggests that imposex in B. finmarkianum is a biomarker of TBT more sensitive than the detection limits, which the analytical chemistry could achieve in this study. - Imposex as a biomarker was more sensitive for TBT than analytical chemical methods

Synthesis, Spectral, Electrochemical and Theoretical Investigation of ...

Indian Academy of Sciences (India)

chemsci

and thermal properties along with computed HOMO-LUMO energy levels were studied for the synthesized compounds. ... anthraquinone (Chart 1) and their photophysical, elec- ... Indolo[2,3-b]quinoxaline based dyes as n–type materials. 485.

JCSC_129_11_1761_1769_SI.docx

Indian Academy of Sciences (India)

rahulwatile

SUPPLEMENTARY INFORMATION. Synthesis of Quinoxaline Derivatives from Terminal Alkynes and o-phenylenediamines by using Copper Alumina Catalyst. AKHIL V NAKHATE, KALIDAS B RASAL, GUNJAN P DESHMUKH, SHYAM SUNDER R GUPTA and MANNEPALLI LAKSHMI KANTAM* ...

Liquid membrane extraction techniques for trace metal analysis and speciation in environmental and biological matrices

Energy Technology Data Exchange (ETDEWEB)

Ndungu, Kuria

1999-04-01

In this thesis, liquid-membrane-based methods for the analysis of trace metal species in samples of environmental and biological origin were developed. By incorporating extracting reagents in the membrane liquid, trace metal ions were selectively separated from humic-rich natural waters and urine samples, prior to their determination using various instrumental techniques. The extractions were performed in closed flow systems thus allowing easy automation of both the sample clean-up and enrichment. An acidic organophosphorus reagent (DEHPA) and a basic tetraalkylammonium reagent (Aliquat-336) were used as extractants in the membrane liquid to selectively extract and enrich cationic and anionic metal species respectively. A speciation method for chromium species was developed that allowed the determination of cationic Cr(III) species and anionic CR(VI) species in natural water samples without the need of a chromatographic separation step prior to their detection. SLM was also coupled on-line to potentiometric stripping analysis providing a fast and sensitive method for analysis of Pb in urine samples. A microporous membrane liquid-liquid extraction (MMLLE) method was developed for the determination of organotin compounds in natural waters that reduced the number of manual steps involved in the LLE of organotin compounds prior to their CC separation. Clean extracts obtained after running unfiltered humic-rich river water samples through the MMLLE flow system allowed selective determination of all the organotin compounds in a single run using GC-MS in the selected ion monitoring mode (SIM) 171 refs, 9 figs, 4 tabs

SEPARATION AND DETECTION OF THREE ARYLTINS BY CAPILLARY ELECTROPHORESIS-UV/VIS DIODE ARRAY

Science.gov (United States)

The trialkyltins and triphenyltins have widespread application as fungicides, antifouling coatings for porous surfaces, herbicides, insecticides, and generic biocides. Due to the varied toxicity of each species of organotins, it is important that methods address the speciation of...

The obesogen tributyltin.

Science.gov (United States)

Grün, Felix

2014-01-01

The obesogen hypothesis postulates the role of environmental chemical pollutants that disrupt homeostatic controls and adaptive mechanisms to promote adipose-dependent weight gain leading to obesity and metabolic syndrome complications. One of the most direct molecular mechanisms for coupling environmental chemical exposures to perturbed physiology invokes pollutants mimicking endogenous endocrine hormones or bioactive dietary signaling metabolites that serve as nuclear receptor ligands. The organotin pollutant tributyltin can exert toxicity through multiple mechanisms but most recently has been shown to bind, activate, and mediate RXR-PPARγ transcriptional regulation central to lipid metabolism and adipocyte biology. Data in support of long-term obesogenic effects on whole body adipose tissue are also reported. Organotins represent an important model test system for evaluating the impact and epidemiological significance of chemical insults as contributing factors for obesity and human metabolic health. © 2014 Elsevier Inc. All rights reserved.

Fasina et al (2)

African Journals Online (AJOL)

DELL

ligands and complexes was dependent on the electronic effect of the halogen substituent, which ... the desired ligand (4 mmol) in ethanol (30 mL) ... for 3 h and allowed to cool to room temperature. ..... oxide-quinoxaline-2-ylmethylene.

Distribution of butyltins (TBT, DBT, MBT) in sediments of Gulf of Cadiz (Spain) and its bioaccumulation in the clam Ruditapes philippinarum

Digital Repository Service at National Institute of Oceanography (India)

Garg, A.; Anton-Martin, R.; Garcia-Luque, E.; Riba, I.; DelValls, T.A.

Surface sediment samples were analyzed for organotins namely tributyltin (TBT), dibutyltin and monobutyltin from six areas located in the Gulf of Cadiz (14 stations), Spain. The total butyltin ranged between undetected and 1,580 ng Sn g sup(-1). TBT...

EFFECTS OF TRIBUTYLTIN ON CA2+ HOMEOSTASIS AND MECHANISMS CONTROLLING CELL CYCLING IN SEA URCHIN EGGS (R823881)

Science.gov (United States)

AbstractTributyltin (TBT) is one of the widespread organotins in the marine environment: we have investigated its cellular targets in the eggs of the marine invertebrate sea urchin Paracentrotus lividus. TBT was used at concentrations ranging from 10-9

supp12a.doc

Indian Academy of Sciences (India)

for. Application of quinoxaline based diimidazolium salt in palladium catalyzed cross-coupling reactions. Mujahuddin M. Siddiqui, Mohammed Waheed, Sajad A. Bhat and Maravanji S. Balakrishna*. Organophosphorus and Homogenous catalysis laboratory, Department of Chemistry, Indian Institute of Technology Bombay, ...

Effects of in utero tributyltin chloride exposure in the rat on pregnancy outcome.

Science.gov (United States)

Adeeko, Adedayo; Li, Daming; Forsyth, Don S; Casey, Valerie; Cooke, Gerard M; Barthelemy, Johanna; Cyr, Daniel G; Trasler, Jacquetta M; Robaire, Bernard; Hales, Barbara F

2003-08-01

Tributyltin, an organotin, is ubiquitous in the environment. The consumption of contaminated marine species leads to human dietary exposure to this compound. Tributyltin is an endocrine disruptor in many wildlife species and inhibits aromatase in mammalian placental and granulosa-like tumor cell lines. We investigated the effects of tributyltin chloride exposure on pregnancy outcome in the Sprague-Dawley rat. Timed pregnant rats were gavaged either with vehicle (olive oil) or tributyltin chloride (0.25, 2.5, 10, or 20 mg/kg) from days 0-19 or 8-19 of gestation. On gestational day 20, dams were sacrificed, and pregnancy outcome was determined. Tributyltin and its metabolites (dibutyltin, monobutyltin) were measured in maternal blood by gas chromatography. Both tributyltin and dibutyltin were present in maternal blood at approximately equal concentrations, whereas monobutyltin contributed minimally to total organotins. Organotin concentrations increased in a dose-dependent pattern in dams, independent of the window of exposure. Tributyltin chloride administration significantly reduced maternal weight gain only at the highest dose (20 mg/kg); a significant increase in post-implantation loss and decreased litter sizes, in addition to decreased fetal weights, was observed in this group. Tributyltin chloride exposure did not result in external malformations, nor was there a change in sex ratios. However, exposure to 0.25, 2.5, or 10 mg/kg tributyltin chloride from gestation days (GD) 0-19 resulted in a significant increase in normalized anogenital distances in male fetuses; exposure from days 8-19 had no effect. There was a dramatic increase in the incidence of low weight (exposure to 20 mg/kg tributyltin chloride. Delayed ossification of the fetal skeleton was observed after in utero exposure to either 10 mg/kg or 20 mg/kg tributyltin chloride. Serum thyroxine and triiodothyronine levels were reduced significantly in dams exposed to 10 and 20 mg/kg tributyltin chloride

Topical viscosity control for light hydrocarbon displacing fluids in petroleum recovery and in fracturing fluids for well stimulation

Science.gov (United States)

Heller, John P.; Dandge, Dileep K.

1986-01-01

Solvent-type flooding fluids comprising light hydrocarbons in the range of ethane to hexane (and mixtures thereof) are used to displace crude oil in formations having temperatures of about 20 degrees to about 150 degrees Centigrade and pressures above about 650 psi, the light hydrocarbons having dissolved therein from about 0.05% to about 3% of an organotin compound of the formula R.sub.3 SnF where each R is independently an alkyl, aryl or alkyaryl group from 3 to 12 carbon atoms. Under the pressures and temperatures described, the organotin compounds become pentacoordinated and linked through the electronegative bridges, forming polymers within the light hydrocarbon flooding media to render them highly viscous. Under ambient conditions, the viscosity control agents will not readily be produced from the formation with either crude oil or water, since they are insoluble in the former and only sparingly soluble in the latter.

Sex steroid imbalances in the muricid Stramonita haemastoma from TBT contaminated sites.

Science.gov (United States)

Rossato, M; Castro, I B; Paganini, C L; Colares, E P; Fillmann, G; Pinho, G L L

2016-04-01

Imposex incidence, organotin tissue levels, and sex steroid (free and esterified testosterone and estradiol) levels were assessed in Stramonita haemastoma from Babitonga Bay (Santa Catarina State, Southern Brazil). The imposex levels showed a reduction when compared to a previous evaluation performed in the same area. In spite of that, the detected imposex incidence indicated the occurrence of tributyltin (TBT) inputs that were still able to produce endocrine disruption in local gastropods. In addition, a high level of organotins was observed in tissues of imposexed females. These females also showed a hormonal imbalance, especially in the total testosterone/total estradiol ratio. These findings obtained under realistic field conditions suggest that the steroid pathway could be responsible by the imposex induction after exposure to TBT. In this case, measurements of sex steroid levels can be an additional evidence for monitoring sites and impose affected gastropod populations.

New biocides for antifouling paints

International Nuclear Information System (INIS)

Mazziotti, Isabella; Massanisso, Paolo; Cremisini, Carlo; Chiavarini, Salvatore; Fantini, Michele; Morabito, Roberto

2005-01-01

The antifouling paints are used for protecting the hulls of the boasts from the undesirable accumulation of micro-organisms, plants, and animals on artificial surfaces (marine biological fouling). These paints constitute a potential risk for the marine environment, because of the presence in their formulation, among the other potentially toxic components, of organic compounds acting as biocide. The environmental problems associated with the use of the organotin compounds as biocides in the antifouling paints, have lead to the international ban of these compounds. In the article the new antifouling paints coming up the national and international market are shortly introduced and discussed, with particular attention respect to the new organic compounds used as biocides. In Italy quite a few marine monitoring campaigns have been carried out for organotin compounds, on the contrary there is a lack of data regarding the presence of other biocides [it

Coupling marine monitoring and risk assessment by integrating exposure, bioaccumulation and effect studies

DEFF Research Database (Denmark)

Strand, J.

This Ph.D. thesis focuses on the highly toxic organotin compounds, mainly tri-n-butyltin (TBT) but also triphenyltin (TPhT), which have been widely used as antifouling agents in ship paints, and covers several aspects investigated by field studies of spatial distributions, bioaccumulation...

78 FR 40017 - Ethalfluralin; Pesticide Tolerances

Science.gov (United States)

2013-07-03

... (NAICS code 112). Food manufacturing (NAICS code 311). Pesticide manufacturing (NAICS code 32532). B. How... system. Additionally, ethalfluralin does not belong to a class of chemicals (e.g., the organotins, heavy... Alimentarius is a joint United Nations Food and Agriculture Organization/World Health Organization food...

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.

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Home; Journals; Journal of Chemical Sciences; Volume 129; Issue 2. Rapid, efficient and eco-friendly procedure for the synthesis of quinoxalines under solvent-free conditions using sulfated polyborate as a recyclable catalyst. KRISHNA S INDALKAR CHETAN K KHATRI GANESH U CHATURBHUJ. Rapid Communication ...

Fulltext PDF

Indian Academy of Sciences (India)

A highly efficient and improved synthetic methodology for the preparation of quinoxaline derivatives from various substituted o-phenylenediamines and 1,2- diketones/α-hydroxy ketones using eco-friendly, economic and recyclable sulfated polyborate catalyst under the solvent-free condition is reported. Mild reaction ...

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Home; Journals; Journal of Chemical Sciences. KRISHNA S INDALKAR. Articles written in Journal of Chemical Sciences. Volume 129 Issue 2 February 2017 pp 141-148 Rapid Communication. Rapid, efficient and eco-friendly procedure for the synthesis of quinoxalines under solvent-free conditions using sulfated ...

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Home; Journals; Journal of Chemical Sciences; Volume 127; Issue 5. Application of quinoxaline based diimidazolium salt in palladium catalyzed cross-coupling reactions. Mujahuddin M Siddiqui Mohammed Waheed Sajad A Bhat Maravanji S Balakrishna. Regular Articles Volume 127 Issue 5 May 2015 pp 879-884 ...

Download this PDF file

African Journals Online (AJOL)

quinoxalin-2-one (5), was identical with that prepared from the D-erythro analog. The IH NMR spectrum of 5 showed two NH protons (6 11.20 and 12.50) and an aldehydic proton (6 9.58). Reduction of 5 with sodium borohydride afforded ...

Occupational irritant contact folliculitis associated with triphenyl tin fluoride (TPTF) exposure

DEFF Research Database (Denmark)

Andersen, Klaus Ejner; Petri, M

1982-01-01

Triphenyl tin fluoride (TPTF) is a bioactive organo-tin compound used in concentrations 2-12% as anti-foulants in boat paints. The chemical is moderately toxic to the skin. An occupational irritant contact folliculitis from TPTF in a marine paint plant worker is described. Contact allergy...

Imposex induction in laboratory reared juvenile Buccinum undatum by tributyltin (TBT

NARCIS (Netherlands)

Mensink, B.P.; Kralt, H.; Vethaak, A.D.; ten Hallers-Tjabbes, C.C.; Koeman, J.H.; van Hattum, A.G.M.; Boon, J.P.

2002-01-01

Here we report a series of experiments on the development and occurrence of imposex in the common whelk, Buccinum undatum, under the influence of (chronic) exposure to butyltin compounds. The main objective of the experiments was to obtain more information about the effects of organotin compounds in

Guide to Technical Documents. Volume I. May 1949 through December 1972

Science.gov (United States)

1972-12-01

tt t Nettl Pretervat ive, Oct 1960, I. S. Ztblodil, 1. I. Joerding. AD 2A«»2 A fill of Teflon «at applied to aott corrodibl...organotin coapounda protected aatchaiicka froa aarine borera for a long time, but mercury coapounda, organic dye!, organic insecticide !, ailver

Synthesis and Characterization of Organ Tin (IV) Complexes ...

African Journals Online (AJOL)

User

2012-08-21

Aug 21, 2012 ... the reference drug. In addition, within the diorganotin(IV) complexes, monomeric type (3) exhibited a slightly better activity as compared to the organodistannoxane dimer types (1 and 4). Key words: Preliminary in vitro cytotoxic assay, organotin(IV) complexes, comparison study. INTRODUCTION. Although ...

Environmental risk limits for organotin compounds

NARCIS (Netherlands)

van Herwijnen R; LER; mev

2012-01-01

Het RIVM heeft in opdracht van het ministerie van Infrastructuur en Milieu (I&M), milieurisicogrenzen voor drie organotinverbindingen in (grond)water, sediment en bodem vastgesteld. De drie meest voorkomende verbindingen in het milieu zijn: dibutyltin, tributyltin en trifenyltin. Dibutyltin wordt in

Butyltins and phenyltins in biota and sediments from the Lagoon of Venice

Directory of Open Access Journals (Sweden)

Angelo Bortoli

2003-03-01

Full Text Available Sediments and organisms were sampled to determine organotin contents - butyltins (BTs and phenyltins (PhTs - at 12 locations in an estuarine ecosystem, the Lagoon of Venice, characterised by varying contamination impacts. The results showed that organotin contamination in sediments is at lower levels, ranging from 2.5 ± 0.1 to 84 ± 1 ng g-1 (d.w. for SigmaBTs and from 0.8 ± 0.2 to 7 ± 1 ng g-1 (d.w., for SigmaPHTs, than in organisms, where the highest concentrations were found infilter feeders like mussels - from 60 ± 3 to 7632 ± 148 ng g-1 (d.w. for SigmaBTs and from 0.80 ± 0.01 to 4005 ± 121 ng g-1 (d.w. for SigmaPHTs. The possible risk to human health was assessed on the basis of the consumption of edible species sampled in some areas of the lagoon.

A temporal and spatial assessment of TBT concentrations at dredged material disposal sites around the coast of England and Wales.

Science.gov (United States)

Bolam, Thi; Barry, Jon; Law, Robin J; James, David; Thomas, Boby; Bolam, Stefan G

2014-02-15

Despite legislative interventions since the 1980s, contemporary concentrations of organotin compounds in marine sediments still impose restrictions on the disposal of dredged material in the UK. Here, we analyse temporal and spatial data to assess the effectiveness of the ban on the use of TBT paints in reducing concentrations at disposal sites. At a national scale, there was a statistically significant increase in the proportion of samples in which the concentration was below the limit of detection (LOD) from 1998 to 2010. This was observed for sediments both inside and outside the disposal sites. However, this temporal decline in organotin concentration is disposal site-specific. Of the four sites studied in detail, two displayed significant increases in proportion of samples below LOD over time. We argue that site-specificity in the effectiveness of the TBT ban results from variations in historical practices at source and unique environmental characteristics of each site. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

Nitrile crosslinked polyphenyl-quinoxaline/graphite fiber composites

Science.gov (United States)

Alston, W. B.

1976-01-01

Studies were performed to reduce the 600 F thermoplasticity of polyphenylquinoxaline (PPQ) matrix resins by introducing crosslinking by the reaction of terminal nitrile groups. Seven solvents and solvent mixtures were studied as the crosslinking catalysts and used to fabricate crosslinked PPQ/HMS graphite fiber composites. The room temperature and 600 F composite mechanical properties after short time and prolonged 600 F air exposure and the 600 F composite weight loss were determined and compared to those properties of high molecular weight, linear PPQ/HMS graphite fiber composites.

High risk of adrenal toxicity of N1-desoxy quinoxaline 1,4-dioxide derivatives and the protection of oligomeric proanthocyanidins (OPC) in the inhibition of the expression of aldosterone synthetase in H295R cells

International Nuclear Information System (INIS)

Wang, Xu; Yang, Chunhui; Ihsan, Awais; Luo, Xun; Guo, Pu; Cheng, Guyue; Dai, Menghong; Chen, Dongmei; Liu, Zhenli; Yuan, Zonghui

2016-01-01

Highlights: • N1-QCT, N1-MEQ and N1-CYA showed more adrenal toxicity than other metabolites. • N1-desoxy QdNOs reduced expression of CYP11B1, CYP11B2 and transcription factors. • OPC increased expression of transcription factors, including CYP11B1 and CYP11B2. • OPC reduced adrenal toxicity induced by N1-desoxy QdNOs. • The results provided a mechanism of adrenal damage caused by QdNO metabolites. - Abstract: Quinoxaline 1,4-dioxide derivatives (QdNOs) with a wide range of biological activities are used in animal husbandry worldwide. It was found that QdNOs significantly inhibited the gene expression of CYP11B1 and CYP11B2, the key aldosterone synthases, and thus reduced aldosterone levels. However, whether the metabolites of QdNOs have potential adrenal toxicity and the role of oxidative stress in the adrenal toxicity of QdNOs remains unclear. The relatively new QdNOs, cyadox (CYA), mequindox (MEQ), quinocetone (QCT) and their metabolites, were selected for elucidation of their toxic mechanisms in H295R cells. Interestingly, the results showed that the main toxic metabolites of QCT, MEQ, and CYA were their N1-desoxy metabolites, which were more harmful than other metabolites and evoked dose and time-dependent cell damage on adrenal cells and inhibited aldosterone production. Gene and protein expression of CYP11B1 and CYP11B2 and mRNA expression of transcription factors, such as NURR1, NGFIB, CREB, SF-1, and ATF-1, were down regulated by N1-desoxy QdNOs. The natural inhibitors of oxidant stress, oligomeric proanthocyanidins (OPC), could upregulate the expression of diverse transcription factors, including CYP11B1 and CYP11B2, and elevated aldosterone levels to reduce adrenal toxicity. This study demonstrated for the first time that N1-desoxy QdNOs have the potential to be the major toxic metabolites in adrenal toxicity, which may shed new light on the adrenal toxicity of these fascinating compounds and help to provide a basic foundation for the

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Synthesis, spectra and electrochemistry of dinitro-bis-{2-(phenylazo)pyrimidine} ruthenium(II). Nitro-nitroso derivatives and reactivity of the electrophilic nitrosyl centre ... functions which are not affected under these conditions. pp 425-428. One-pot efficient green synthesis of 1,4-dihydro-quinoxaline-2,3-dione derivatives.

Effect of phenolic compounds from spices consumed in China on heterocyclic amine profiles in roast beef patties by UPLC-MS/MS and multivariate analysis.

Science.gov (United States)

Zeng, Maomao; Li, Yang; He, Zhiyong; Qin, Fang; Chen, Jie

2016-06-01

Ultra performance liquid chromatography-tandem mass spectrometry and multivariate analysis were used to exploit the effect and further synergistic or antagonistic interactions of main phenolic compounds with the same ratios as in spices consumed in China, on the profiles of HAs in roast beef patties. Quantitative levels of harman (1-methyl-9H-pyrido[3,4-b]indole), norharman (9H-pyrido[3,4-b]indole), PhIP (2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine), DMIP (2-amino-1,6-dimethylimidazo[4,5-b]pyridine), 1,5,6-TMIP (2-amino-1,5,6-trimethylimidazo[4,5-b]pyridine), MeIQx (2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline) and 4,8-DiMeIQx (2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline) were detected in all of the beef patties. The formation of most of these seven HAs was significantly (Pspices on the formation of HAs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Immunocytological and biochemical analysis of the mode of action of bis (tri-n-butyltin) tri-oxide (TBTO) in Jurkat cells

NARCIS (Netherlands)

Katika, M.R.; Hendriksen, P.J.M.; Ruijter, de N.C.A.; Loveren, van H.; Peijnenburg, A.A.C.M.

2012-01-01

Bis (tri-n-butyltin) oxide (TBTO) is one of the organotin compounds known to induce immunosuppression. Previously, we examined the effect of TBTO on whole-genome mRNA expression in the human T lymphocyte cell line Jurkat, which led to the hypothesis that induction of endoplasmic reticulum (ER)

Miljøfarlige stoffer i sediment og muslinger - Delrapport III

DEFF Research Database (Denmark)

Dahllöf, Ingela; Strand, Jakob

Koncentrationer af miljøfarlige stoffer i sediment og muslinger blev sammenholdt med forekomst af misdannelser i ålekvabbeunger. Tungmetaller, organotin, dioxiner, dioxinlignende PCB’er, samt bromerede flammehæmmer blev vurderet som stærke kandidatstoffer til at kunne være årsag til de observered...

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...

Pharmacokinetics of Mequindox and Its Marker Residue 1,4-Bisdesoxymequindox in Swine Following Multiple Oral Gavage and Intramuscular Administration : An Experimental Study Coupled with Population Physiologically Based Pharmacokinetic Modeling

NARCIS (Netherlands)

Zeng, Dongping; Lin, Zhoumeng; Fang, Binghu; Li, Miao; Gehring, Ronette; Riviere, Jim E; Zeng, Zhenling

2017-01-01

Mequindox (MEQ) is a quinoxaline-N,N-dioxide antibiotic used in food-producing animals. MEQ residue in animal-derived foods is a food safety concern. The tissue distribution of MEQ and its marker residue 1,4-bisdesoxymequindox (M1) were determined in swine following oral gavage or intramuscular

Diorganotin(IV) Complexes with Methionine Methyl Ester. Equilibria ...

African Journals Online (AJOL)

NICO

to optimize the features of classical platinum drugs containing the basic cisplatin framework, viz. their toxic side ... cases, organotins have emerged as a promising class of cancer chemotherapeutics. It has been well ... place in cancer chemotherapy.4–7 Blower8 described thirty interest- ing inorganic pharmaceuticals, four of ...

Proteomic analysis of mouse thymoma EL4 cells treated with bis (tri-n-butyltin)oxide (TBTO)

NARCIS (Netherlands)

Osman, A.M.; Kol, S.; Peijnenburg, A.A.C.M.; Blokland, M.H.; Pennings, J.L.A.; Kleinjans, J.C.S.; Loveren, van H.

2009-01-01

Here, we report the results of proteomic analysis of the mouse thymoma EL4 cell line exposed to bis(tri-n-butylin)oxide (TBTO), an immunotoxic organotin compound. The objective of the work was to examine whether TBTO affects the expression of proteins in this cell line and to compare the

The C–F bond as a conformational tool in organic and biological chemistry

Directory of Open Access Journals (Sweden)

Luke Hunter

2010-04-01

Full Text Available Organofluorine compounds are widely used in many different applications, ranging from pharmaceuticals and agrochemicals to advanced materials and polymers. It has been recognised for many years that fluorine substitution can confer useful molecular properties such as enhanced stability and hydrophobicity. Another impact of fluorine substitution is to influence the conformations of organic molecules. The stereoselective introduction of fluorine atoms can therefore be exploited as a conformational tool for the synthesis of shape-controlled functional molecules. This review will begin by describing some general aspects of the C–F bond and the various conformational effects associated with C–F bonds (i.e. dipole–dipole interactions, charge–dipole interactions and hyperconjugation. Examples of functional molecules that exploit these conformational effects will then be presented, drawing from a diverse range of molecules including pharmaceuticals, organocatalysts, liquid crystals and peptides.

VUF10166, a novel compound with differing activities at 5-HT₃A and 5-HT₃AB receptors

NARCIS (Netherlands)

Thompson, Andrew J; Verheij, M H P; de Esch, I J P; Lummis, S.C.R.

The actions of a novel, potent 5-HT₃ receptor ligand, [2-chloro-(4-methylpiperazine-1-yl)quinoxaline (VUF10166)], were examined at heterologously expressed human 5-HT₃A and 5-HT₃AB receptors. VUF10166 displaced [³H]granisetron binding to 5-HT₃A receptors expressed in human embryonic kidney cells

random polyfluorene co-polymers designed for a better optical ...

African Journals Online (AJOL)

Preferred Customer

GPCV instrument at 135 oC using RI detection and 1,2,4-trichlorobenzene as ... Silicon cantilevers (NSG10) with a force constant of 5.5–22.5 N m-1, .... electron accepting capacity of the quinoxaline unit in APFO15-F8BT is lower due to the.

Molecular recognition of halogen-tagged aromatic VOCs at the air-silicon interface.

Science.gov (United States)

Condorelli, Guglielmo G; Motta, Alessandro; Favazza, Maria; Gurrieri, Ettore; Betti, Paolo; Dalcanale, Enrico

2010-01-14

Selective and reversible complexation of halogen-tagged aromatic VOCs by a quinoxaline cavitand-decorated Si surface is demonstrated. The specific host-guest interactions of the Si-bonded receptors are proved to be responsible of the surface recognition properties, while extracavity non specific adsorptions are totally suppressed compared to the bulk material.

Photoinduced electron transfer and photocurrent in multicomponent organic molecular films containing oriented porphyrin-fullerene dyad

NARCIS (Netherlands)

Kaunisto, Kimmo; Vuorinen, Tommi; Vahasalo, Heidi; Chukharev, Vladimir; Tkachenko, Nikolai V.; Efimov, Alexander; Tolkki, Antti; Lehtivuori, Heli; Lemmetyinen, Helge

2008-01-01

Layers of poly(3-hexylthiophene), PHT, phenyl vinyl thiophene, PVT3, poly(p-phenylene-2,3′-bis(3,2′-diphenyl)-quinoxaline-7-7′- diyl), PPQ, and covalently linked porphyrin-fullerene donor-acceptor dyad, P-F, were deposited as various multilayer films, which then were used to study photoinduced

Military Wastes-to-Energy Applications,

Science.gov (United States)

1980-11-01

6 Residual) and Used Oil ( Automotive Crankcase Drainings) .......... ........................ 109 60 Properties of Coal: Bituminous, Subbituminous...facilities Physical/Chemical e Biomass removal from forest land may upset the Environment natural balance of terrestrial, aquatic, and atmospheric...ripout wastes (asbestos), sand- blasting wasts (organotin), and welding wastes (acetylene sludge); * Miscellaneous aircraft repair wastes -- brake

Endothelium-independent and endothelium-dependent ...

African Journals Online (AJOL)

This endothelium-independent relaxant effect was also sensitive to combination of 1H-[1,2,4]-oxadiazole-[4,3-á]-quinoxalin- 1-one (ODQ, 10 ìM, soluble guanylyl cyclase inhibitor) and N-[2-(p-Bromocinnamylamino)ethyl]-5-isoquinoline sulfonamide dihydrochloride (H89, 100 nM, Protein Kinase A inhibitor). Taken together ...

The in-feed antibiotic carbadox induces phage gene transcription in the swine gut microbiome

Science.gov (United States)

Carbadox is a quinoxaline-di-N-oxide antibiotic fed to over 40 percent of young pigs in the U.S. and has been shown to induce phage DNA transduction in vitro; however, the effects of carbadox on swine microbiome functions are poorly understood. We investigated the in vivo effects of carbadox on swin...

Ability of Group IVB metallocene polyethers containing dienestrol to arrest the growth of selected cancer cell lines

International Nuclear Information System (INIS)

Roner, Michael R; Carraher, Charles E Jr; Shahi, Kimberly; Ashida, Yuki; Barot, Girish

2009-01-01

Monomeric Group IVB (Ti, Zr and Hf) metallocenes represent a new class of antitumor compounds. There is literature on the general biological activities of some organotin compounds. Unfortunately, there is little information with respect to the molecular level activity of these organotin compounds. We recently started focusing on the anti-cancer activity of organotin polymers that we had made for other purposes and as part of our platinum anti-cancer effort. For this study, we synthesized a new series of metallocene-containing compounds coupling the metallocene unit with dienestrol, a synthetic, nonsteroidal estrogen. This is part of our effort to couple known moieties that offer antitumor activity with biologically active units hoping to increase the biological activity of the combination. The materials were confirmed to be polymeric using light scattering photometry and the structural repeat unit was verified employing matrix assisted laser desorption ionization mass spectrometry and infrared spectroscopy results. The polymers demonstrated the ability to suppress the growth of a series of tumor cell lines originating from breast, colon, prostrate, and lung cancers at concentrations generally lower than those required for inhibition of cell growth by the commonly used antitumor drug cisplatin. These drugs show great promise in vitro against a number of cancer cell lines and due to their polymeric nature will most likely be less toxic than currently used metal-containing drugs such as cisplatin. These drugs also offer several addition positive aspects. First, the reactants are commercially available so that additional synthetic steps are not needed. Second, synthesis of the polymer is rapid, occurring within about 15 seconds. Third, the interfacial synthetic system is already industrially employed in the synthesis of aromatic nylons and polycarbonates. Thus, the ability to synthesize large amounts of the drugs is straight forward

Metabolism of tributyltin and triphenyltin by rat, hamster and human hepatic microsomes

Energy Technology Data Exchange (ETDEWEB)

Ohhira, Shuji; Watanabe, Masatomo; Matsui, Hisao [Department of Hygiene, Dokkyo University School of Medicine, Mibu-machi, 321-0293, Tochigi (Japan)

2003-03-01

Tributyltin and triphenyltin are metabolized by cytochrome P-450 system enzymes, and their metabolic fate may contribute to the toxicity of the chemicals. In the current study, the in vitro metabolism of tributyltin and triphenyltin by rat, hamster and human hepatic microsomes was investigated to elucidate the metabolic competence for these compounds in humans. The metabolic reaction using microsome-NADPH system that is usually conducted was not applicable to in vitro metabolism of organotins, especially triphenyltin. We therefore examined the effects of dithiothreitol (DTT), one of the antioxidants for sulfhydryl groups, to determine the in vitro metabolism of tributyltin and triphenyltin. As a result, the treatment with 0.1 mM DTT in vitro increased the activity of the microsomal monooxygenase system for metabolism of tributyltin as well as triphenyltin; the total yield of tributyltin and triphenyltin metabolites as tin increased, respectively, by approximately 1.8 and 8.9 times for rat, 2.1 and 1.2 times for hamster, and 1.6 and 1.5 times for human. It is suggested that the organotins directly inactivate cytochrome P-450 because of the interaction with critical sulfhydryl groups of the hemoprotein. We confirmed the utility of this in vitro metabolic system using DTT in the hepatic microsomes of phenobarbital (PB)-pretreated and untreated hamsters. Thus, the in vitro metabolic system described here was applied to a comparative study of the metabolism of organotins in rats, hamsters and humans. Tributyltin was metabolized more readily than triphenyltin in all the species. In humans, the in vitro metabolic pattern resembled that of hamsters, which were susceptible to in vivo triphenyltin toxicity because of incompetent metabolism. It is possible that the hamster is a qualitatively and quantitatively suitable animal model for exploring the influence of tributyltin and triphenyltin in humans. (orig.)

Ability of Group IVB metallocene polyethers containing dienestrol to arrest the growth of selected cancer cell lines

Directory of Open Access Journals (Sweden)

Ashida Yuki

2009-10-01

Full Text Available Abstract Background Monomeric Group IVB (Ti, Zr and Hf metallocenes represent a new class of antitumor compounds. There is literature on the general biological activities of some organotin compounds. Unfortunately, there is little information with respect to the molecular level activity of these organotin compounds. We recently started focusing on the anti-cancer activity of organotin polymers that we had made for other purposes and as part of our platinum anti-cancer effort. Methods For this study, we synthesized a new series of metallocene-containing compounds coupling the metallocene unit with dienestrol, a synthetic, nonsteroidal estrogen. This is part of our effort to couple known moieties that offer antitumor activity with biologically active units hoping to increase the biological activity of the combination. The materials were confirmed to be polymeric using light scattering photometry and the structural repeat unit was verified employing matrix assisted laser desorption ionization mass spectrometry and infrared spectroscopy results. Results The polymers demonstrated the ability to suppress the growth of a series of tumor cell lines originating from breast, colon, prostrate, and lung cancers at concentrations generally lower than those required for inhibition of cell growth by the commonly used antitumor drug cisplatin. Conclusion These drugs show great promise in vitro against a number of cancer cell lines and due to their polymeric nature will most likely be less toxic than currently used metal-containing drugs such as cisplatin. These drugs also offer several addition positive aspects. First, the reactants are commercially available so that additional synthetic steps are not needed. Second, synthesis of the polymer is rapid, occurring within about 15 seconds. Third, the interfacial synthetic system is already industrially employed in the synthesis of aromatic nylons and polycarbonates. Thus, the ability to synthesize large amounts of

The effects of tributyltin oxide and deoxynivalenol on the transcriptome of the mouse thymoma cell line EL-4

NARCIS (Netherlands)

Schmeits, P.J.M.; Kol, S.; Loveren, van H.; Peijnenburg, A.A.C.M.; Hendriksen, P.J.M.

2014-01-01

The main goal of this study was to assess the potential of the mouse thymoma EL-4 cell line in screening for chemical induced immunotoxicity. Therefore, EL-4 cells were exposed to two well-known immunotoxicants, organotin compound tributyltin oxide (TBTO, 0.5 and 1 µM for 3 or 6 h) and the mycotoxin

Trioorganotin compounds, cognate ligands, of nuclear retinoid X receptors - biological effects in human breats cancer cell lines

Czech Academy of Sciences Publication Activity Database

Brtko, J.; Toporová, L.; Macejová, D.; Hunáková, L.; Bobálová, Janette

2017-01-01

Roč. 10, suppl. 1 (2017), s. 19-19 ISSN 1337-6853. [Mezioborová toxikologická konference /22./ TOXCON 2017. 21.06.2017-23.06.2017, Plzeň] Grant - others:AV ČR(CZ) SAV-15-01 Program:Bilaterální spolupráce Institutional support: RVO:68081715 Keywords : receptor * organotin compounds * cancer

The role of retinoic acid receptors and their cognate ligands in reproduction in a context of triorganotin based endocrine disrupting chemicals

Directory of Open Access Journals (Sweden)

Macejova Dana

2016-07-01

Full Text Available Retinoic acid (RA, an active form of vitamin A, regulates the embryonic development, male and female reproduction and induces important effects on the cell development, proliferation, and differentiation. These effects are mediated by the retinoid (RAR and rexinoid nuclear receptors (RXR, which are considered to be a ligand-activated, DNA-binding, trans-acting, and transcription-modulating proteins, involved in a general molecular mechanism responsible for the transcriptional responses in target genes. Organotin compounds are typical environmental contaminants and suspected endocrine disrupting substances. They may affect processes of reproductive system in mammals, predominantly via nuclear receptor signaling pathways. Triorganotins, such as tributyltin chloride (TBTCl and triphenyltin chloride (TPTCl, are capable to bind to RXR molecules, and thus represent potent agonists of RXR subtypes of nuclear receptors not sharing any structural characteristics with endogenous ligands of nuclear receptors. Th is article summarizes selected effects of biologically active retinoids and rexinoids on both male and female reproduction and also deals with the effects of organotin compounds evoking endocrine disrupting actions in reproduction.

Tributyltin and triphenyltin inhibit osteoclast differentiation through a retinoic acid receptor-dependent signaling pathway

International Nuclear Information System (INIS)

Yonezawa, Takayuki; Hasegawa, Shin-ichi; Ahn, Jae-Yong; Cha, Byung-Yoon; Teruya, Toshiaki; Hagiwara, Hiromi; Nagai, Kazuo; Woo, Je-Tae

2007-01-01

Organotin compounds, such as tributyltin (TBT) and triphenyltin (TPT), have been widely used in agriculture and industry. Although these compounds are known to have many toxic effects, including endocrine-disrupting effects, their effects on bone resorption are unknown. In this study, we investigated the effects of organotin compounds, such as monobutyltin (MBT), dibutyltin (DBT), TBT, and TPT, on osteoclast differentiation using mouse monocytic RAW264.7 cells. MBT and DBT had no effects, whereas TBT and TPT dose-dependently inhibited osteoclast differentiation at concentrations of 3-30 nM. Treatment with a retinoic acid receptor (RAR)-specific antagonist, Ro41-5253, restored the inhibition of osteoclastogenesis by TBT and TPT. TBT and TPT reduced receptor activator of nuclear factor-κB ligand (RANKL) induced nuclear factor of activated T cells (NFAT) c1 expression, and the reduction in NFATc1 expression was recovered by Ro41-5253. Our results suggest that TBT and TPT suppress osteoclastogenesis by inhibiting RANKL-induced NFATc1 expression via an RAR-dependent signaling pathway

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.

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®

DFT theoretical study of 7-R-3methylquinoxalin-2(1H)-thiones (R=H; CH3; Cl) as corrosion inhibitors in hydrochloric acid

International Nuclear Information System (INIS)

El Adnani, Z.; Mcharfi, M.

2013-01-01

Highlights: ► A theoretical study of three quinoxaline derivatives. ► We try to explain their experimental mild steel corrosion inhibition efficiencies. ► The solvent effect was also depicted using the PCM model. ► Most of the global reactivity descriptors agree well with the experimental results. ► The results show that the sulphur atom is probably the main adsorption site. - Abstract: Quantum chemical approach at B3LYP/6-31G(d,p) level of theory, was used to calculate some structural and electronic properties of three quinoxaline derivatives, recently reported as mild steel corrosion inhibitors in acidic media, to ascertain the correlation between their experimental inhibitive efficiencies and some of the computed parameters. The results of most of the global reactivity descriptors show that the experimental and theoretical studies agree well and confirm that Me-Q=S is a better inhibitor than Q=S and Cl-Q=S, respectively. In addition, the local reactivity, analyzed through Fukui functions, show that the sulphur atom will be the main adsorption site.

New m-alkoxy-p-fluorophenyl difluoroquinoxaline based polymers in efficient fullerene solar cells with high fill factor

Czech Academy of Sciences Publication Activity Database

Xu, S.; Feng, L.; Yuan, J.; Cimrová, Věra; Chen, G.; Zhang, Z.-G.; Li, Y.; Peng, H.; Zou, Y.

2017-01-01

Roč. 50, November (2017), s. 7-15 ISSN 1566-1199 R&D Projects: GA ČR(CZ) GA13-26542S Institutional support: RVO:61389013 Keywords : quinoxaline * D-A copolymer * fullerene solar cells Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 3.399, year: 2016

Structures and Redox Properties of Metal Complexes of the Electron-Deficient Diphosphine Chelate Ligand R,R-QuinoxP

Czech Academy of Sciences Publication Activity Database

Das, A. K.; Bulak, E.; Sarkar, B.; Lissner, F.; Schleid, T.; Niemeyer, M.; Fiedler, Jan; Kaim, W.

2008-01-01

Roč. 27, č. 2 (2008), s. 218-223 ISSN 0276-7333 R&D Projects: GA MŠk OC 139; GA MŠk OC 140 Institutional research plan: CEZ:AV0Z40400503 Keywords : 2,3-bis(tert-butylmethylphosphino)quinoxaline * radical complexes * phosphine ligand Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.815, year: 2008

Synthesis, Photophysical, Electrochemical and Thermal Studies of ...

Indian Academy of Sciences (India)

of Triarylamines based on benzo[g]quinoxalines. AZAM M ...... Son H-J, Han W-S, Wee K-R, Yoo D-H, Lee J-H, Kwon. S-N, Ko J ... Kim S K, Yang B, Park Y I, Ma Y J -Y and Lee H -J K ... M, Wang R-Y, Tao Y and Wang S 2004 J. Mater. Chem.

Expanding the scope of organofluorine biochemistry through the study of natural and engineered systems

OpenAIRE

Walker, Mark Chalfant

2013-01-01

Fluorination has become a very useful tool in the design and optimization of bioactive small molecules ranging from pesticides to pharmaceuticals. Its small size allows a sterically conservative substitution for a hydrogen or hydroxyl, thus maintaining the overall size and shape of a molecule. However, the extreme electronegativity of fluorine can dramatically alter other properties of the molecule. As a result, the development of new methods for fluorine incorporation is currently a major fo...

Sublethal Growth Effects and Mortality to Marine Bivalves and Fish from Long-Term Exposure to Tributyltin.

Science.gov (United States)

1985-07-01

sublethal toxicity of tributyltin oxide (TBTO) and its putative environmental product, tribu- tyltin sulfide ( TBTS ) to zoeal mud crabs, RIthropanopeus...Organotin .,’vwfuf coatingsu~~ study better defines the longterm toxicity and bloaccumnulation potential of tributyltin released from antifouting...larval fish survival at low tributyltin concentrations were also tested. Acute toxicity tests (96 hours) were con- ducted with mysid shrmp (Aawhomyot

Migration of nanosized layered double hydroxide platelets from polylactide nanocomposite films

DEFF Research Database (Denmark)

Schmidt, Bjørn; Katiyar, Vimal; Plackett, David

2011-01-01

(OLLA). This is the first reported investigation on the migration properties of PLA-LDH nanocomposite films. The tests were carried out as part of an overall assessment of the suitability of such films for use as food contact materials (FCM). Total migration was determined according to a European...... detected arises from the use of organotin catalysts in the manufacture of PLA....

The binding characteristics and orientation of a novel radioligand with distinct properties at 5-HT3A and 5-HT3AB receptors

NARCIS (Netherlands)

Thompson, Andrew J; Verheij, Mark H P; Verbeek, Joost; Windhorst, Albert D; de Esch, Iwan J P; Lummis, Sarah C R

2014-01-01

VUF10166 (2-chloro-3-(4-methyl piperazin-1-yl)quinoxaline) is a ligand that binds with high affinity to 5-HT3 receptors. Here we synthesise [(3)H]VUF10166 and characterise its binding properties at 5-HT3A and 5-HT3AB receptors. At 5-HT3A receptors [(3)H]VUF10166 displayed saturable binding with a Kd

Synthesis of 9H-Indeno [1, 2-b] Pyrazine and 11H-Indeno [1, 2-b ...

African Journals Online (AJOL)

NICO

Synthesis of 9H-Indeno [1, 2-b] Pyrazine and. 11H-Indeno [1, 2-b] Quinoxaline Derivatives in. One-step Reaction from 2-Bromo-4-chloro-1-indanone. S. Jasouri1,2, J. Khalafy1,*, M. Badali2 and R.H. Prager3. 1Department of Chemistry, Urmia University, Urmia 57154, Iran. 2Daana Pharmaceutical Co., P.O. Box 5181, Tabriz ...

Retinoid X receptor gene expression and protein content in tissues of the rock shell Thais clavigera

Energy Technology Data Exchange (ETDEWEB)

Horiguchi, Toshihiro [Research Center for Environmental Risk, National Institute for Environmental Studies, 16-2 Onogawa, Tsukuba, Ibaraki 305-8506 (Japan)], E-mail: thorigu@nies.go.jp; Nishikawa, Tomohiro [Research Center for Environmental Risk, National Institute for Environmental Studies, 16-2 Onogawa, Tsukuba, Ibaraki 305-8506 (Japan); Ohta, Yasuhiko [Department of Veterinary Science, Faculty of Agriculture, Tottori University, 4-101 Koyamacho-Minami, Tottori 680-8553 (Japan); Shiraishi, Hiroaki; Morita, Masatoshi [Research Center for Environmental Risk, National Institute for Environmental Studies, 16-2 Onogawa, Tsukuba, Ibaraki 305-8506 (Japan)

2007-10-15

To elucidate the role of retinoid X receptor (RXR) in the development of imposex caused by organotin compounds in gastropod molluscs, we investigated RXR gene expression and RXR protein content in various tissues of male and female wild rock shells (Thais clavigera). Quantitative real-time polymerase chain reaction, Western blotting, and immunohistochemistry with a commercial antibody against human RXR {alpha} revealed that RXR gene expression was significantly higher in the penises of males and imposex-exhibiting females than in the penis-forming areas of normal females (P < 0.01 and P < 0.05, respectively). Western blotting demonstrated that the antibody could detect rock shell RXR and showed that the male penis had the highest content of RXR protein among the analyzed tissues of males and normal females. Immunohistochemical staining revealed nuclear localization of RXR protein in the epithelial and smooth muscle cells of the vas deferens and in the interstitial or connective tissues and epidermis of the penis in males and imposex-exhibiting females. RXR could be involved in the mechanism of induction of male-type genitalia (penis and vas deferens) by organotin compounds in female rock shells.

Transformation of tributyltin in zebrafish eleutheroembryos (Danio rerio).

Science.gov (United States)

Borges, Aline Rocha; López-Serrano Oliver, Ana; Gallego-Gallegos, Mercedes; Muñoz-Olivas, Riansares; Rodrigues Vale, Maria Goreti; Cámara, Carmen

2014-12-01

Organotin compounds are highly versatile group of organometallic chemicals used in industrial and agricultural applications. Their endocrine-disrupting effects are well known and their extensive uses as biocide materials, e.g., in antifouling paints, for many years have led to serious environmental problems. So far, attention has mainly been given to tributyltin pollution in water, sediments, and marine organisms because of its highly toxic effects and high accumulation levels at very low concentrations. In this study, we will focus on the conversion of tributyltin after it is absorbed by zebrafish eleutheroembryos, presented here as an alternative model to adult fish for describing bioconcentration. A simplified analytical extraction procedure based on the use of an assisted ultrasonic probe and derivatization by ethylation, followed by gas chromatography with a flame photometric detector (GC-FPD) is proposed. This classical methodology for organotin determination has been validated by inductively coupled plasma mass spectrometry (ICP-MS) and Zeeman graphite furnace atomic absorption spectrometry (ZGF-AAS) in terms of total tin content. The speciation analysis results show that zebrafish eleutheroembryos absorb high amounts of tributyltin and convert it into monobutyltin and likely in inorganic tin.

Meat-related compounds and colorectal cancer risk by anatomical subsite.

Science.gov (United States)

Miller, Paige E; Lazarus, Philip; Lesko, Samuel M; Cross, Amanda J; Sinha, Rashmi; Laio, Jason; Zhu, Jay; Harper, Gregory; Muscat, Joshua E; Hartman, Terryl J

2013-01-01

Since meat may be involved in the etiology of colorectal cancer, associations between meat-related compounds were examined to elucidate underlying mechanisms in a population-based case-control study. Participants (989 cases/1,033 healthy controls) completed a food frequency questionnaire with a meat-specific module. Multivariable logistic regression was used to examine associations between meat variables and colorectal cancer; polytomous logistic regression was used for subsite-specific analyses. The following significant positive associations were observed for meat-related compounds: 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (DiMeIQx) and colorectal, distal colon, and rectal tumors; 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) and colorectal and colon cancer tumors; nitrites/nitrates and proximal colon cancer; 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) and rectal cancer; and benzo[a]pyrene and rectal cancer (P-trends cancer and pan-fried red meat and colorectal cancer were found (P-trends cancer; and well-done/charred poultry and colorectal, colon, and proximal colon tumors (P-trends nitrates may be involved in colorectal cancer etiology. Further examination into the unexpected inverse associations between poultry and colorectal cancer is warranted.

A prospective investigation of fish, meat and cooking-related carcinogens with endometrial cancer incidence.

Science.gov (United States)

Arem, H; Gunter, M J; Cross, A J; Hollenbeck, A R; Sinha, R

2013-08-06

There are limited prospective studies of fish and meat intakes with risk of endometrial cancer and findings are inconsistent. We studied associations between fish and meat intakes and endometrial cancer incidence in the large, prospective National Institutes of Health-AARP Diet and Health Study. Intakes of meat mutagens 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-trimethylimidazo[4,5-f]quinoxaline (DiMeIQx) and benzo(a)pyrene (BaP) were also calculated. We used Cox proportional hazards regression models to estimate hazard ratios (HRs) and 95% confidence intervals (CIs). We observed no associations with endometrial cancer risk comparing the highest to lowest intake quintiles of red (HR=0.91, 95% CI 0.77-1.08), white (0.98, 0.83-1.17), processed meats (1.02, 0.86-1.21) and fish (1.10, 95% CI 0.93-1.29). We also found no associations between meat mutagen intakes and endometrial cancer. Our findings do not support an association between meat or fish intakes or meat mutagens and endometrial cancer.

Effects of glucose on the formation of PhIP in a model system.

Science.gov (United States)

Skog, K; Jägerstad, M

1991-12-01

The effect of glucose on the formation of the food mutagen PhIP (2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine) was studied in a model system. When a mixture of creatine (0.9 mmol), phenylalanine (0.9 mmol) and glucose (0.45 mmol) was heated in diethylene glycol and water (3 ml, 5:1) for 10 min at 180 or 225 degrees C several mutagens were produced. Identification by HPLC, UV absorption spectroscopy and mass spectrometry revealed the presence of PhIP as well as 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline and minor amounts of 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline. Heating the system without glucose produced PhIP as a single mutagen, but in considerably lower amount. An inhibiting effect of glucose in high concentrations was demonstrated. When glucose was added in more than or equimolar amounts of the other two reactants, the formation of mutagens was markedly reduced. Tyrosine heated under the same conditions, with creatine and glucose, showed mutagenic activity. However, no PhIP nor any other known food mutagen was identified from the tyrosine mixture.

Butyltin Concentrations in Selected US Harbor Systems. A Baseline Assessment.

Science.gov (United States)

1987-04-01

these locations will provide important reference points for future monitoring studies. Impacted sites near vessels coated with tributyltin ( TBT ...few years. the Navy intends to start gradually using organotin antifouling (AF) paints that contain tributyltin ( TBT ) as a biocide. These commercially...the last several years (Seligman, et al., 1986. & Valkirs, et al., 1986). The degradation of TBT in seawater is of major interest es toxicity greatly

Pharmacokinetics and metabolism of cyadox and its main metabolites in beagle dogs following oral, intramuscular and intravenous administration

Directory of Open Access Journals (Sweden)

Adeel Sattar

2016-08-01

Full Text Available Cyadox (Cyx is an antibacterial drug of the quinoxaline group that exerts markedly lower toxicity in animals, compared to its congeners. Here, the pharmacokinetics and metabolism of Cyx after oral (PO, intramuscular (IM and intravenous (IV routes of administration were studied to establish safety criteria for the clinical use of Cyx in animals. Six beagle dogs (3 males, 3 females were administered Cyx through PO (40 mg kg-1 b.w., IM (10 mg kg-1 b.w. and IV (10 mg kg-1 b.w. routes with a washout period of 2 weeks in a crossover design. Highly sensitive high-performance liquid chromatography with ultraviolet detection (HPLC-UV was employed for determination of Cyx and its main metabolites, 1, 4-bisdesoxycyadox (Cy1, cyadox-1-monoxide (Cy2, N-(quinoxaline-2-methyl-cyanide acetyl hydrazine (Cy4 and quinoxaline-2-carboxylic acid (Cy6 in plasma, urine and feces of dogs. The oral bioavailability of Cyx was 4.75%, suggesting first-pass effect in dogs. The concentration vs. time profile in plasma after PO administration indicates that Cyx is rapidly dissociated into its metabolites and eliminated from plasma earlier, compared to its metabolites. The areas under the curve (AUC of Cyx after PO, IM and IV administration were 1.22 h×µg mL-1, 6.3 h×µg mL-1, and 6.66 h×µg mL-1, while mean resident times (MRT were 7.32, 3.58 and 0.556 h, respectively. Total recovery of Cyx and its metabolites was >60% with each administration route. In feces, 48.83% drug was recovered after PO administration, while 18.15% and 17.11% after IM and IV injections, respectively, suggesting renal clearance as the major route of excretion with IM and IV administration and feces as the major route with PO delivery. Our comprehensive evaluation of Cyx has uncovered detailed information that should facilitate its judicious use in animals by improving understanding of its pharmacology.

Distribution of butyltins in waters and sediments of the Mandovi and Zuari estuaries, west coast of India

Digital Repository Service at National Institute of Oceanography (India)

Garg, A.; Meena, R; Bhosle, N.B.

., Philips, I. R., & Hawker, D. W. (2004). Sorption and desorption behaviour of tributyltin with natural sediments. Environmental Science Technology, 38, 6694-6700. CCME (1992). Canadian water quality guidelines: Canadian Council of Ministers..., agrichemicals and in glass coatings (Bhosle 2006). The predominant source of organotins in the marine waters is related to their use as biocides in antifouling paints, especially tributyltin (TBT). In order to control biofouling about 70% of the worlds...

Treatability Studies of Tributyltin in Activated Sludge

Science.gov (United States)

1989-12-01

per liter pg/L Picograms per liter ppb Parts per billion RREL Risk Reduction Engineering Laboratory TBT Tributyltin Chloride TKN Total Kjeldahl number...success of tributyltin ( TBT ) compounds in inhibiting the growth of marine organisms has led to their use as pesticides in marine antifouling paints...organotin wastes because: (1) substan- tial dilution is available, which minimizes the toxic impacts of TBT compounds; (2) a diverse biomass is present, which

Microencapsulation of Biocides for Reduced Copper, Long-life Antifouling Coatings

Science.gov (United States)

2007-02-01

NEHC - Naval Environmental Health Center ONR – Office of Naval Research PVA – polyvinyl alcohol QPL – qualified products list TBT – tributyltin ...also organotin) TSCA - Toxic Substance Control Act UNDS - Uniform National Discharge Standards US – United States VOC – volatile organic content...mechanisms, and are designed to erode or polish with time to ensure long service lives (Yebra et. al., 2004). Fouling release coatings are a non- toxic

Occurrence of imposex in Thais haemastoma: possible evidence of environmental contamination derived from organotin compounds in Rio de Janeiro and Fortaleza, Brazil Ocorrência de imposex em Thais haemastoma: possíveis evidências de contaminação ambiental por compostos organotínicos no Rio de Janeiro e em Fortaleza, Brasil

Directory of Open Access Journals (Sweden)

Marcos Antonio Fernandez

2002-04-01

Full Text Available There are indications that the widespread use of organotin compounds (TBT and TPT as antifoulings, as stabilizers in plastic and as pesticides, has severely affected several species of marine organisms. The most striking effect of TBT and TPT as hormonal disruptors is the development of male organs in females of gastropods, currently denominated imposex. This syndrome can lead to the sterilization and death of affected organisms. The present work gives an overview of the present state of knowledge on imposex occurrence and reports results of a survey conducted in Guanabara Bay, Rio de Janeiro and in several sites along the coast of Fortaleza, Ceará State. Different stages of imposex development were verified in this survey, however, the most prominent levels appeared associated to known spot sources of TBT and TPT.Existem evidências de que a utilização amplamente disseminada de compostos organoestânicos (TBT e TPT como antiincrustantes, estabilizadores em plásticos e como pesticidas tenha afetado severamente diversas espécies de organismos marinhos. O mais característico efeito do TBT e do TPT como desreguladores endócrinos é o desenvolvimento de caracteres sexuais masculinos em fêmeas de gastrópodos, conhecido como imposex. Esta síndrome pode levar à esterelização e morte dos organismos afetados. O presente trabalho apresenta uma vista geral ao estado atual do conhecimento sobre a ocorrência do imposex, e reporta os resultados de um estudo conduzido na Baía de Guanabara, Rio de Janeiro, e ao longo da costa de Fortaleza, no Ceará. Diferentes estágios de desenvolvimento do imposex foram verificados neste estudo, os mais proeminentes parecendo associados às fontes pontuais locais conhecidas de TBT e TPT.

Effects of tributyltin on early life-stage, reproduction, and gonadal sex differentiation in Japanese medaka (Oryzias latipes).

Science.gov (United States)

Horie, Yoshifumi; Yamagishi, Takahiro; Shintaku, Yoko; Iguchi, Taisen; Tatarazako, Norihisa

2018-07-01

Tributyltin, an organotin compound, was used worldwide as an antifouling agent in aquatic environments and there has been much concern about the toxicological and ecotoxicological properties of organotin compounds. Even though it has been prohibited worldwide, tributyltin is still detected at low concentrations in aquatic environments. Here we investigated the effects of tributyltin on the early life-stage, reproduction, and gonadal sex differentiation in Japanese medaka (Oryzias latipes). In adults, exposure to tributyltin at 3.82 μg/L suppressed fecundity and fertility and increased mortality. At 10.48 μg/L all medaka died by the sixth day of exposure. Exposure to tributyltin during early life-stages induced no significant differences in mortality or embryonic development, but growth was suppressed in groups exposed to 0.13 and 0.68 μg/L. Furthermore, there was no abnormal gonadal development in Japanese medaka exposed to tributyltin. These results provide evidence of the negative effects of tributyltin on reproduction in a teleost fish. Tributyltin did not affect gonadal sex differentiation in Japanese medaka, but fecundity and fertility were suppressed, although it is not clear whether this suppression resulted from the endocrine-disrupting action of tributyltin or its toxicity. Copyright © 2018 Elsevier Ltd. All rights reserved.

Meat-Related Compounds and Colorectal Cancer Risk by Anatomical Subsite

Science.gov (United States)

Miller, Paige E.; Lazarus, Philip; Lesko, Samuel M.; Cross, Amanda J.; Sinha, Rashmi; Laio, Jason; Zhu, Jay; Harper, Gregory; Muscat, Joshua E.; Hartman, Terryl J.

2012-01-01

Since meat may be involved in the etiology of colorectal cancer, associations between meat-related compounds were examined to elucidate underlying mechanisms in a population-based case-control study. Participants (989 cases/1,033 healthy controls) completed a food frequency questionnaire with a meat-specific module. Multivariable logistic regression was used to examine associations between meat variables and colorectal cancer; polytomous logistic regression was used for subsite-specific analyses. The following significant positive associations were observed for meat-related compounds: 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (DiMeIQx) and colorectal, distal colon, and rectal tumors; 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) and colorectal and colon cancer tumors; nitrites/nitrates and proximal colon cancer; 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) and rectal cancer; and benzo[a]pyrene and rectal cancer (P-trends meat type, cooking method, and doneness preference, positive associations between red processed meat and proximal colon cancer and pan-fried red meat and colorectal cancer were found (P-trends nitrites, and nitrates may be involved in colorectal cancer etiology. Further examination into the unexpected inverse associations between poultry and colorectal cancer is warranted. PMID:23441608

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.

The National Shipbuilding Research Program. Development of a Quick TBT Analytical Method

Science.gov (United States)

2000-08-16

Development of a Quick TBT Analytical Method 09/25/2000 Page 3 of 38 Executive Summary Concern about the toxic effect of tributyltin have caused the...Antifouling Paints on the Environment Tributyl tin ( TBT ) has been shown to be highly toxic to certain aquatic organisms at concentrations measured in the...paints, developed in the 1960s, contains the organotin tributyltin ( TBT ), which has been proven to cause deformations in oysters and sex changes in

Biofouling and Design of a Biomimetic Hull-Grooming Tool

Science.gov (United States)

2007-09-14

have barred the use of organotin compounds such as tributyltin ( TBT ) and copper-based paints, which are currently used by the Navy and have become...copper into the water, killing the fouling organisms. There is new research in biomimetic polymers that deter fouling, but are non- toxic . These polymers...is new research in biomimetic polymers that deter fouling, but are non- toxic . These polymers are rigidly attached to the hull surface extending

Management of Bottom Sediments Containing Toxic Substances: Proceedings of the U.S./Japan Experts Meeting (11th) Held in Seattle, Washington, on 4-6 November 1985.

Science.gov (United States)

1987-04-01

potential environmental impact of organotins and their effect on the dredging permit proenp, Eighteen-day-old mysids were exposed to tributyltin ( TBT ...sediment. The TBT toxicant became a significant deleterious factor by day 8. After 10 days control survival was 100 per- cent with sediment and 95 percent...It is generally accepted that the TBT cation is the toxic component and the anion is not a factor in its toxicity . TBT degradation products are less

Underwater Ship Husbandry Discharges

Science.gov (United States)

2011-11-01

which entered into force in September of 2008, prohibits the use of harmful organotins such as tributyltin ( TBT ) in AFCs used on international...States. The use of TBT AFCs is explicitly prohibited under the VGP, and vessels must remove such coatings or paint over them to prevent toxic ...to hull husbandry include (1) the discharge of toxic chemicals used as biocides in AFCs and (2) biofouling as a vector for aquatic nuisance species

Imposex in Crassilabrum crassilabrum (Neogastropoda: Muricidae) in the Peruvian central coast

OpenAIRE

Rivas, Rolf; Hurtado, Soledad; Cornelio, Dayanne; Mendoza, Jorge; Guabloche, Angélica; Iannacone, José; Alvariño, Lorena; Castañeda, Luz

2017-01-01

The imposex is a phenomenon that consists in the development of masculine sexual characteristics on the reproductive system of the gastropod female snails by organotin compounds (OTs), like tributyl tin (TBT). In the present study, the imposex was evaluated in Crassilabrum crassilabrum Sowerby, 1834 (Neogastropoda: Muricidae) from the central coast of Peru, for which individuals were collected from the intertidal zone of Pucusana and Ancon, Lima. Biometric measurements were taken and the rate...

The environmental chemical tributyltin chloride (TBT) shows both estrogenic and adipogenic activities in mice which might depend on the exposure dose

International Nuclear Information System (INIS)

Penza, M.; Jeremic, M.; Marrazzo, E.; Maggi, A.; Ciana, P.; Rando, G.; Grigolato, P.G.; Di Lorenzo, D.

2011-01-01

Exposure during early development to chemicals with hormonal action may be associated with weight gain during adulthood because of altered body homeostasis. It is known that organotins affect adipose mass when exposure occurs during fetal development, although no knowledge of effects are available for exposures after birth. Here we show that the environmental organotin tributyltin chloride (TBT) exerts adipogenic action when peripubertal and sexually mature mice are exposed to the chemical. The duration and extent of these effects depend on the sex and on the dose of the compound, and the effects are relevant at doses close to the estimated human intake (0.5 μg/kg). At higher doses (50-500 μg/kg), TBT also activated estrogen receptors (ERs) in adipose cells in vitro and in vivo, based on results from acute and longitudinal studies in ERE/luciferase reporter mice. In 3T3-L1 cells (which have no ERs), transiently transfected with the ERE-dependent reporter plus or minus ERα or ERβ, TBT (in a dose range of 1-100 nM) directly targets each ER subtype in a receptor-specific manner through a direct mechanism mediated by ERα in undifferentiated preadipocytic cells and by ERβ in differentiating adipocytes. The ER antagonist ICI-182,780 inhibits this effect. In summary, the results of this work suggest that TBT is adipogenic at all ages and in both sexes and that it might be an ER activator in fat cells. These findings might help to resolve the apparent paradox of an adipogenic chemical being also an estrogen receptor activator by showing that the two apparently opposite actions are separated by the different doses to which the organism is exposed. - Research highlights: → The environmental organotin tributyltin chloride shows dose-dependent estrogenic and adipogenic activities in mice. → The duration and extent of these effects depend on the sex and the dose of the compound. → The estrogenic and adipogenic effects of TBT occur at doses closed to the estimated

Conformational impact of structural modifications in 2-fluorocyclohexanone

Directory of Open Access Journals (Sweden)

Francisco A. Martins

2017-08-01

Full Text Available 2-Haloketones are building blocks that combine physical, chemical and biological features of materials and bioactive compounds, while organic fluorine plays a fundamental role in the design of performance organic molecules. Since these features are dependent on the three-dimensional chemical structure of a molecule, simple structural modifications can affect its conformational stability and, consequently, the corresponding physicochemical/biological property of interest. In this work, structural changes in 2-fluorocyclohexanone were theoretically studied with the aim at finding intramolecular interactions that induce the conformational equilibrium towards the axial or equatorial conformer. The interactions evaluated were hydrogen bonding, hyperconjugation, electrostatic and steric effects. While the gauche effect, originated from hyperconjugative interactions, does not appear to cause some preferences for the axial conformation of organofluorine heterocycles, more classical effects indeed rule the conformational equilibrium of the compounds. Spectroscopic parameters (NMR chemical shifts and coupling constants, which can be useful to determine the stereochemistry and the interactions operating in the series of 2-fluorocyclohexanone derivatives, were also calculated.

Effects of TBT (Tributyltin) on Marine Organisms: Field Assessment of a New Site-Specific Bioassay System.

Science.gov (United States)

1987-12-01

evaluated in San Diego Bay over a 7-month period using tributyltin ( TBT ) antifouling leachates. Three TBT concentrations (k = 0.065, 0.077 and 0.193 ug...tional value and epifaunal organisms and 2) test using tributyltin (TT) antifouling leachates. the efficacy of the PETS. The results of the TBT Three...Conoentrations of 0.200, study the effects of tributyltin (TBI), the primary 0.050 and 0.020 ug/l, respectively. Unfiltered toxic component of organotin AF

Synthesis of Tetraphenylstannacyclopentadienes (Stannoles). II. Derivatives and Adducts of 1,1-Dihalo-2,3,4,5-tetraphenylstannoles.

Science.gov (United States)

1981-04-15

Organotin compounds with high molecular weight (over 700) would often not give consistent analyses. Tin was determined gravimetri - cally as the oxide...0.05 mol) wire. A red solution formed after 10 minutes and a yellow solid precipitated . The slurry was added rapidly to a solution of phenyltin... precipitation achieved by cooling the green solution to -780C in Dry Ice. The white solid product (m.p. 156-158*C) was identified as 1,2,3,4

Controllable electrochemical growth protection system based on pH variation. Final report; Steuerbares elektrochemisches Bewuchsschutzsystem auf der Basis von pH-Aenderungen. Endbericht

Energy Technology Data Exchange (ETDEWEB)

Sandrock, S.; Scharf, E.M.; Reiter, K.; Neumann, H.G.; Guenther, E.; Franz, A.

2003-10-01

Preventing growth on ships is an economic as well as an ecological necessity. The current state of the art is to use antifoulings containing organotin compounds or copper for this purpose. What makes antifoulings effective are their heavy metal components. However, these also pose a formidable hazard to the marine ecosystem. This has led IMO to issue restrictive regulations aimed in particular at the organotin component. Alternative antifoulings based on silicone are only suitable for relatively fast going vessels. The purpose of the present project was to develop to market maturity a new, environmentally acceptable growth protection strategy that had already been tested at a small scale. The action principle of this protection consists in a discontinuous current induced pH change on the surface to be protected. [German] Nach gegenwaertigem Stand der Technik erfolgt die aus wirtschaftlichen und oekologischen Gruenden unverzichtbare Verhinderung von Bewuchs an Schiffen durch organozinn- bzw. kupferhaltige Unterwasseranstriche (Antifoulings). Von den Schwermetallen, auf denen das Wirkprinzip beruht, gehen erhebliche Gefahren fuer das marine Oekosystem aus. Die IMO hat deshalb speziell bezueglich des Organozinns bereits entsprechende restriktive Regelungen beschlossen. Alternative, silikonhaltige Anstriche sind nur fuer relativ schnell fahrende Schiffstypen geeignet. Im Rahmen des Projekts soll eine neue umweltvertraegliche Bewuchsschutzstrategie, die in kleinem Massstab bereits erprobt wurde, zur Praxisreife gefuehrt werden. Das Wirkprinzip besteht hier in einer diskontinuierlichen strominduzierten pH-Aenderung auf der zu schuetzenden Oberflaeche. (orig.)

Occurrence of tributyltin compounds and characteristics of heavy metals

International Nuclear Information System (INIS)

Sheikh, M. A.; Oomori, T.; Noah, N. M.; Tsuha, K.

2007-01-01

Surface sediment samples were collected from Tanzanian major commercial ports and studied for the distribution and behavior of tributyltin compounds and heavy metals. The content of tributyltin in sediments ranged from ND-3670 ng (Sn) g 1 dry wt (1 780 ± 1720) (Mean ± SD) at Zanzibar and from ND-16700 ng (Sn)g 1 dry wt (4080 ± 7540) at Dar Es Salaam ports, respectively. Maximum tributyltin levels were detected inside the both ports. Metabolic degradation of butyltin compounds showed that MBT + DBT > TBT %, this may be attributed by the warm ambient water and intense sunlight in the tropical regions. A sequential extraction procedure was undertaken to provide detailed chemical characteristics of heavy metals in the sediments. The procedure revealed that about 50 % of Fe in the both ports is in immobile fraction (residual fraction) while other metals; Cd, Cu, Ni, Co, Zn, Pb. and Mn were mostly found in exchangeable or carbonate fractions and thus can be easily remobilized and enter the aquatic food chain. This paper provides basic information of tributyltin compounds contamination and chemical characteristics of heavy metals in the marine ecosystem in Tanzania. To our knowledge, this is the first documentation of Organotin compounds in marine environments in East Africa and suggests the importance of further detailed Organotin compounds studies in other sub-Saharan Africa regions

A comparison of the effects of tributyltin chloride and triphenyltin chloride on cell proliferation, proapoptotic p53, Bax, and antiapoptotic Bcl-2 protein levels in human breast cancer MCF-7 cell line.

Science.gov (United States)

Fickova, Maria; Macho, Ladislav; Brtko, Julius

2015-06-01

In recent years it was disclosed, that numerous organotin(IV) derivatives have remarkable cytotoxicity against several types of cancer cells. The property to inhibit cell growth makes these compounds promising for antitumor therapy, as the clinical effectiveness of cisplatin is limited by drug resistance and significant side effects. Tributyltin and triphenyltin are known as endocrine disruptors. Moreover, the compounds exert their toxicity in mammals predominantly through nuclear receptor signaling. Here we present the effects of tributyltin chloride (TBT-Cl) and triphenyltin chloride (TPT-Cl) on cell proliferation, expression of proapoptotic p53, Bax, and antiapoptotic Bcl-2 proteins in human breast cancer MCF-7 cell line. Dose and time dependent (24, 48 and 72 h) cell expositions have demonstrated TBT-Cl as more effective in inhibiting MCF-7 cell proliferation than TPT-Cl. Short time treatment with TBT-Cl displayed marked stimulation of p53 protein expression when compared to TPT-Cl. Both organotin compounds displayed similar mild enhancement of Bax protein expression. The 24h exposition of TPT-Cl induced substantial diminution of Bcl-2 protein expression in comparison with both, untreated cells and TBT-Cl treated cells. Our observations indicate that TBT-Cl and TPT-Cl have different antiproliferative potency and distinct impact on expression of apoptosis marker proteins. Copyright © 2015 Elsevier Ltd. All rights reserved.

Tributyltin (TBT) and dibutyltin (DBT) differently inhibit the mitochondrial Mg-ATPase activity in mussel digestive gland.

Science.gov (United States)

Nesci, Salvatore; Ventrella, Vittoria; Trombetti, Fabiana; Pirini, Maurizio; Borgatti, Anna Rosa; Pagliarani, Alessandra

2011-02-01

Tri-n-butyltin (TBT) has long been considered as the most toxic among organotins, especially to membrane systems. The partially dealkylated derivative di-n-butyltin (DBT) has up to now received poor attention and, whenever considered, shown to be less toxic than TBT except on the immune system. The present kinetic approach evidences that both TBT and DBT in vitro inhibit the Mg-ATPase in mussel digestive gland mitochondria by a different mechanism. DBT even displays a higher efficiency than TBT (IC(50)=0.32 μM for TBT vs. 0.19 μM for DBT) in inhibiting the enzyme hydrolytic activity. Differently from TBT which at high concentrations (>1 μM) apparently decreases the oligomycin-sensitivity of the Mg-ATPase, DBT at any concentration tested does not affect the oligomycin sensitivity. TBT probably binds to F(0), either in the form of free enzyme or of enzyme-substrate complex (Ki=K'i), acting as non-competitive inhibitor with respect to the ATP substrate. Conversely DBT, which acts as uncompetitive inhibitor of ATP and as competitive inhibitor of Mg(2+) cofactor, may bind strongly to F(1) subunit, thus preventing ATP hydrolysis. The Mg-ATPase inhibition by both organotins warns against a potential threat to crucial cell energy metabolism processes even after years from contamination and partial TBT debutylation. Copyright © 2010 Elsevier Ltd. All rights reserved.

Toxicology of tetramethyltin and other organometals used in photovoltaic cell manufacture

Science.gov (United States)

Hamilton, L. D.; Medeiros, W. H.; Moskowitz, P. D.; Rybicka, K.

1988-07-01

In photovoltaic cell fabrication, organometals (alkyl metals) may be used in such processes as metalorganic chemical vapor deposition, transparent contact oxide deposition, doping, and ion implantation. Although these compounds offer potential performance advantages over earth metals and possibly greater safety in handling than metal hydrides, they are not without risk to health and property. Most organometals can ignite spontaneously in air. Some also react violently with water. Oxidation by-products from these reactions are hazardous to health. Of the organometals used in photovoltaic cell fabrication, only the toxicology of organotins (triethyl-, trimethyl- and tetramethyltin) was studied extensively. In mammalian systems, tetramethyltin is rapidly dealkylated to trimethyltin. Although tin was classified by some investigators as an essential trace element, the effects of organotin compounds on humans are poorly known. Animal studies show that the most prominent effects of trimethyltin are on the central nervous system. Several observations of poisoning were reported; effects ranged from reversible neurologic disorders to death. Limited available data suggest that humans respond to single acute doses and more alarmingly to repeated sub-toxic doses, suggesting a cumulative effect. Toxicologic properties of diethyltelluride also were evaluated in animal experiments. The compound had toxic effects on the blood, liver, kidney, heart, and skin. Based on these studies and others of related compounds (e.g., methylmercury, tributyltin) extreme caution should be exercised in using organometal compounds in photovoltaic cell manufacturing.

TBTC induces adipocyte differentiation in human bone marrow long term culture

International Nuclear Information System (INIS)

Carfi, M.; Croera, C.; Ferrario, D.; Campi, V.; Bowe, G.; Pieters, R.; Gribaldo, L.

2008-01-01

Organotins are widely used in agriculture and the chemical industry, causing persistent and widespread pollution. Organotins may affect the brain, liver and immune system and eventually human health. Recently, it has been shown that tri-butyltin (TBT) interacts with nuclear receptors PPARγ (peroxisome proliferator-activated receptor γ) and RXR (retinoid x receptor) leading to adipocyte differentiation in the 3T3 cell line. Since adipocytes are known to influence haematopoiesis, for instance through the expression of cytokines and adhesion molecules, it was considered of interest to further study the adipocyte-stimulating effect of TBTC in human bone marrow cultures. Nile Red spectrofluorimetric analysis showed a significant increase of adipocytes in TBTC-treated cultures after 14 days of long term culture. Real-time PCR and Western blot analysis confirmed the high expression of the specific adipocyte differentiation marker aP2 (adipocyte-specific fatty acid binding protein). PPARγ, but not RXR, mRNA was increased after 24 h and 48 h exposure. TBTC also induced a decrease in a number of chemokines, interleukins, and growth factors. Also the expression of leptin, a hormone involved in haematopoiesis, was down regulated by TBTC treatment. It therefore appears that TBTC induced adipocyte differentiation, whilst reducing a number of haematopoietic factors. This study indicates that TBTC may interfere in the haematopoietic process through an alteration of the stromal layer and cytokine homeostasis

Potential of mercury-resistant marine bacteria for detoxification of chemicals of environmental concern

Digital Repository Service at National Institute of Oceanography (India)

De, J.; Ramaiah, N.; Bhosle, N.B.; Garg, A.; Vardanyan, L.; Nagle, V.L.; Fukami, K.

-resistant Pseudomonas putida strain. Appl. Environ. Microbiol. 65: 5279-5284. 11) Champ, M.A. 2000. A review of organotin regulatory strategies: pending actions, related costs and benefits. Sci. Total Environ. 258: 21-71. 12) Chang, J.S., R. Law, and C.C. Chang. 1997... indicating that TBT were degraded by bacterial action. With organic enrichment, the amounts of TBT degraded were similar by both strains but the degradation rate was faster. Discussion Lower costs and higher efficiency at low metal concentrations...

Biological effects of tributyltin chloride (TBTC) in carp (Cyprinus carpio L.); Effetti biologici del tributilstagno cloruro (TBTC) in carpa (Cyprinus carpio L.)

Energy Technology Data Exchange (ETDEWEB)

Bressa, Giuliano [ENEL-CRAM Spa, Milan (Italy); Giombelli, Rossana [Milan, Univ. (Italy). Dipt. di Biologia; Prearo, Marino; Bozzetta, Elena [Istituto Zooprofilattico del Piemonte, Liguria e Valle D`Aosta, Turin (Italy); Sisti, Elivio [Centro Studi Ambientali, Rimini (Italy); Cima, Francesca [Padua, Univ. (Italy). Dipt. di Biologia

1997-01-01

Organotin compounds are widely used as biocides. In particular, tributyltin chloride (TBTC) is used for the preservation of wood and as antifouling agent in marine paints. The aim of the present investigation was to evaluate the uptake of the TBTC by fish (Cyprinus carpio) fed with contaminated pellets. Histological examination of the thymus of fish treated for 7 days with TBTC showed atrophy with severe lymphocytic depletion. TBTC and its metabolite DBTC were detected in the kidney, liver, spleen, thymus and muscle tissue.

The EU network on trace element speciation in full swing

DEFF Research Database (Denmark)

Cornelis, R.; Camara, C.; Ebdon, L.

2000-01-01

health and hygiene. The network covers a number of important issues including organotin compounds, chromium and nickel species, chemical characterisation of environmental and industrial particulate samples, risk assessment, selenium and a series of other essential and toxic elements in food, as well......The EC-funded thematic network 'Speciation 21' links scientists in analytical chemistry working in method development for the chemical speciation of trace elements, and potential users from industry and representatives of legislative agencies, in the field of environment, food and occupational...

A general approach for the synthesis of bimetallic M–Sn (M = Ru, Rh and Ir) catalysts for efficient hydrogenolysis of ester

KAUST Repository

Samal, Akshaya Kumar

2016-11-24

A versatile synthetic method was applied for the preparation of Sn containing bimetallic catalysts. The synthesis was performed by simply mixing the super hydride [LiB(C2H5)(3)H], with a metal (Ru, Rh or Ir) salt and an organotin complex in tetrahydrofuran solvent without using any surfactant. This leads to the formation of monodispersed M-Sn (M = Ru, Rh or Ir) bimetallic nanoparticles (NPs). These bimetallic catalysts show high performances in the hydrogenolysis of ester to the corresponding alcohol.

Synthesis of [3-14C]- and [phenyl-U-14C] olaquindox

International Nuclear Information System (INIS)

Maul, W.; Scherling, D.; Seng, F.

1981-01-01

Olaquindox is a new feed additive. [ 14 C]Olaquindox, labelled in different positions, was needed for tracer-studies of pharmacokinetics, biotransformation and residues in several species of animals. 2-[N-(2-hydroxethyl)-carbamoyl]-3-methyl-[3- 14 C]quinoxaline-1,4-dioxide([3- 14 C]Olaquindox) was synthesized from barium[ 14 C]carbonate (22 mmoles; 1.15 Ci) via [1- 14 C]acetic acid, sodium[1- 14 C]acetate, [1- 14 C]acetylchloride, ethyl[3- 14 C]acetoacetate and 2-carbethoxy-3-methyl-[3- 14 C]quinoxaline-1,4-dioxide with an overall yield of 10%, based on barium[ 14 C]carbonate. The radiochemical purity was better than 98% (tlc). The specific activities of three preparations were 10.5, 8.4 and 5.45 μCi/mg respectively. [phenyl-U- 14 C]Olaquindox was synthesized starting from [U- 14 C]aniline (19.8 mmoles; 284.4 mCi). Intermediate products were N-acetyl[U- 14 C]aniline, 2-nitro-N-acetyl[U- 14 C]aniline, 2-nitro[U- 14 C]aniline and [U- 14 C]benzofurazanoxide. The total yield was 50% as calculated for [U- 14 C]aniline. At calibration samples of two preparations showed specific activities of 49.5 and 11.1 μCi/mg respectively. The radiochemical purity was checked by tlc and exceeded 98%. (author)

Sampling and Analytical Method for Alpha-Dicarbonyl Flavoring Compounds via Derivatization with o-Phenylenediamine and Analysis Using GC-NPD

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Stephanie M. Pendergrass

2016-01-01

Full Text Available A novel methodology is described for the sampling and analysis of diacetyl, 2,3-pentanedione, 2,3-hexanedione, and 2,3-heptanedione. These analytes were collected on o-phenylenediamine-treated silica gel tubes and quantitatively recovered as the corresponding quinoxaline derivatives. After derivatization, the sorbent was desorbed in 3 mL of ethanol solvent and analyzed using gas chromatography/nitrogen-phosphorous detection (GC/NPD. The limits of detection (LOD achieved for each analyte were determined to be in the range of 5–10 nanograms/sample. Evaluation of the on-tube derivatization procedure indicated that it is unaffected by humidities ranging from 20% to 80% and that the derivatization procedure was quantitative for analyte concentrations ranging from 0.1 μg to approximately 500 μg per sample. Storage stability studies indicated that the derivatives were stable for 30 days when stored at both ambient and refrigerated temperatures. Additional studies showed that the quinoxaline derivatives were quantitatively recovered when sampling up to a total volume of 72 L at a sampling rate of 50 cc/min. This method will be important to evaluate and monitor worker exposures in the food and flavoring industry. Samples can be collected over an 8-hour shift with up to 288 L total volume collected regardless of time, sampling rate, and/or the effects of humidity.

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.

Crystal structure of 2,3-bis(4-methylphenylbenzo[g]quinoxaline

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Young-Inn Kim

2018-04-01

Full Text Available The title compound, C26H20N2, was obtained during a search for new π-extended ligands with the potential to generate efficient phosphors with iridium(III for organic light-emitting devices (OLEDs. The benzoquinoxaline ring system is almost planar (r.m.s. deviation = 0.076 Å. A pseudo-twofold rotation axis runs through the midpoints of the C2—C3 and C9—C10 bonds. The two phenyl rings are twisted relative to the benzoquinoxaline ring system, making dihedral angles of 53.91 (4 and 36.86 (6°. In the crystal, C—H...π (arene interactions link the molecules, but no π–π interactions between aromatic rings are observed.

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...

1,4-Dihydroxyquinoxaline-2,3(1H,4H-dione

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Wolfgang Frey

2008-03-01

Full Text Available The asymmetric unit of the title compound, C8H6N2O4, contains one half-molecule; a twofold rotation axis bisects the molecule. The quinoxaline ring is planar, which can be attributed to electron delocalization. In the crystal structure, intermolecular O—H...O hydrogen bonds link the molecules into R22(10 motifs, leading to layers, which interact via phenyl–phenyl interactions (C...C distances in the range 3.238–3.521 Å.

Dibutyltin Compounds Effects on PPARγ/RXRα Activity, Adipogenesis, and Inflammation in Mammalians Cells

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Flora A. Milton

2017-08-01

Full Text Available Organotins are a group of chemical compounds that have a tin atom covalently bound to one or more organic groups. The best-studied organotin is tributyltin chloride, which is an environmental pollutant and an endocrine disruptor. Tributyltin chloride has been shown to bind to PPARγ/RXRα and induces adipogenesis in different mammalian cells. However, there are few studies with other organotin compounds, such as dibutyltins. The aim of this study was to investigate the effect of dibutyltins diacetate, dichloride, dilaurate, and maleate on the transcriptional activity of the nuclear PPARγ and RXRα receptors, and on adipogenesis and inflammation. Analogous to tributyltin chloride, in reporter gene assay using HeLa cells, we observed that dibutyltins diacetate, dichloride, dilaurate, and maleate are partial agonists of PPARγ. Unlike tributyltin chloride, which is a full agonist of RXRα, dibutyltins dichloride and dilaurate are partial RXRα agonists. Additionally, the introduction of the C285S mutation, which disrupts tributyltin chloride binding to PPARγ, abrogated the dibutyltin agonistic activity. In 3T3-L1 preadipocytes, all dibutyltin induced adipogenesis, although the effect was less pronounced than that of rosiglitazone and tributyltin chloride. This adipogenic effect was confirmed by the expression of adipogenic markers Fabp4, Adipoq, and Glut4. Exposure of 3T3-L1 cells with dibutyltin in the presence of T0070907, a specific PPARγ antagonist, reduced fat accumulation, suggesting that adipogenic effect occurs through PPARγ. Furthermore, dibutyltins dichloride, dilaurate, and maleate inhibited the expression of proinflammatory genes in 3T3-L1 cells, such as Vcam1, Dcn, Fn1, S100a8, and Lgals9. Additionally, in RAW 264.7 macrophages, tributyltin chloride and dibutyltin dilaurate reduced LPS-stimulated TNFα expression. Our findings indicate that dibutyltins diacetate, dichloride, dilaurate, and maleate are PPARγ partial agonists and

Effects of Antifouling Biocides on Molecular and Biochemical Defense System in the Gill of the Pacific Oyster Crassostrea gigas.

Science.gov (United States)

Park, Mi Seon; Kim, Young Dae; Kim, Bo-Mi; Kim, Youn-Jung; Kim, Jang Kyun; Rhee, Jae-Sung

2016-01-01

Antifouling biocides such as organotin compounds and their alternatives are potent toxicants in marine ecosystems. In this study, we employed several molecular and biochemical response systems of the Pacific oyster Crassostrea gigas to understand a potential mode of action of antifouling biocides (i.e. tributyltin (TBT), diuron and irgarol) after exposure to different concentrations (0.01, 0.1, and 1 μg L-1) for 96 h. As a result, all the three antifouling biocides strongly induced the antioxidant defense system. TBT reduced both enzymatic activity and mRNA expression of Na+/K+-ATPase and acetylcholinesterase (AChE). Lower levels of both Na+/K+-ATPase activity and AChE mRNA expression were observed in the diuron-exposed oysters compared to the control, while the irgarol treatment reduced only the transcriptional expression of AChE gene. We also analyzed transcript profile of heat shock protein (Hsp) superfamily in same experimental conditions. All antifouling biocides tested in this study significantly modulated mRNA expression of Hsp superfamily with strong induction of Hsp70 family. Taken together, overall results indicate that representative organotin TBT and alternatives have potential hazardous effects on the gill of C. gigas within relatively short time period. Our results also suggest that analyzing a series of molecular and biochemical parameters can be a way of understanding and uncovering the mode of action of emerging antifouling biocides. In particular, it was revealed that Pacific oysters have different sensitivities depend on the antifouling biocides.

Exposure to sublethal concentrations of tributyltin reduced survival, growth, and 20-hydroxyecdysone levels in a marine mysid.

Science.gov (United States)

Kim, Bo-Mi; Saravanan, Manoharan; Lee, Do-Hee; Kang, Jung-Hoon; Kim, Moonkoo; Jung, Jee-Hyun; Rhee, Jae-Sung

2018-06-07

Tributyltin (TBT) is as an antifouling organotin compound used in boat paints. Although organotin-based antifouling agents have been banned on a global scale, the mode of action of TBT has been studied in numerous aquatic species because of its toxicity, persistence, bioaccumulation potential, and endocrine-disrupting characteristics. In this study, we conducted 96-h acute toxicity tests wherein we exposed juvenile and adult marine mysids to waterborne TBT. Over 4 weeks of exposure, mortality was dose-dependently increased in juveniles and adult mysids. To test sublethal effects of TBT on juvenile development, newborn juvenile mysids were exposed to 1, 5, or 10 ng L -1  TBT for 4 weeks. Subsequently, we measured morphological growth parameters and quantified the hormone ecdysterone (20-hydroxyecdysone: 20E), which controls molting in mysids. The lengths of the whole body, antennal scale, exopod, endopod, and telson were significantly smaller in the 5 and/or 10 ng L -1 TBT-exposed juvenile mysids than in control and DMSO-exposed groups. Levels of 20E were significantly lower at 5 and 10 ng L -1  TBT exposures. Additionally, the number of newly hatched juveniles was significantly lower from females previously exposed to 10 ng L -1  TBT. Our results indicate sublethal concentrations of TBT have inhibitory effects on the survival, growth, and production of juveniles. The lower 20E levels could be strongly associated with TBT-triggered inhibition. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effects of Antifouling Biocides on Molecular and Biochemical Defense System in the Gill of the Pacific Oyster Crassostrea gigas

Science.gov (United States)

Park, Mi Seon; Kim, Young Dae; Kim, Bo-Mi; Kim, Youn-Jung; Kim, Jang Kyun; Rhee, Jae-Sung

2016-01-01

Antifouling biocides such as organotin compounds and their alternatives are potent toxicants in marine ecosystems. In this study, we employed several molecular and biochemical response systems of the Pacific oyster Crassostrea gigas to understand a potential mode of action of antifouling biocides (i.e. tributyltin (TBT), diuron and irgarol) after exposure to different concentrations (0.01, 0.1, and 1 μg L-1) for 96 h. As a result, all the three antifouling biocides strongly induced the antioxidant defense system. TBT reduced both enzymatic activity and mRNA expression of Na+/K+-ATPase and acetylcholinesterase (AChE). Lower levels of both Na+/K+-ATPase activity and AChE mRNA expression were observed in the diuron-exposed oysters compared to the control, while the irgarol treatment reduced only the transcriptional expression of AChE gene. We also analyzed transcript profile of heat shock protein (Hsp) superfamily in same experimental conditions. All antifouling biocides tested in this study significantly modulated mRNA expression of Hsp superfamily with strong induction of Hsp70 family. Taken together, overall results indicate that representative organotin TBT and alternatives have potential hazardous effects on the gill of C. gigas within relatively short time period. Our results also suggest that analyzing a series of molecular and biochemical parameters can be a way of understanding and uncovering the mode of action of emerging antifouling biocides. In particular, it was revealed that Pacific oysters have different sensitivities depend on the antifouling biocides. PMID:28006823

Effect of tributyltin on trout blood cells: changes in mitochondrial morphology and functionality.

Science.gov (United States)

Tiano, Luca; Fedeli, Donatella; Santoni, Giorgio; Davies, Ian; Falcioni, Giancarlo

2003-05-12

The aquatic environment is the largest sink for the highly toxic organotin compounds, particularly as one of the main sources is the direct release of organotins from marine antifouling paints. The aim of this study was to investigate the mitochondrial toxicity and proapoptotic activity of tributyltin chloride (TBTC) in teleost leukocytes and nucleated erythrocytes, by means of electron microscopy investigation and mitochondrial membrane potential evaluation, in order to provide an early indicator of aquatic environmental pollution. Erythrocytes and leukocytes were obtained from an inbred strain of rainbow trout (Oncorhynchus mykiss). Transmission electronic micrographs of trout red blood cells (RBC) incubated in the presence of TBTC at 1 and 5 microM for 60 min showed remarkable mitochondrial morphological changes. TBTC-mediated toxicity involved alteration of the cristae ultrastructure and mitochondrial swelling, in a dose-dependent manner. Both erythrocytes and leukocytes displayed a consistent drop in mitochondrial membrane potential following TBTC exposure at concentrations >1 microM. The proapoptotic effect of TBTC on fish blood cells, and involvement of mitochondrial pathways was also investigated by verifying the release of cytochrome c, activation of caspase-3 and the presence of "DNA laddering". Although mitochondrial activity was much more strongly affected in erythrocytes, leukocytes incubated in the presence of TBTC showed the characteristic features of apoptosis after only 1 h of incubation. Longer exposures, up to 12 h, were required to trigger an apoptotic response in erythrocytes.

Extraction of tributyltin and triphenyltin across a single oil droplet/water interface

International Nuclear Information System (INIS)

Chikama, Katsumi; Negishi, Takayuki; Nakatani, Kiyoharu

2004-01-01

Tributyltin (TBT + ) and triphenyltin (TPT + ) were extracted with merocyanine 540 (MC - ) from water into a 1,6-dichlorohexane droplet with the radius of 40 μm and the absorption spectra of MC - were measured by a single microdroplet manipulation and microabsorption technique. The mass transfer rate and the partitioning ratio of MC - were characteristically influenced by the TBT + , TPT + , MC - , and Cl - concentrations in water. The ion pair extraction processes of the organotin compounds with the anions were discussed in terms of the ion transfer and adsorption-desorption of the solutes

X-ray intensifying screens

International Nuclear Information System (INIS)

Bossomaier, T.R.J.; Sangway, P.C.

1979-01-01

It is claimed that stabilization of X-ray intensifying screens against discolouration and hydrolysis of lanthanum or gadolinium oxyhalide phosphors can be achieved by incorporating into the phosphor/binder formulation a compound containing free epoxy groups. Suitable epoxy compounds include gamma glycidoxy trimethoxy silane and dimethyl di(m-glycidoxy methylphenyl) methane. The oxyhalide may be activated by Tb, Tm or Yb and may be mixed with other phosphors. Plasticisers and organo-tin stabilisers for the formulation are given. Many binders are specified, preferably these should not react with the free epoxy groups. (UK)

The Cycloaddition of the Benzimidazolium Ylides with Alkynes: New Mechanistic Insights.

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Costel Moldoveanu

Full Text Available New insights concerning the reaction mechanism in the cycloaddition reaction of benzimidazolium ylides to activated alkynes are presented. The proposed pathway leading both to 2-(1H-pyrrol-1-ylanilines and to pyrrolo[1,2-a]quinoxalin-4(5H-ones involves an opening of the imidazole ring from the cycloaddition product, followed by a nucleophilic attack of the aminic nitrogen to a proximal carbonyl group and the elimination of a leaving group. The mechanistic considerations are fully supported by experimental data, including the XRD resolved structure of the key reaction intermediate.

The Cycloaddition of the Benzimidazolium Ylides with Alkynes: New Mechanistic Insights.

Science.gov (United States)

Moldoveanu, Costel; Zbancioc, Gheorghita; Mantu, Dorina; Maftei, Dan; Mangalagiu, Ionel

2016-01-01

New insights concerning the reaction mechanism in the cycloaddition reaction of benzimidazolium ylides to activated alkynes are presented. The proposed pathway leading both to 2-(1H-pyrrol-1-yl)anilines and to pyrrolo[1,2-a]quinoxalin-4(5H)-ones involves an opening of the imidazole ring from the cycloaddition product, followed by a nucleophilic attack of the aminic nitrogen to a proximal carbonyl group and the elimination of a leaving group. The mechanistic considerations are fully supported by experimental data, including the XRD resolved structure of the key reaction intermediate.

Ethanol Does Not Promote MeIQx-initiated Rat Colon Carcinogenesis Based on Evidence from Analysis of a Colon Cancer Surrogate Marker

OpenAIRE

Kushida, Masahiko; Wanibuchi, Hideki; Wei, Min; Kakehashi, Anna; Ozaki, Keisuke; Sukata, Tokuo; Miyata, Kaori; Ogata, Keiko; Uwagawa, Satoshi; Fukushima, Shoji

2009-01-01

Epidemiological studies suggest that alcohol consumption increases the risk of developing colorectal cancer. However, the data are confounded by numerous cosegregating variables. To cast further light on the relationships between alcohol intake and colon cancer development, 21-day-old male F344/DuCrj rats were fed 200 ppm 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) in their diet for 8 weeks and doses of 0, 0.1, 0.3, 1, 3, 10 and 20% of ethanol in their drinking water ad libitum for ...

One-pot, Facile Synthesis of Quinoxaline Derivatives from Bis-aryl a ...

African Journals Online (AJOL)

NICO

Bis-aryl a-Hydroxyketones and o-Arenediamines using. KMnO. 4. /CuSO. 4 ... Faculty of Chemistry, Bu-Ali Sina University, Hamedan 65174, Iran. Received 31 ... cent materials,6 organic semiconductors,7 building blocks for the synthesis of ...

21 CFR 178.2650 - Organotin stabilizers in vinyl chloride plastics.

Science.gov (United States)

2010-04-01

... extraction tests shall cover at least three equilibrium periodic determinations, as follows: (i) The exposure... Furnace,” Analytical Chemistry, Vol. 49, p. 1090-1093 (1977), which is incorporated by reference. Copies...,” Analytical Chemistry, Vol. 49, pp. 1090-1093 (1977), which is incorporated by reference in accordance with 5...

Speciation of organotin compounds in environmental samples by GC-ICPMS

International Nuclear Information System (INIS)

Vahcic, M.; Milacic, R.; Scancar, J.

2009-01-01

Full text: Analytical procedure using 15 m GC column was applied for simultaneous speciation of OTCs in various environmental samples. Methyl-, butyl-, phenyl- and octyl- tin species were quantitatively determined. different extraction reagents and conditions were studied. OTCs species were derivatized by NaBEt 4 and extracted into isooctane or hexane. The applied analytical procedure considerably shortened analytical time and enabled simultaneous determination of 12 OTCs in environmental samples. (author)

Tributyltin and triphenyltin exposure promotes in vitro adipogenic differentiation but alters the adipocyte phenotype in rainbow trout.

Science.gov (United States)

Lutfi, Esmail; Riera-Heredia, Natàlia; Córdoba, Marlon; Porte, Cinta; Gutiérrez, Joaquim; Capilla, Encarnación; Navarro, Isabel

2017-07-01

Numerous environmental pollutants have been identified as potential obesogenic compounds affecting endocrine signaling and lipid homeostasis. Among them, well-known organotins such as tributyltin (TBT) and triphenyltin (TPT), can be found in significant concentrations in aquatic environments. The aim of the present study was to investigate in vitro the effects of TBT and TPT on the development and lipid metabolism of rainbow trout (Onchorynchus mykiss) primary cultured adipocytes. Results showed that TBT and TPT induced lipid accumulation and slightly enhanced peroxisome proliferator-activated receptor gamma (PPARγ) and CCAAT enhancer binding protein alpha (C/EBPα) protein expression when compared to a control, both in the presence or absence of lipid mixture. However, the effects were higher when combined with lipid, and in the absence of it, the organotins did not cause complete mature adipocyte morphology. Regarding gene expression analyses, exposure to TBT and TPT caused an increase in fatty acid synthase (fasn) mRNA levels confirming the pro-adipogenic properties of these compounds. In addition, when added together with lipid, TBT and TPT significantly increased cebpa, tumor necrosis factor alpha (tnfa) and ATP-binding cassette transporter 1 (abca1) mRNA levels suggesting a synergistic effect. Overall, our data highlighted that TBT and TPT activate adipocyte differentiation in rainbow trout supporting an obesogenic role for these compounds, although by themselves they are not able to induce complete adipocyte development and maturation suggesting that these adipocytes might not be properly functional. Copyright © 2017 Elsevier B.V. All rights reserved.

[Examination of analytical method for triphenyltin (TPT) and tributyltin (TBT) to revise the official methods based on "Act on the Control of Household Products Containing Harmful Substances"].

Science.gov (United States)

Kawakami, Tsuyoshi; Isama, Kazuo; Nakashima, Harunobu; Yoshida, Jin; Ooshima, Tomoko; Ohno, Hiroyuki; Uemura, Hitoshi; Shioda, Hiroko; Kikuchi, Yoko; Matsuoka, Atsuko; Nishimura, Tetsuji

2012-01-01

The use of triphenyltin (TPT) and tributyltin (TBT) in some household products is banned by "Act on the Control of Household Products Containing Harmful Substances" in Japan. To revise the official analytical method, the method for detecting these organotin compounds was examined in six laboratories using a textile product, water-based adhesive, oil-based paint, which contained known amounts of TPT and TBT (0.1, 1.0, 10 μg/g). TPT and TBT were measured by GC-MS after ethyl-derivation with sodium tetraethylborate. The TBT recoveries in the samples were 70-120%. The TPT recoveries in the water-based adhesive samples were 80-110%, while its concentrations in the textile product and oil-based paint samples decreased because of dephenylation during storage. However, the precision of the method examined was satisfactory because most coefficients of variation for TPT and TBT in the samples were less than 10%. Furthermore, the revised method was able to detect concentrations lower than the officially regulated value. However, the sample matrix and the condition of analytical instrument might affect the estimated TPT and TBT concentrations. Therefore, the revised method may not be suitable for quantitative tests; rather, it can be employed to judge the acceptable levels of these organotin compounds by comparing the values of control sample containing regulated amounts of TPT and TBT with those for an unknown sample, with deuterated TPT and TBT as surrogate substances. It is desirable that TPT in textile and oil-based paint samples are analyzed immediately after the samples obtained because of the decomposition of TPT.

Record of imposex in Cronia konkanensis (Gastropoda, Muricidae) from Indian waters

Digital Repository Service at National Institute of Oceanography (India)

VishwaKiran, Y.; Anil, A.C.

that concentrations as low as 1 ng Sn/l induce imposex in Nucella lapillus and sterilization of females is initiated at around 4 ng Sn/l (Gibbs et al., 1988). This has led to the decline in the population of dog-whelks in and around the coast of the UK (Bryan et al..., G. W., Gibbs, P. E., & Burt, G. R. (1988). A comparison of the eC128ectiveness of Tri-n-buytin chloride and five other organotin compounds in promoting the development of imposex in the dog- whelk Nucella lapillus. Journal of Marine Biological...

Triorganotin as a compound with potential reproductive toxicity in mammals

Directory of Open Access Journals (Sweden)

V.S. Delgado Filho

2011-09-01

Full Text Available Organotin compounds are typical environmental contaminants and suspected endocrine-disrupting substances, which cause irreversible sexual abnormality in female mollusks, called "imposex". However, little is known about the capability of triorganotin compounds, such as tributyltin and triphenyltin, to cause disorders in the sexual development and reproductive functions of mammals, including humans and rodents. Moreover, these compounds can act as potential competitive inhibitors of aromatase enzyme and other steroidogenic enzymes, affecting the reproductive capacity of male and female mammals. In this review, we discuss the cellular, biochemical, and molecular mechanisms by which triorganotin compounds induce adverse effects in the mammalian reproductive function.

Extraction of tributyltin and triphenyltin across a single oil droplet/water interface

Energy Technology Data Exchange (ETDEWEB)

Chikama, Katsumi; Negishi, Takayuki; Nakatani, Kiyoharu

2004-07-01

Tributyltin (TBT{sup +}) and triphenyltin (TPT{sup +}) were extracted with merocyanine 540 (MC{sup -}) from water into a 1,6-dichlorohexane droplet with the radius of 40 {mu}m and the absorption spectra of MC{sup -} were measured by a single microdroplet manipulation and microabsorption technique. The mass transfer rate and the partitioning ratio of MC{sup -} were characteristically influenced by the TBT{sup +}, TPT{sup +}, MC{sup -}, and Cl{sup -} concentrations in water. The ion pair extraction processes of the organotin compounds with the anions were discussed in terms of the ion transfer and adsorption-desorption of the solutes.

Monitored Natural Recovery at Contaminated Sediment Sites

Science.gov (United States)

2009-05-01

extracted metal  SERDP  Strategic Environmental Research and Development Program  SWAC  spatially weighted average concentration  TBT   tributyltin   TTBT... tributyltin ( TBT ) in both field and laboratory settings. Organotins are used as marine antifouling agents and in the manufacture of plastics and other...endpoints as  evidence of risk reduction in the Black River, Ohio.  4‐11  HIGHLIGHT 4‐2. Biotransformation of  tributyltin  to tin in a  freshwater system

NEW [SnR2(C2O42]2- (R = Ph, Bu MOIETY CONTAINING ADDUCTS AND COMPLEXES: SYNTHESIS, INFRARED AND MOSSBAUER STUDIES

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YAYA SOW

2015-05-01

Full Text Available New oxalato and hydrogenoxalato organotin (IV derivatives containing mono- and bichelating oxalates or a monochelating hydrogenoxalate, have been synthesized and characterized by elemental analyses, infrared and Mossbauer spectroscopy. The suggested structures are discrete, the environments around the tin (IV atoms being trans octahedral, seven coordinated or tetrahedral. The cations when present are involved in NH…O bonds. A 1 D supramolecular architecture is suggested for SnPh2 (HC2O42.1/2 C6H6. The C6H6 molecules obtained in situ molecules are lattice. SnPh3OH is involved in hydrogen bonding.

Effects of ionizing radiation on plastic food packaging materials: a review. 2. Global migration, sensory changes and the fate of additives

International Nuclear Information System (INIS)

Buchalla, R.; Schuttler, C.; Bogl, K.W.

1993-01-01

Increased ''global'' migration into food simulants has been described as a consequence of irradiation, particularly with fatty media; development of off-odors and taint transfer into food simulants have been observed with various plastics. Additives, especially antioxidants, are destroyed during irradiation, and increased ''specific'' migration values have been observed under certain circumstances. Organotin stabilizers in PVC are ultimately degraded to SnCl4, and increased migration of tin compounds was observed after gamma irradiation. Degradation products of phenol antioxidants, that were also found as migrants, have only recently been identified; some of these structures seem to be radiation specific

Dietary Intake of Meat Cooking-Related Mutagens (HCAs) and Risk of Colorectal Adenoma and Cancer: A Systematic Review and Meta-Analysis.

Science.gov (United States)

Chiavarini, Manuela; Bertarelli, Gaia; Minelli, Liliana; Fabiani, Roberto

2017-05-18

Much evidence suggests that the positive association between meat intake and colorectal adenoma (CRA) and cancer (CRC) risk is mediated by mutagenic compounds generated during cooking at high temperature. A number of epidemiological studies have estimated the effect of meat-related mutagens intake on CRC/CRA risk with contradictory and sometimes inconsistent results. A literature search was carried out (PubMed, Web of Science and Scopus) to identify articles reporting the relationship between the intake of meat-related mutagens (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-trimethylimidazo[4,5-f] quinoxaline: DiMeIQx, benzo(a) pyrene (B(a)P) and "meat derived mutagenic activity" (MDM)) and CRC/CRA risk. A random-effect model was used to calculate the risk association. Thirty-nine studies were included in the systematic review and meta-analysis. Polled CRA risk (15229 cases) was significantly increased by intake of PhIP (OR = 1.20; 95% CI: 1.13,1.28; p CRA risk in association with PhIP, MDM, and MeIQx. CRC risk (21,344 cases) was increased by uptake of MeIQx (OR = 1.14; 95% CI: 1.04,1.25; p = 0.004), DiMeIQx (OR = 1.12; 95% CI: 1.02,1.22; p = 0.014) and MDM (OR = 1.12; 95% CI: 1.06,1.19; p meat at high temperature may be responsible of its carcinogenicity.

Meat intake is not associated with risk of non-Hodgkin lymphoma in a large prospective cohort of U.S. men and women.

Science.gov (United States)

Daniel, Carrie R; Sinha, Rashmi; Park, Yikyung; Graubard, Barry I; Hollenbeck, Albert R; Morton, Lindsay M; Cross, Amanda J

2012-06-01

Meat intake has been inconsistently associated with risk of non-Hodgkin lymphoma (NHL), a heterogeneous group of malignancies of the lymphoid tissue etiologically linked to immunomodulatory factors. In a large U.S. cohort, we prospectively investigated several biologically plausible mechanisms related to meat intake, including meat-cooking and meat-processing compounds, in relation to NHL risk by histologic subtype. At baseline (1995-1996), participants of the NIH-AARP Diet and Health Study completed a diet and lifestyle questionnaire (n = 492,186), and a subcohort (n = 302,162) also completed a questionnaire on meat-cooking methods and doneness levels. Over a mean of 9 y of follow-up, we identified 3611 incident cases of NHL. In multivariable Cox proportional hazards regression models, we found no association between intake of red meat, processed meat, fish, poultry, heme iron, nitrite, nitrate, animal fat, or protein and NHL risk. MeIQx (2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline) and DiMeIQx (2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline), heterocyclic amines formed in meats cooked to well done at high temperatures, were inversely associated with chronic lymphocytic leukemia/small lymphocytic lymphoma [n = 979; HR (95% CI) for the highest vs. lowest quintile of intake: 0.73 (0.55, 0.96) and 0.77 (0.61, 0.98), respectively]. In this large U.S. cohort, meat intake was not associated with NHL or any histologic subtypes of NHL. Contrary to findings in animal models and other cancer sites, meat-cooking and -processing compounds did not increase NHL risk.

Mechanisms of the Testis Toxicity Induced by Chronic Exposure to Mequindox

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Qianying Liu

2017-09-01

Full Text Available Mequindox (MEQ is a synthetic antimicrobial agent widely used in China since the 1980s. Although the toxicity of MEQ is well recognized, its testis toxicity has not been adequately investigated. In the present study, we provide evidence that MEQ triggers oxidative stress, mitochondrion dysfunction and spermatogenesis deficiency in mice after exposure to MEQ (0, 25, 55, and 110 mg/kg in the diet for up to 18 months. The genotoxicity and adrenal toxicity may contribute to sperm abnormalities caused by MEQ. Moreover, using LC/MS-IT-TOF analysis, two metabolites, 3-methyl-2-(1-hydroxyethyl quinoxaline-N4-monoxide (M4 and 3-methyl-2-(1-hydroxyethyl quinoxaline-N1-monoxide (M8, were detected in the serum of mice, which directly confirms the relationship between the N→O group reduction metabolism of MEQ and oxidative stress. Interestingly, only M4 was detected in the testes, suggesting that the higher reproductive toxicity of M4 than M8 might be due to the increased stability of M4-radical (M4-R compared to M8-radical (M8-R. Furthermore, the expression of the blood-testis barrier (BTB-associated junctions such as tight junctions, gap junctions and basal ectoplasmic specializations were also examined. The present study demonstrated for the first time the role of the M4 in testis toxicity, and illustrated that the oxidative stress, mitochondrion dysfunction and interference in spermatogenesis, as well as the altered expression of BTB related junctions, were involved in the reproductive toxicity mediated by MEQ in vivo.

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.

Anthropogenic pollution indicators in marine environment of the Eastern Part of the Gulf of Finland

Science.gov (United States)

Zhakovskaya, Zoya; Nikiforov, Vladimir; Mamontova, Varvara; Khoroshko, Larisa; Chernova, Ekaterina; Russkikh, Iana

2014-05-01

Pollution involving hazardous substances is considered one of the major problems affecting the state of the Baltic marine environment. However, assessment of the vast majority of the hazardous substances (including accepted as pollution indicators) in the environment have not been monitored in Russian Federation yet. Moreover there are no official guideline values for their presence or release in environment. For our investigation we have selected the organotin biocides and widespread pharmaceutical diclofenac. The study is focused on surface marine water and bottom sediments, collected from the eastern part of the Gulf of Finland during the navigation seasons of 2012-2013. Organotin compounds belong to a large group of key marine contaminants. They had been widely used in the world industry as antifouling paints, fungicides and biocides until the middle of 1980s. Tributyltin (TBT) and triphenyltin (TPhT) are the most hazardous of all organotin compounds, causing such biological effects as shell deformation, endocrine disruption, imposex and intersex phenomena at the concentration of 2 ng/L. The use of TBT in antifouling paints was banned within EU in 2003 and within Russian Federation in 2008. Monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT) and triphenyltin (TPhT) were analysed as ethyl derivatives using electron impact gas chromatography-mass spectrometry (GC-MS-EI) in single ion monitoring mode (SIM). TBT and TPhT were frequently found above MAC of 1.5 ng/L and 2 ng/g dw respectively in both water and bottom sediment samples collected from the Gulf of Finland water basin. The highest detected concentration detected mainly in coastal areas with dense ship traffic were 670 ng/L (TBT) in water samples, 440 ng/g dw (TBT), 160 ng/g dw (TPhT) in sediment samples. Potential risks from the environmental presence of pharmaceuticals and personal care products (PPCP), such as medicine, hormones, means of personal hygiene, etc. reveal in abnormal physiological

6,7-Dichloro-3-(2,4-dichlorobenzylquinoxalin-2(1H-one

Directory of Open Access Journals (Sweden)

Jinpeng Zhang

2012-08-01

Full Text Available In the title compound, C15H8Cl4N2O, the quinoxaline ring system is almost planar, with a dihedral angle between the benzene and pyrazine rings of 3.1 (2°. The 2,4-dichlorophenyl ring is approximately perpendicular to the pyrazine ring, with a dihedral angle of 86.47 (13° between them. The crystal packing features intermolecular N—H...O hydrogen bonds and π–π stacking interactions, with centroid–centroid distances in the range 3.699 (3–4.054 (3 Å.

Study of physicochemical stability of the copper/polyphenylquinoxaline interfaces

Science.gov (United States)

Even, R.; Palleau, J.; Oberlin, J. C.; Pantel, R.; Laviale, D.; Templier, F.; Torres, J.; Giustiniani, R.; Cros, A.

Thin film technologies are now applied in building up multilayered chip to chip interconnections to achieve agressive requirement such as high electrical performance or extreme compactness. Copper as conductor and a new polymeric material, a poly phenyl quinoxaline, as dielectric have been chose to fulfill demanding electrical and physical conditions. Thermal stability at the interface Cu/polymer and polymer/Cu during polymer curing process is very important to preserve good adhesion between the conductor and dielectric materials. We have studied in this work the interfacial behavior as a function of annealing temperature and of annealing atmosphere.

Total fluorine, extractable organic fluorine, perfluorooctane sulfonate and other related fluorochemicals in liver of Indo-Pacific humpback dolphins (Sousa chinensis) and finless porpoises (Neophocaena phocaenoides) from South China

Energy Technology Data Exchange (ETDEWEB)

Yeung, L.W.Y. [Centre for Coastal Pollution and Conservation, Department of Biology and Chemistry, City University of Hong Kong, Kowloon Tong, Hong Kong (China); National Institute of Advanced Industrial Science and Technology (AIST), Onogawa 16-1, Tsukuba, Ibaraki 305-8569 (Japan); Miyake, Y. [National Institute of Advanced Industrial Science and Technology (AIST), Onogawa 16-1, Tsukuba, Ibaraki 305-8569 (Japan); Wang, Y. [Centre for Coastal Pollution and Conservation, Department of Biology and Chemistry, City University of Hong Kong, Kowloon Tong, Hong Kong (China); National Institute of Advanced Industrial Science and Technology (AIST), Onogawa 16-1, Tsukuba, Ibaraki 305-8569 (Japan); Taniyasu, S. [National Institute of Advanced Industrial Science and Technology (AIST), Onogawa 16-1, Tsukuba, Ibaraki 305-8569 (Japan); Yamashita, N. [National Institute of Advanced Industrial Science and Technology (AIST), Onogawa 16-1, Tsukuba, Ibaraki 305-8569 (Japan)], E-mail: nob.yamashita@aist.go.jp; Lam, P.K.S. [Centre for Coastal Pollution and Conservation, Department of Biology and Chemistry, City University of Hong Kong, Kowloon Tong, Hong Kong (China)], E-mail: bhpksl@cityu.edu.hk

2009-01-15

The concentrations of 10 PFCs (perfluorinated compounds: PFOS, PFHxS, PFOSA, N-EtFOSA, PFDoDA, PFUnDA, PFDA, PFNA, PFOA, and PFHpA) were measured in liver samples of Indo-Pacific humpback dolphins (Sousa chinensis) (n = 10) and finless porpoises (Neophocaena phocaenoides) (n = 10) stranded in Hong Kong between 2003 and 2007. PFOS was the dominant PFC in the tissues at concentrations ranging at 26-693 ng/g ww in dolphins and 51.3-262 ng/g ww in porpoises. A newly developed combustion ion chromatography for fluorine was applied to measure total fluorine (TF) and extractable organic fluorine (EOF) in these liver samples to understand PFC contamination using the concept of mass balance analysis. Comparisons between the amounts of known PFCs and EOF in the livers showed that a large proportion ({approx}70%) of the organic fluorine in both species is of unknown origin. These investigations are critical for a comprehensive assessment of the risks of these compounds to humans and other receptors. - Comparison between the amounts of known PFCs and EOF in the livers of Indo-Pacific humpback dolphin and finless porpoise in South China showed that a large proportion ({approx}70%) of the organofluorine is of unknown origin.

Total fluorine, extractable organic fluorine, perfluorooctane sulfonate and other related fluorochemicals in liver of Indo-Pacific humpback dolphins (Sousa chinensis) and finless porpoises (Neophocaena phocaenoides) from South China

International Nuclear Information System (INIS)

Yeung, L.W.Y.; Miyake, Y.; Wang, Y.; Taniyasu, S.; Yamashita, N.; Lam, P.K.S.

2009-01-01

The concentrations of 10 PFCs (perfluorinated compounds: PFOS, PFHxS, PFOSA, N-EtFOSA, PFDoDA, PFUnDA, PFDA, PFNA, PFOA, and PFHpA) were measured in liver samples of Indo-Pacific humpback dolphins (Sousa chinensis) (n = 10) and finless porpoises (Neophocaena phocaenoides) (n = 10) stranded in Hong Kong between 2003 and 2007. PFOS was the dominant PFC in the tissues at concentrations ranging at 26-693 ng/g ww in dolphins and 51.3-262 ng/g ww in porpoises. A newly developed combustion ion chromatography for fluorine was applied to measure total fluorine (TF) and extractable organic fluorine (EOF) in these liver samples to understand PFC contamination using the concept of mass balance analysis. Comparisons between the amounts of known PFCs and EOF in the livers showed that a large proportion (∼70%) of the organic fluorine in both species is of unknown origin. These investigations are critical for a comprehensive assessment of the risks of these compounds to humans and other receptors. - Comparison between the amounts of known PFCs and EOF in the livers of Indo-Pacific humpback dolphin and finless porpoise in South China showed that a large proportion (∼70%) of the organofluorine is of unknown origin

Development of new methods in modern selective organic synthesis: preparation of functionalized molecules with atomic precision

International Nuclear Information System (INIS)

Ananikov, V P; Khemchyan, L L; Ivanova, Yu V; Dilman, A D; Levin, V V; Bukhtiyarov, V I; Sorokin, A M; Prosvirin, I P; Romanenko, A V; Simonov, P A; Vatsadze, S Z; Medved'ko, A V; Nuriev, V N; Nenajdenko, V G; Shmatova, O I; Muzalevskiy, V M; Koptyug, I V; Kovtunov, K V; Zhivonitko, V V; Likholobov, V A

2014-01-01

The challenges of the modern society and the growing demand of high-technology sectors of industrial production bring about a new phase in the development of organic synthesis. A cutting edge of modern synthetic methods is introduction of functional groups and more complex structural units into organic molecules with unprecedented control over the course of chemical transformation. Analysis of the state-of-the-art achievements in selective organic synthesis indicates the appearance of a new trend — the synthesis of organic molecules, biologically active compounds, pharmaceutical substances and smart materials with absolute selectivity. Most advanced approaches to organic synthesis anticipated in the near future can be defined as 'atomic precision' in chemical reactions. The present review considers selective methods of organic synthesis suitable for transformation of complex functionalized molecules under mild conditions. Selected key trends in the modern organic synthesis are considered including the preparation of organofluorine compounds, catalytic cross-coupling and oxidative cross-coupling reactions, atom-economic addition reactions, methathesis processes, oxidation and reduction reactions, synthesis of heterocyclic compounds, design of new homogeneous and heterogeneous catalytic systems, application of photocatalysis, scaling up synthetic procedures to industrial level and development of new approaches to investigation of mechanisms of catalytic reactions. The bibliography includes 840 references

Superhydrophobic titania nanoparticles for fabrication of paper-based analytical devices: An example of heavy metals assays.

Science.gov (United States)

Xu, Wenjian; Chen, Xi; Cai, Songcai; Chen, Jin; Xu, Zhen; Jia, Hongpeng; Chen, Jing

2018-05-01

A new strategy has been introduced to successfully fabricate the hydrophobic barriers of PADs by using organofluorine-modified superhydrophobic TiO 2 NPs. Superhydrophobic TiO 2 -140 NPs with high-photoactivity can be converted to hydrophilicity by self-degradation of surface organic moieties under full spectrum light irradiation. Superhydrophobic TiO 2 -RT NPs with low-photoactivity exhibits good hydrophobic stability under light irradiation. Thus, combining these features, the PADs have been designed and constructed by photo-induced fabrication of hydrophobic barriers on the surface of the paper. To demonstrate the effectiveness of the constructed PADs, colorimetric detections have been displayed for Fe 3+ and Ni 2+ ions. The synchronous multi-component detections based on the "multi-channel" PADs and the intuitive detections based on the "chemical-symbol-style" PADs are rapid and feasible. A detection range of Fe 3+ and Ni 2+ ions based on the "circle-array" PAD is applicable and reliable in 0.2-6.0 mM and 0.4-4.0 mM, respectively. Thus, these results make it to be believed that this new strategy provides an alternative way to effectively construct the PADs. Copyright © 2018 Elsevier B.V. All rights reserved.

One-pot efficient green synthesis of 1,4-dihydro-quinoxaline-2,3

Indian Academy of Sciences (India)

3-dione (1) has been achieved in a one-pot reaction at room temperature from substituted -phenylene diamine and oxalic acid under solvent-free conditions by a simple grinding method with unsurpassed atom economy. Thermal and powder ...

Synthesis and characterization of novel organotin carboxylate maleimide monomers and copolymers

Directory of Open Access Journals (Sweden)

2009-06-01

Full Text Available Two novel tributyltin carboxylate maleimide monomers, tributyltin(maleimidoacetate and tributyltin(4-maleimidobenzoate, were synthesized by condensation reaction of maleimidoacetic acid or 4-maleimidobenzoic acid with bis(tributyltin oxide. Copolymerization of these monomers with styrene was carried in dioxane at 70°C using asobisisobutyronitrile as free radical initiator. The structures of monomers and copolymers were confirmed by FT-IR (Fourier Transform Infrared, 1H and 13C NMR (nuclear magnetic resonance spectroscopy and elemental analysis. The copolymers were characterized by solubility and thermal analysis.

Influence of the land use pattern on the concentrations and fluxes of priority pollutants in urban stormwater.

Science.gov (United States)

Zgheib, S; Moilleron, R; Chebbo, G

2011-01-01

This paper presents the results of the concentrations (μg/L) and fluxes (g/ha) of priority substances in stormwater from three watersheds with different land use patterns (namely, residential, urban dense, high urban density). Samples were collected at the outlet of these watersheds. Thirteen chemical groups were investigated corresponding to 88 individual substances before treatment. Results showed that stormwater discharges contained 55 substances, among them some metals, organotins, PAHs, PCBs, alkylphenols, pesticides, phthalates, cholorophenols and volatile organic compounds. Therefore, stormwater was highly contaminated. However, this contamination was often comparable from site to site, since no significant difference of the pollutant load was observed between the land use patterns.

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.

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.

Long-term mequindox treatment induced endocrine and reproductive toxicity via oxidative stress in male Wistar rats

International Nuclear Information System (INIS)

Ihsan, Awais; Wang Xu; Liu Zhaoying; Wang Yulian; Huang Xianju; Liu Yu; Yu Huan; Zhang Hongfei; Li Tingting; Yang Chunhui; Yuan Zonghui

2011-01-01

Mequindox (MEQ) is a synthetic antimicrobial chemical of quinoxaline 1, 4-dioxide group. This study was designed to investigate the hypothesis that MEQ exerts testicular toxicity by causing oxidative stress and steroidal gene expression profiles and determine mechanism of MEQ testicular toxicity. In this study, adult male Wistar rats were fed with MEQ for 180 days at five different doses as 0, 25, 55, 110 and 275 mg/kg, respectively. In comparison to control, superoxide dismutase (SOD), reduced glutathione (GSH) and 8-hydroxydeoxyguanosine (8-OHdG) levels were elevated at 110 and 275 mg/kg MEQ, whereas the malondialdehyde (MDA) level was slightly increase at only 275 mg/kg. Furthermore, in LC/MS-IT-TOF analysis, one metabolite 2-isoethanol 4-desoxymequindox (M11) was found in the testis. There was significant decrease in body weight, testicular weight and testosterone at 275 mg/kg, serum follicular stimulating hormone (FSH) at 110 and 275 mg/kg, while lutinizing hormone (LH) levels were elevated at 110 mg/kg. Moreover, histopathology of testis exhibited germ cell depletion, contraction of seminiferous tubules and disorganization of the tubular contents of testis. Compared with control, mRNA expression of StAR, P450scc and 17β-HSD in testis was significantly decreased after exposure of 275 mg/kg MEQ while AR and 3β-HSD mRNA expression were significantly elevated at the 110 mg/kg MEQ group. Taken together, our findings provide the first and direct evidence in vivo for the formation of free radicals during the MEQ metabolism through N → O group reduction, which may have implications to understand the possible mechanism of male infertility related to quinoxaline derivatives.

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®

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.

The environmental chemical tributyltin chloride (TBT) shows both estrogenic and adipogenic activities in mice which might depend on the exposure dose.

Science.gov (United States)

Penza, M; Jeremic, M; Marrazzo, E; Maggi, A; Ciana, P; Rando, G; Grigolato, P G; Di Lorenzo, D

2011-08-15

Exposure during early development to chemicals with hormonal action may be associated with weight gain during adulthood because of altered body homeostasis. It is known that organotins affect adipose mass when exposure occurs during fetal development, although no knowledge of effects are available for exposures after birth. Here we show that the environmental organotin tributyltin chloride (TBT) exerts adipogenic action when peripubertal and sexually mature mice are exposed to the chemical. The duration and extent of these effects depend on the sex and on the dose of the compound, and the effects are relevant at doses close to the estimated human intake (0.5μg/kg). At higher doses (50-500μg/kg), TBT also activated estrogen receptors (ERs) in adipose cells in vitro and in vivo, based on results from acute and longitudinal studies in ERE/luciferase reporter mice. In 3T3-L1 cells (which have no ERs), transiently transfected with the ERE-dependent reporter plus or minus ERα or ERβ, TBT (in a dose range of 1-100nM) directly targets each ER subtype in a receptor-specific manner through a direct mechanism mediated by ERα in undifferentiated preadipocytic cells and by ERβ in differentiating adipocytes. The ER antagonist ICI-182,780 inhibits this effect. In summary, the results of this work suggest that TBT is adipogenic at all ages and in both sexes and that it might be an ER activator in fat cells. These findings might help to resolve the apparent paradox of an adipogenic chemical being also an estrogen receptor activator by showing that the two apparently opposite actions are separated by the different doses to which the organism is exposed. Copyright © 2011 Elsevier Inc. All rights reserved.

Priority substances in a SW European coastal lagoon - Ria Formosa, Portugal. Twenty years of temporal evolution of metals and butyltins

Science.gov (United States)

Moreira da Silva, Manuela; Carvalho, Pedro; Paquete, Rita; Nuno Duarte, Duarte; Chícharo, Luís

2013-04-01

In the last years the European Union has decided to specifically include nickel, cadmium, plumb and TBT in its list of priority substances in water. Trace metals pose a significant threat to organisms because above threshold availability, act as enzyme inhibitors resulting in adverse ecological effects to sediment-associated biota (e.g. macrophytes, benthos, demersal fish) and to higher-biota (e.g. pelagic fish and aquatic birds). Since 2003 International Maritime Organization called for a ban of the application of tributyltin-based paints. Wide distribution, high hydrophobicity, and persistence of organotin compounds have raised concern about their bioaccumulation, their potential biomagnification in the food webs, and their adverse effects to human health and environment, particularly most recent reviews focuses on possible endocrine disrupting effects of OT's (Galloway, 2006; Nakanishi, 2007; Takahashi et al., 1999; Veltman et al., 2006). Saltmarshes are highly heterogeneous environments that have been suffered pressures by the increasing urbanization and industrialization in the adjacent areas. Saltmarsh sediments integrate inputs of contaminants, like metals and organotin compounds and may act as long-term sources of contaminants. At the Ria Formosa saltmarsh several activities were responsible for long-term contaminants, some of them considered priority substances. This work aims to provide information about the present levels and temporal evolution in the last decades of metals (Mn, Zn, Cu, Cr, Ni, Pb, Mo, Cd and Ag, in addition to Fe and Al) and butyltins (TBT, DBT and MBT) in saltmarsh sediments at south of Portugal. Metals were analysed by atomic absorption spectrometry-AAS. Butyltins were determined, after derivatization, by solid phase micro extraction combined with gas chromatography with mass spectrometry (MS/MS). Results showed that legislation was an effective instrument for the decreasing of contamination levels, to sustainable values to ecosystem

Effect of triorganotin compounds on calcium transport mechanisms in rat cardiac sarcoplasmic reticulum

International Nuclear Information System (INIS)

Cameron, J.A.; Kodavanti, P.R.S.; Yallapragada, P.R.; Desaiah, D.

1990-01-01

Although organotin compounds, in general, are neurotoxicants, recent studies indicate that these tin compounds affect heme metabolism as well as cardiovascular system. Sarcoplasmic reticulum (SR) calcium pump together with phosphorylation of phospholamban has an important role in myocardial contraction and relaxation. Since organotin compounds interfere with cardiovascular system, we have studied the in vitro as well as in vivo effects of tributyltin bromide (TBT), triethyltin bromide (TET) and trimethyltin chloride (TMT) on cardiac SR Ca 2+ -pump activity, in order to know the relative potency of these tin compounds. SR was isolated from heart ventricles of male Sprague-Dawley rats and used for in vitro studies. For in vivo studies, rats were treated orally in corn oil for 6 days with different doses of TET (0.5, 1.0 and 1.5 mg/kg/d), TMT (0.75, 1.5 and 2.5 mg/kg/d) and TBT (0.75, 1.5 and 2.5 mg/kg/d). Rats were sacrificed 24 hr after the last dosage and cardiac SR was prepared. Cardiac SR Ca 2+ -ATPase and 45 Ca-uptake were measured. All the three tin compounds inhibited Ca 2+ -ATPase and 45 Ca-uptake in vitro in a concentration dependent manner. The order of potency for Ca 2+ -ATPase as determined IC 50 , is TBT (2 uM) > TET (63 uM) > TMT (280 uM). For 45 Ca-uptake, if followed the same order i.e., TBT (0.35 uM) > TET (10 uM) > TMT (440 uM). In agreement with in vitro results, both SR Ca 2+ -ATPase and 45 Ca-uptake were significantly inhibited in rats treated with these tin compounds. These studies indicate that triorganotin compounds affect Ca 2+ -pumping mechanisms and thereby alter cardiac contraction-relaxation process

Structurally-diverse, PPARγ-activating environmental toxicants induce adipogenesis and suppress osteogenesis in bone marrow mesenchymal stromal cells

International Nuclear Information System (INIS)

Watt, James; Schlezinger, Jennifer J.

2015-01-01

Environmental obesogens are a newly recognized category of endocrine disrupting chemicals that have been implicated in contributing to the rising rates of obesity in the United States. While obesity is typically regarded as an increase in visceral fat, adipocyte accumulation in the bone has been linked to increased fracture risk, lower bone density, and osteoporosis. Exposure to environmental toxicants that activate peroxisome proliferator activated receptor γ (PPARγ), a critical regulator of the balance of differentiation between adipogenesis and osteogenesis, may contribute to the increasing prevalence of osteoporosis. However, induction of adipogenesis and suppression of osteogenesis are separable activities of PPARγ, and ligands may selectively alter these activities. It currently is unknown whether suppression of osteogenesis is a common toxic endpoint of environmental PPARγ ligands. Using a primary mouse bone marrow culture model, we tested the hypothesis that environmental toxicants acting as PPARγ agonists divert the differentiation pathway of bone marrow-derived multipotent mesenchymal stromal cells towards adipogenesis and away from osteogenesis. The toxicants tested included the organotins tributyltin and triphenyltin, a ubiquitous phthalate metabolite (mono-(2-ethylhexyl) phthalate, MEHP), and two brominated flame retardants (tetrabromobisphenol-a, TBBPA, and mono-(2-ethylhexyl) tetrabromophthalate, METBP). All of the compounds activated PPARγ1 and 2. All compounds increased adipogenesis (lipid accumulation, Fabp4 expression) and suppressed osteogenesis (alkaline phosphatase activity, Osx expression) in mouse primary bone marrow cultures, but with different potencies and efficacies. Despite structural dissimilarities, there was a strong negative correlation between efficacies to induce adipogenesis and suppress osteogenesis, with the organotins being distinct in their exceptional ability to suppress osteogenesis. As human exposure to a mixture of

Evaluation of toxicological effects induced by tributyltin in clam Ruditapes decussatus using high-resolution magic angle spinning nuclear magnetic resonance spectroscopy: Study of metabolic responses in heart tissue and detection of a novel metabolite.

Science.gov (United States)

Hanana, H; Simon, G; Kervarec, N; Cérantola, S

2014-01-01

Tributyltin (TBT) is a highly toxic pollutant present in many aquatic ecosystems. Its toxicity in mollusks strongly affects their performance and survival. The main purpose of this study was to elucidate the mechanisms of TBT toxicity in clam Ruditapes decussatus by evaluating the metabolic responses of heart tissues, using high-resolution magic angle-spinning nuclear magnetic resonance (HRMAS NMR), after exposure to TBT (10 -9 , 10 -6 and 10 -4 M) during 24 h and 72 h. Results show that responses of clam heart tissue to TBT exposure are not dose dependent. Metabolic profile analyses indicated that TBT 10 -6 M, contrary to the two other doses tested, led to a significant depletion of taurine and betaine. Glycine levels decreased in all clam groups treated with the organotin. It is suggested that TBT abolished the cytoprotective effect of taurine, betaine and glycine thereby inducing cardiomyopathie. Moreover, results also showed that TBT induced increase in the level of alanine and succinate suggesting the occurrence of anaerobiosis particularly in clam group exposed to the highest dose of TBT. Taken together, these results demonstrate that TBT is a potential toxin with a variety of deleterious effects on clam and this organotin may affect different pathways depending to the used dose. The main finding of this study was the appearance of an original metabolite after TBT treatment likely N-glycine-N'-alanine. It is the first time that this molecule has been identified as a natural compound. Its exact role is unknown and remains to be elucidated. We suppose that its formation could play an important role in clam defense response by attenuating Ca 2+ dependent cell death induced by TBT. Therefore this compound could be a promising biomarker for TBT exposure.

Testosterone conjugating activities in invertebrates: are they targets for endocrine disruptors?

Science.gov (United States)

Janer, G; Sternberg, R M; LeBlanc, G A; Porte, C

2005-02-10

Testosterone conjugation activities, microsomal acyltransferases and cytosolic sulfotransferases, were investigated in three invertebrate species, the gastropod Marisa cornuarietis, the amphipod Hyalella azteca, and the echinoderm Paracentrotus lividus. The goals of the study were to characterize steroid conjugation pathways in different invertebrate phyla and to assess the susceptibility of those processes to disruption by environmental chemicals. All three species exhibited palmitoyl-CoA: testosterone acyltransferase activity (ATAT) in the range of 100-510 pmol/min/mg protein. Despite similarities in specific activities, kinetic studies indicated that ATAT had a higher affinity for testosterone but a lower V(max) in M. cornuarietis than in P. lividus, and intermediate values were found for H. azteca. In contrast, the activity of testosterone sulfotransferase (SULT) was rather low (0.05-0.18 pmol/min/mg protein) in M. cornuarietis and H. azteca. The low activity precluded kinetic analyses and inhibition studies with these species. P. lividus digestive tube displayed high SULT activity (50-170 pmol/min/mg protein) at moderate testosterone concentrations, but was inhibited at high testosterone concentrations. The interference of model pollutants (triphenyltin (TPT), tributyltin (TBT), and fenarimol) with these conjugation pathways was investigated in vitro. Both TPT and TBT (100 microM) inhibited ATAT in P. lividus (68 and 42% inhibition, respectively), and appeared to act as non-competitive inhibitors. ATAT activity in M. cornuarietis was less affected by organotins, and a significant inhibition (20% inhibition) was detected only with TBT. Fenarimol (100 microM) did not affect ATAT in any of the species tested. Sulfation of testosterone was suppressed by the organotins as well as fenarimol when using cytosolic preparations from P. lividus. These results demonstrated the existence of interphyla differences in testosterone conjugation, and revealed that these

Extraction of butyltins from sediments and their determination by liquid chromatography interfaced to inductively coupled plasma atomic emission detector

International Nuclear Information System (INIS)

Rivaro, P.; Frache, R.

2000-01-01

A liquid-liquid extraction of the butyltin compounds from sediment, suitable for their subsequent following determination by high performance liquid chromatography-hydride generation inductively coupled plasma atomic emission detector system, is proposed. Recoveries of 86%, 80% and 42% for tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) respectively were achieved. The relative detection limits of butyltin compounds by this method ranged from 27 to 62 ng of tin per gram of dry sediment. The method was applied to real sediment samples collected in the Venice lagoon (Italy). The results showed that, despite the restrictions on the use of butyltin contained in antifoulting paints, a considerable amount of organotin compounds is still present in Venice sediments [it

Persistent organic pollutants in selected fishes of the Gulf of Finland

Science.gov (United States)

Järv, Leili; Kiviranta, Hannu; Koponen, Jani; Rantakokko, Panu; Ruokojärvi, Päivi; Radin, Maia; Raid, Tiit; Roots, Ott; Simm, Mart

2017-07-01

Fish samples of Baltic herring, sprat, flounder, perch, salmon, and river lamprey were collected from the Gulf of Finland in 2013 and 2014 with the aim to get an overview of the occurrence of pollutants in fish caught in Estonian waters. The content of non-dioxin-like polychlorinated biphenyls (ndl PCBs), polybrominated diphenyl ethers (PBDEs), organic tin (OT) and perfluorocompounds (PFAS) are examined and discussed in the study. The results revealed that potentially higher content of organo-tin compounds, perfluorocompounds and polybrominated diphenyl ethers in Baltic herring, salmon and river lamprey may cause concern regarding human exposure. It is important to link pollutant content to lipid content of fish taking into account their seasonal variation in different age classes.

(N-Benzyl-N-isopropyldithiocarbamatochloridodiphenyltin(IV

Directory of Open Access Journals (Sweden)

Amirah Faizah Abdul Muthalib

2010-09-01

Full Text Available The SnIV atom in the title organotin dithiocarbamate, [Sn(C6H52(C11H14NS2Cl], is penta-coordinated by an asymmetrically coordinating dithiocarbamate ligand, a Cl and two ispo-C atoms of the Sn-bound phenyl groups. The resulting C2ClS2 donor set defines a coordination geometry intermediate between square-pyramidal and trigonal-bipyramidal with a slight tendency towards the latter. The formation of close intramolecular C–H...Cl and C–H...S contacts precludes the Cl and S atoms from forming significant intermolecular contacts. The presence of C–H...π contacts leads to the formation of supramolecular arrays that stack along the b axis.

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.

Effect of dietary olaquindox on the growth of large yellow croaker ( Pseudosciaena crocea R.) and the distribution of its residues in fish tissues

Science.gov (United States)

Li, Huitao; Wang, Weifang; Mai, Kangsen; Ai, Qinghui; Zhang, Chunxiao; Zhang, Lu

2014-10-01

Olaquindox (OLA), one of quinoxaline-N, N-dioxides, has been put under ban. However it was used as a medicinal feed additive early; it promotes the growth of livestock and prevents them from dysentery and bacterial enteritis. In this study, we evaluated the effect of dietary OLA on the growth of large yellow croaker ( Pseudosciaena crocea R.) and the histological distribution of OLA and its metabolite 3-methyl-quinoxaline-2-carboxylic acid (MQCA) in fish tissues. Four diets containing 0 (control), 42.5, 89.5 and 277.2 mg kg-1 OLA, respectively, were formulated and tested, 3 cages (1.0 m × 1.0 m × 1.5 m) each diet and 100 juveniles (9.75 ± 0.35 g) each cage. The fish were fed to satiation twice a day at 05:00 am and 17:00 pm for 8 weeks. The survival rate of fish fed the diet containing 42.5 and 89.5 mg kg-1 OLA was significantly higher than that of fish fed the diet containing 0 and 277.2 mg kg-1 OLA ( P diet containing 42.5 and 89.5 mg·kg-1 OLA was significantly higher than that of fish fed the diet without OLA (control) ( Pdiet with 277.2 mg kg-1 OLA. Fish fed the diet with 277.2 mg kg-1 OLA had the highest content of OLA and MQCA in liver (3.44 and 0.39 mg kg-1, respectively), skin (0.46 and 0.09 mg kg-1, respectively) and muscle (0.24 and 0.06 mg kg-1, respectively). In average, fish fed the diet containing OLA had the highest content of OLA and MQCA in liver which was followed by skin and muscle ( P diet containing OLA, thus imposing a potential safety risk to human health.

Quantification of the neurotoxic beta-carboline harmane in barbecued/grilled meat samples and correlation with level of doneness.

Science.gov (United States)

Louis, Elan D; Zheng, Wei; Jiang, Wendy; Bogen, Kenneth T; Keating, Garrett A

2007-06-01

Harmane, one of the heterocyclic amines (HCAs), is a potent neurotoxin linked to human diseases. Dietary exposure, especially in cooked meats, is the major source of exogenous exposure for humans. However, knowledge of harmane concentrations in cooked meat samples is limited. Our goals were to (1) quantify the concentration of harmane in different types of cooked meat samples, (2) compare its concentration to that of other more well-understood HCAs, and (3) examine the relationship between harmane concentration and level of doneness. Thirty barbecued/grilled meat samples (8 beef steak, 12 hamburger, 10 chicken) were analyzed for harmane and four other HCAs (2-amino-1-methyl-6-phenylimidazo [4,5-b]pyridine [PhIP], amino-3,8-dimethylimidazo[4,5-f]quinoxaline [MeIQx], 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline [DiMeIQx], and 2-amino-1,6-dimethylfuro[3,2-e]imidazo[4,5-b]pyridine [IFP]). Mean (+/- SD) harmane concentration was 5.63 (+/- 6.63) ng/g; harmane concentration was highest in chicken (8.48 +/- 9.86 ng/g) and lowest in beef steak (3.80 +/- 3.6 ng/g). Harmane concentration was higher than that of the other HCAs and significantly correlated with PhIP concentration. Harmane concentration was associated with meat doneness in samples of cooked beef steak and hamburger, although the correlation between meat doneness and concentration was greater for PhIP than for harmane. Evidence indicates that harmane was detectable in nanograms per gram quantities in cooked meat (especially chicken) and, moreover, was more abundant than other HCAs. There was some correlation between meat doneness and harmane concentration, although this correlation was less robust than that observed for PhIP. Data such as these may be used to improve estimation of human dietary exposure to this neurotoxin.

Quantification of the Neurotoxic β-Carboline Harmane in Barbecued/Grilled Meat Samples and Correlation with Level of Doneness

Science.gov (United States)

Louis, Elan D.; Zheng, Wei; Jiang, Wendy; Bogen, Kenneth T.; Keating, Garrett A.

2016-01-01

Harmane, one of the heterocyclic amines (HCAs), is a potent neurotoxin linked to human diseases. Dietary exposure, especially in cooked meats, is the major source of exogenous exposure for humans. However, knowledge of harmane concentrations in cooked meat samples is limited. Our goals were to (1) quantify the concentration of harmane in different types of cooked meat samples, (2) compare its concentration to that of other more well-understood HCAs, and (3) examine the relationship between harmane concentration and level of doneness. Thirty barbecued/grilled meat samples (8 beef steak, 12 hamburger, 10 chicken) were analyzed for harmane and four other HCAs (2-amino-1-methyl-6-phenylimidazo [4,5-b]pyridine [PhIP], amino-3,8-dimethylimidazo[4,5-f]quinoxaline [MeIQx], 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline [DiMeIQx], and 2-amino-1,6-dimethylfuro[3,2-e]imidazo[4,5-b]pyridine [IFP]). Mean (± SD) harmane concentration was 5.63 (± 6.63) ng/g; harmane concentration was highest in chicken (8.48 ± 9.86 ng/g) and lowest in beef steak (3.80 ± 3.6 ng/g). Harmane concentration was higher than that of the other HCAs and significantly correlated with PhIP concentration. Harmane concentration was associated with meat doneness in samples of cooked beef steak and hamburger, although the correlation between meat doneness and concentration was greater for PhIP than for harmane. Evidence indicates that harmane was detectable in nanograms per gram quantities in cooked meat (especially chicken) and, moreover, was more abundant than other HCAs. There was some correlation between meat doneness and harmane concentration, although this correlation was less robust than that observed for PhIP. Data such as these may be used to improve estimation of human dietary exposure to this neurotoxin. PMID:17497412

Fused thiophene/quinoxaline low band gap polymers for photovoltaic's with increased photochemical stability

DEFF Research Database (Denmark)

Carlé, Jon Eggert; Jørgensen, Mikkel; Manceau, Matthieu

2011-01-01

and inverted geometry were prepared and tested in air. The normal geometry devices showed the highest efficiencies compared to the inverted, in particular owing to a higher Voc, with TQ1 being the most efficient with a power conversion efficiency (PCE) of 1.5% (1000 W m−2, AM1.5 G). For the inverted devices TQ...

Organotins in the sediments of the Zuari estuary, west coast of India

Digital Repository Service at National Institute of Oceanography (India)

Jadhav, S.; Bhosle, N.B.; Massanisso, P.; Morabito, R

., Jadhav, S., Harji, R., Sawant, S., Venket, K., Anil, A. C., 2004. Butyltins in water, biofilm and sediments of the west coast of India. Chemosphere 57, 897-907. Burton, E. D., Phillips, I. R., Hawker, D. W., 2004. Sorption and desorption behaviour... of tributyltin with natural sediments. Environmental Science & Technology 38, 6694 – 6700. Burton, E. D., Phillips, I. R., Hawker, D. W., 2005. In-situ partitioning of butyltin species in estuarine sediments. Chemosphere 59, 585 – 592. Burton, E. D., Phillips...

Distribution of organotin compounds in the bivalves of the Aegean Sea, Greece

NARCIS (Netherlands)

Chandrinou, S.; Pappas, K.; Nikolaou, A.; Stasinakis, A.S.; Wegener, J.W.M.; Alexandropoulos, Th.; Thomaidis, N.S.

2007-01-01

Five bivalve species - Mytilus galloprovinciallis (Mediterranean mussels), Venus gallina (stripped venus), Modiola barbatus L. (bearded horse mussels), Pecten jacobeus (scallops) and Callista chione (hard clams) - were collected from seven areas in Aegean Sea, Greece, between August 2001 and January

The Biological Fate and Effects of Organotin Compounds in the Marine Environment.

Science.gov (United States)

1983-07-01

Chlorella vulgaris , and Scenedesmus quadricauda. They 7 p...compared with seawater. In cephalopods (Sepia officinalis, Octopus vulgaris ), the concentration of tin was significantly higher in the liver than in

(N-Benzyl-N-isopropyl-dithio-carbamato)chloridodiphenyl-tin(IV).

Science.gov (United States)

Abdul Muthalib, Amirah Faizah; Baba, Ibrahim; Mohamed Tahir, Mohamed Ibrahim; Ng, Seik Weng; Tiekink, Edward R T

2010-08-11

The Sn(IV) atom in the title organotin dithio-carbamate, [Sn(C(6)H(5))(2)(C(11)H(14)NS(2))Cl], is penta-coordinated by an asymmetrically coordinating dithio-carbamate ligand, a Cl and two ispo-C atoms of the Sn-bound phenyl groups. The resulting C(2)ClS(2) donor set defines a coordination geometry inter-mediate between square-pyramidal and trigonal-bipyramidal with a slight tendency towards the latter. The formation of close intra-molecular C-H⋯Cl and C-H⋯S contacts precludes the Cl and S atoms from forming significant inter-molecular contacts. The presence of C-H⋯π contacts leads to the formation of supra-molecular arrays that stack along the b axis.

Investigation on the formation of monomethylmercury(II) in the Elbe

International Nuclear Information System (INIS)

Ebinghaus, R.; Wilken, R.D.; Gisder, P.

1994-01-01

Very little is known about transformation reactions of pollutants attached to suspended materials in the Elbe. In the present study, the influence of bacteria present in suspended particulate matter and in Elbe sediments, on dynamic transformations of mercury species was investigated. The formation of highly toxic monomethylmercury is more effective in the presence of organotin, - lead and arsenic compounds, via transmethylation reactions, than in the presence of biogenic methyldonors. Under oxic conditions, bacteria isolated from suspended particulate matter decompose methlmercury very rapidly to inorganic Hg(II), which is immobilized by the cells. In sediments, redox potential and pH value are important for the formation of methylmercury. Under anoxic conditions a pH of 6.5 is advantageous for the methylation of mercury(II)ions. (orig.) [de

Electrochemical hydrogen Storage Systems

International Nuclear Information System (INIS)

Macdonald, Digby

2010-01-01

previous literature for electrochemical reduction of spent fuels, have been attempted. A quantitative analytical method for measuring the concentration of sodium borohydride in alkaline aqueous solution has been developed as part of this work and is described herein. Finally, findings from stability tests for sodium borohydride in aqueous solutions of several different compositions are reported. For aminoborane, other research institutes have developed regeneration schemes involving tributyltin hydride. In this report, electrochemical reduction experiments attempting to regenerate tributyltin hydride from tributyltin chloride (a representative by-product of the regeneration scheme) are described. These experiments were performed in the non-aqueous solvents acetonitrile and 1,2-dimethoxyethane. A non-aqueous reference electrode for electrolysis experiments in acetonitrile was developed and is described. One class of boron hydrides, called polyhedral boranes, became of interest to the DOE due to their ability to contain a sufficient amount of hydrogen to meet program goals and because of their physical and chemical safety attributes. Unfortunately, the research performed here has shown that polyhedral boranes do not react in such a way as to allow enough hydrogen to be released, nor do they appear to undergo hydrogenation from the spent fuel form back to the original hydride. After the polyhedral boranes were investigated, the project goals remained the same but the hydrogen storage material was switched by the DOE to ammonia borane. Ammonia borane was found to undergo an irreversible hydrogen release process, so a direct hydrogenation was not able to occur. To achieve the hydrogenation of the spent ammonia borane fuel, an indirect hydrogenation reaction is possible by using compounds called organotin hydrides. In this process, the organotin hydrides will hydrogenate the spent ammonia borane fuel at the cost of their own oxidation, which forms organotin halides. To enable a

Electrochemical hydrogen Storage Systems

Energy Technology Data Exchange (ETDEWEB)

Dr. Digby Macdonald

2010-08-09

described in the previous literature for electrochemical reduction of spent fuels, have been attempted. A quantitative analytical method for measuring the concentration of sodium borohydride in alkaline aqueous solution has been developed as part of this work and is described herein. Finally, findings from stability tests for sodium borohydride in aqueous solutions of several different compositions are reported. For aminoborane, other research institutes have developed regeneration schemes involving tributyltin hydride. In this report, electrochemical reduction experiments attempting to regenerate tributyltin hydride from tributyltin chloride (a representative by-product of the regeneration scheme) are described. These experiments were performed in the non-aqueous solvents acetonitrile and 1,2-dimethoxyethane. A non-aqueous reference electrode for electrolysis experiments in acetonitrile was developed and is described. One class of boron hydrides, called polyhedral boranes, became of interest to the DOE due to their ability to contain a sufficient amount of hydrogen to meet program goals and because of their physical and chemical safety attributes. Unfortunately, the research performed here has shown that polyhedral boranes do not react in such a way as to allow enough hydrogen to be released, nor do they appear to undergo hydrogenation from the spent fuel form back to the original hydride. After the polyhedral boranes were investigated, the project goals remained the same but the hydrogen storage material was switched by the DOE to ammonia borane. Ammonia borane was found to undergo an irreversible hydrogen release process, so a direct hydrogenation was not able to occur. To achieve the hydrogenation of the spent ammonia borane fuel, an indirect hydrogenation reaction is possible by using compounds called organotin hydrides. In this process, the organotin hydrides will hydrogenate the spent ammonia borane fuel at the cost of their own oxidation, which forms organotin

New type of transformation of a 1,2,4-triazine ring to pyrazine derivatives

International Nuclear Information System (INIS)

Alekseev, S.G.; Charushin, V.N.; Chupakhin, O.N.

1987-01-01

We have discovered a new type of transformation of a triazine ring in which the l-ethyl-1,2,4-triazine cation participates. It has been established that the cation reacts at 20 0 C with ortho-phenylenediamine (in methylene chloride) and 5,6-diaminopyrimidin-4-one (in 9:1 ethanol-DMF) with the formation of quinoxaline (yield 43%) and pteridin-4-one (yield 23%). This transformation is based on the susceptibility of the cation to bi-addition of nucleophiles and proceeds via cyclic adducts which are then aromatized on account of separation of 3-morpholinoamidrazone. The reaction products were identified by comparison of their melting points and spectroscopic characteristics (NMR, mass-spectra) with those of samples whose structure is definitely known

Development of solid electrolytes for water electrolysis at intermediate temperatures. Task 3 report; Annual report

Energy Technology Data Exchange (ETDEWEB)

Linkous, C.A.; Anderson, R.; Kopitzke, R.W.

1995-12-01

This project is an attempt to synthesize and fabricate proton exchange membranes for hydrogen production via water electrolysis that can take advantage of the better kinetic and thermodynamic conditions that exist at higher temperatures. Current PEM technology is limited to the 125--150 C range. Based on previous work evaluating thermohydrolytic stability, some 5 families of polymers were chosen as viable candidates: polyether ketones, polyether sulfones, fluorinated polyimides, polybenzimidazoles, and polyphenyl quinoxalines. Several of these have been converted into ionomers via sulfonation and fashioned into membranes for evaluation. In particular, the sulfonated polyetheretherketone, or SPEEK, was tested for water uptake, thermo-conductimetric analysis, and performance as the solid electrolyte material in an electrolysis cell. Results comparable to commercial perfluorocarbon sulfonates were obtained.

Metals and organotins in multiple bivalve species in a one-off global survey

DEFF Research Database (Denmark)

Larsen, Martin Mørk; Strand, Jakob; Christensen, Jan H.

2011-01-01

contamination levels on a global scale. Metal concentrations in nine bivalve species were normalised to the Mytilidae family using conversion factors based on cosampled species and literature bioconcentration factors. The lowest metal and tributyltin concentrations were below background assessment...... were low, but not always lower than expected impacted areas. The most contaminated areas were harbours, where especially Copenhagen, St Croix and Sydney, can be considered hotspots of tributyltin as well as a number of metals....

The Evidence of Imposex in Turbo sp. from Ujungpiring Waters of Jepara

Science.gov (United States)

Nuraini, RAT; Hartati, R.; Endrawati, H.; Widianingsih; Rachma, MJ; Mahendrajaya, RT

2018-02-01

Imposex is an endocrine disruption syndrome, in which females of marine gastropods develop sexual characteristics of males (penis and/or vas deferens). This syndrome is caused by tributyltin (TBT) or triphenyltin (TPT), toxic organotin compounds found in naval paints used as antifouling system in boats and artificial structures. The main objective of this study was to assess the incidence and severity of imposex in Turbosp.A hundred individus of Turbo sp was collected from Ujung Piring waters of Jepara, and observed for their sex and imposex. The results showed that the ratio male and female was 1.13 : 1, and the frequency of imposex females was 64.58%. The relative penis size were longer in imposex female than in male. The possibility of pollution was clearly shown from high evidence of imposex female.

Evaluation and selection of test methods for assessment of contaminated sediments in the Baltic Sea

DEFF Research Database (Denmark)

Lehtonen, Kari; Ahvo, Aino; Berezina, Nadya

The purpose of the CONTEST project (2014-15) is to test, develop, evaluate and select suitable biological methods to be applied in the quantitative and qualitative assessment of toxicity of anthropogenically contaminated sediments in the Baltic Sea marine region. Here is presented results from...... showed large variability in the sensitivity of the different biotests. Most of the tests applied showed concentration-dependent effects on the test organisms. New experiments will be carried out in 2015. The CONTEST project is funded by the Nordic Council of Ministers and the Finnish Ministry...... a set of pilot experiments, which were performed by the participating laboratories. Chemical analysis of the contaminated harbour sediment chosen as the test matrix confirmed the presence of high concentrations of polycyclic aromatic hydrocarbons, organotins and trace metals, and the sediment...

Marisa cornuarietis (Gastropoda, prosobranchia): a potential TBT bioindicator for freshwater environments.

Science.gov (United States)

Schulte-Oehlmann, U; Bettin, C; Fioroni, P; Oehlmann, J; Stroben, E

1995-12-01

: The ramshorn snail Marisa cornuarietis (L., 1767) exhibits imposex (occurrence of male parts in addition to the female genital duct) under the influence of TBT (tributyltin) in laboratory experiments and accumulates this biocide in a time-and concentration-dependent manner. A comparison of BCF (bioconcentration factors) demonstrates that this limnic species accumulates more TBT than marine species. Evidence is given that TBT causes hormonal disorders which are responsible for imposex development. The testosterone/oestradiol quotient reflects the imposex development which can be described by a classification scheme differentiating four stages in Marisa cornuarietis. In the background of the constantly increasing organotin concentration in the limnic environment Marisa cornuarietis could be a well-suited bioindicator for TBT pollution. No other limnic species with a lower threshold concentration for measurable TBT effects is reported within the literature.

(N-Benzyl-N-isopropyl­dithio­carbamato)chloridodiphenyl­tin(IV)

Science.gov (United States)

Abdul Muthalib, Amirah Faizah; Baba, Ibrahim; Mohamed Tahir, Mohamed Ibrahim; Ng, Seik Weng; Tiekink, Edward R. T.

2010-01-01

The SnIV atom in the title organotin dithio­carbamate, [Sn(C6H5)2(C11H14NS2)Cl], is penta-coordinated by an asymmetrically coordinating dithio­carbamate ligand, a Cl and two ispo-C atoms of the Sn-bound phenyl groups. The resulting C2ClS2 donor set defines a coordination geometry inter­mediate between square-pyramidal and trigonal-bipyramidal with a slight tendency towards the latter. The formation of close intra­molecular C–H⋯Cl and C–H⋯S contacts precludes the Cl and S atoms from forming significant inter­molecular contacts. The presence of C–H⋯π contacts leads to the formation of supra­molecular arrays that stack along the b axis. PMID:21588504

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®

NMR studies of echinomycin bisintercalation complexes with d(A1-C2-G3-T4) and d(T1-C2-G3-A4) duplexes in aqueous solution: sequence-dependent formation of Hoogsteen A1 x T4 and Watson-Crick T1 x A4 base pairs flanking the bisintercalation site

International Nuclear Information System (INIS)

Gao, X.; Patel, D.J.

1988-01-01

The authors report on two-dimensional proton NMR studies of echinomycin complexes with the self-complementary d(A1-C2-G3-Tr) and d(T1-C2-G3-A4) duplexes in aqueous solution. The exchangeable and nonexchangeable antibiotic and nucleic acid protons in the 1 echinomycin per tetranucleotide duplex complexes have been assigned from analyses of scalar coupling and distance connectivities in two-dimensional data sets records in H 2 O and D 2 O solution. An analysis of the intermolecular NOE patterns for both complexes combined with large upfield imino proton and large downfield phosphorus complexation chemical shift changes demonstrates that the two quinoxaline chromophores of echinomycin bisintercalate into the minor groove surrounding the dC-dG step of each tetranucleotide duplex. Further, the quinoxaline rings selectively stack between A1 and C2 bases in the d(ACGT) complex and between T1 and C2 bases in the d(TCGA) complex. The intermolecular NOE patterns and the base and sugar proton chemical shifts for residues C2 and G3 are virtually identical for the d(ACGT) and d(TCGA) complexes. A large set of intermolecular contacts established from nuclear Overhauser effects (NOEs) between antibiotic and nucleic acid protons in the echinomycin-tetranucleotide complexes in solution are consistent with corresponding contacts reported for echinomycin-oligonucleotide complexes in the crystalline state. The authors demonstrate that the G x G base pairs adopt Watson-Crick pairing in both d(ACGT) and d(TCGA) complexes in solution. By contrast, the A1 x T4 base pairs adopt Hoogsteen pairing for the echinomycin-d(A1-C2-G3-Tr) complex while the T1 x A4 base pairs adopt Watson-Crick pairing for the echinomycin-d(T1-C2-G3-A4) complex in aqueous solution. These results emphasize the role of sequence in discriminating between Watson-Crick and Hoogsteen pairs at base pairs flanking the echinomycin bisintercalation site in solution

Anti-Inflammatory Effects and Joint Protection in Collagen-Induced Arthritis after Treatment with IQ-1S, a Selective c-Jun N-Terminal Kinase Inhibitor.

Science.gov (United States)

Schepetkin, Igor A; Kirpotina, Liliya N; Hammaker, Deepa; Kochetkova, Irina; Khlebnikov, Andrei I; Lyakhov, Sergey A; Firestein, Gary S; Quinn, Mark T

2015-06-01

c-Jun N-terminal kinases (JNKs) participate in many physiologic and pathologic processes, including inflammatory diseases. We recently synthesized the sodium salt of IQ-1S (11H-indeno[1,2-b]quinoxalin-11-one oxime) and demonstrated that it is a high-affinity JNK inhibitor and inhibits murine delayed-type hypersensitivity. Here we show that IQ-1S is highly specific for JNK and that its neutral form is the most abundant species at physiologic pH. Molecular docking of the IQ-1S syn isomer into the JNK1 binding site gave the best pose, which corresponded to the position of cocrystallized JNK inhibitor SP600125 (1,9-pyrazoloanthrone). Evaluation of the therapeutic potential of IQ-1S showed that it inhibited matrix metalloproteinase 1 and 3 gene expression induced by interleukin-1β in human fibroblast-like synoviocytes and significantly attenuated development of murine collagen-induced arthritis (CIA). Treatment with IQ-1S either before or after induction of CIA resulted in decreased clinical scores, and joint sections from IQ-1S-treated CIA mice exhibited only mild signs of inflammation and minimal cartilage loss compared with those from control mice. Collagen II-specific antibody responses were also reduced by IQ-1S treatment. By contrast, the inactive ketone derivative 11H-indeno[1,2-b]quinoxalin-11-one had no effect on CIA clinical scores or collagen II-specific antibody titers. IQ-1S treatment also suppressed proinflammatory cytokine and chemokine levels in joints and lymph node cells. Finally, treatment with IQ-1S increased the number of Foxp3(+)CD4(+)CD25(+) regulatory T cells in lymph nodes. Thus, IQ-1S can reduce inflammation and cartilage loss associated with CIA and can serve as a small-molecule modulator for mechanistic studies of JNK function in rheumatoid arthritis. Copyright © 2015 by The American Society for Pharmacology and Experimental Therapeutics.

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.

Butyltin speciation in sediments from Todos os Santos Bay (Bahia, Brazil by GC-PFPD

Directory of Open Access Journals (Sweden)

Juliana Feitosa Felizzola

2008-01-01

Full Text Available Butyltin compounds were investigated in surface sediments from 17 stations in Todos os Santos Bay. Analytical conditions for organotin determination in marine sediments were optimized for GC with pulsed flame photometric detection. Detection limits were: 5.4 µg kg-1 for TBT; 0.2 µg kg-1 for DBT; and 2.1 µg kg-1 for MBT, using a 610-nm filter. In general, TBT concentrations were low and in the range of

Linear solvation energy relationships (LSER): 'rules of thumb' for Vi/100, π*, Βm, and αm estimation and use in aquatic toxicology

Science.gov (United States)

Hickey, James P.

1996-01-01

This chapter provides a listing of the increasing variety of organic moieties and heteroatom group for which Linear Solvation Energy Relationship (LSER) values are available, and the LSER variable estimation rules. The listings include values for typical nitrogen-, sulfur- and phosphorus-containing moieties, and general organosilicon and organotin groups. The contributions by an ion pair situation to the LSER values are also offered in Table 1, allowing estimation of parameters for salts and zwitterions. The guidelines permit quick estimation of values for the four primary LSER variables Vi/100, π*, Βm, and αm by summing the contribtuions from its components. The use of guidelines and Table 1 significantly simplifies computation of values for the LSER variables for most possible organic comppounds in the environment, including the larger compounds of environmental and biological interest.

Novel Organotin(IV) Schiff Base Complexes with Histidine Derivatives: Synthesis, Characterization, and Biological Activity

Science.gov (United States)

Garza-Ortiz, Ariadna; Camacho-Camacho, Carlos; Sainz-Espuñes, Teresita; Rojas-Oviedo, Irma; Gutiérrez-Lucas, Luis Raúl; Gutierrez Carrillo, Atilano; Vera Ramirez, Marco A.

2013-01-01

Five novel tin Schiff base complexes with histidine analogues (derived from the condensation reaction between L-histidine and 3,5-di-tert-butyl-2-hydroxybenzaldehyde) have been synthesized and characterized. Characterization has been completed by IR and high-resolution mass spectroscopy, 1D and 2D solution NMR (1H, 13C  and 119Sn), as well as solid state 119Sn NMR. The spectroscopic evidence shows two types of structures: a trigonal bipyramidal stereochemistry with the tin atom coordinated to five donating atoms (two oxygen atoms, one nitrogen atom, and two carbon atoms belonging to the alkyl moieties), where one molecule of ligand is coordinated in a three dentate fashion. The second structure is spectroscopically described as a tetrahedral tin complex with four donating atoms (one oxygen atom coordinated to the metal and three carbon atoms belonging to the alkyl or aryl substituents), with one molecule of ligand attached. The antimicrobial activity of the tin compounds has been tested against the growth of bacteria in vitro to assess their bactericidal properties. While pentacoordinated compounds 1, 2, and 3 are described as moderate effective to noneffective drugs against both Gram-positive and Gram-negative bacteria, tetracoordinated tin(IV) compounds 4 and 5 are considered as moderate effective and most effective compounds, respectively, against the methicillin-resistant Staphylococcus aureus strains (Gram-positive). PMID:23864839

Concentrations of organotin compounds in sediment and clams collected from coastal areas in Vietnam

International Nuclear Information System (INIS)

Midorikawa, Sayaka; Arai, Takaomi; Harino, Hiroya; Ohji, Madoka; Nguyen Duc Cu; Miyazaki, Nobuyuki

2004-01-01

Levels of butyltin (BT) and phenyltin (PT) compounds were determined in sediments and clam Meretrix spp. collected from north and central coastal areas in Vietnam. Concentrations of TBT in sediments ranged from 0.89 to 34 ng g -1 dry wt and those in clams ranged from 1.4 to 56 ng g -1 wet wt. The levels of TBT in sediments and clams from Vietnam were within limits reported from other countries. Further, the TBT level in clams was lower than the tolerable average residue level (TARL) estimated based on tolerable daily intake (TDI). Trace amounts of PTs were also found in both sediment and clam samples. In sediments from north and central Vietnam, the concentrations of TBT were highest in the order of Hue (28 ng g -1 dry wt), Cua Luc (15 ng g -1 dry wt), Sam Son (6.3 ng g -1 dry wt), and Tra Co (5.5 ng g -1 dry wt). Among the clams from north and central Vietnam, the levels of TBT in clams from Cua Luc were dramatically high at 47 ng g -1 wet wt. TBT formed the principal butyltin species in sediment at all sites studied. The ratios of TBT in sediment were higher among BT compounds at all study sites. Of total BTs, TBT was the dominant species in clams from almost all sites studied. In spatial distribution, TPT showed a pattern similar to TBT, suggesting the use of TPT as an antifouling paint. The partition coefficient between sediment and calms was calculated. The partition coefficients of TBT and TPT were 2.01 (0.56-5.5) and 9.23 (3.1-20), respectively. These results show that sediment-bound TBT is a source of contamination to clams in addition to dissolved TBT

Determination and depletion of residues of carbadox, tylosin, and virginiamycin in kidney, liver, and muscle of pigs in feeding experiments.

Science.gov (United States)

Lauridsen, M G; Lund, C; Jacobsen, M

1988-01-01

The results of residue determinations of the growth promotors carbadox, tylosin, and virginiamycin in kidney, liver, and muscle from pigs in feeding experiments are described as well as the analytical methods used. Residues of the carbadox metabolite quinoxaline-2-carboxylic acid were found in liver from pigs fed 20 mg/kg in the diet with a withdrawal time of 30 days. No residues were detected in muscle with zero withdrawal time. The limit of determination was 0.01 mg/kg for both tissues. No residues of virginiamycin and tylosin were found in pigs fed 50 and 40 mg/kg, respectively, in the diet, even with zero withdrawal time. Residues of tylosin of 0.06 mg/kg and below were detected in liver and kidney from pigs fed 200 or 400 mg/kg and slaughtered within 3 h after the last feeding.

Binding of 14C-labeled food mutagens (IQ, MeIQ, MeIQx) by dietary fiber in vitro

International Nuclear Information System (INIS)

Sjoedin, P.B.; Nyman, M.E.; Nilsson, L.; Asp, N.L.; Jaegerstad, M.

1985-01-01

Binding of three mutagens, known to occur in fried or broiled foods, by thirteen different types of dietary fiber was investigated in vitro. Nonspecific binding by other food polymers was minimized by using protease and amylase treatment. Water-insoluble fiber components were responsible for most of the binding capacity. Generally, a slightly larger proportion of 2-amino-3,4-dimethylimidazo [4,5-f]quinoline (MeIQ) than of 2-amino-3-methylimidazo [4,5-f]quinoline (IQ) and 2-amino-3,8-dimethylimidazo] -4,5-f]quinoxaline (MeIQx) was bound. There was a significant correlation between Klason lignin content and binding of mutagens. Optimum pH for binding was between 4 and 6. Dietary fiber from sorghum had the highest binding capacity, which could be due to the presence of a large Klason lignin fraction

Hydroamination reactions of alkynes with ortho-substituted anilines in ball mills: synthesis of benzannulated N-heterocycles by a cascade reaction.

Science.gov (United States)

Weiße, Maik; Zille, Markus; Jacob, Katharina; Schmidt, Robert; Stolle, Achim

2015-04-20

It was demonstrated that ortho-substituted anilines are prone to undergo hydroamination reactions with diethyl acetylenedicarboxylate in a planetary ball mill. A sequential coupling of the intermolecular hydroamination reaction with intramolecular ring closure was utilized for the syntheses of benzooxazines, quinoxalines, and benzothiazines from readily available building blocks, that is, electrophilic alkynes and anilines with OH, NH, or SH groups in the ortho position. For the heterocycle formation, it was shown that several stress conditions were able to initiate the reaction in the solid state. Processing in a ball mill seemed to be advantageous over comminution with mortar and pestle with respect to process control. In the latter case, significant postreaction modification occurred during solid-state analysis. Cryogenic milling proved to have an adverse effect on the molecular transformation of the reagents. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hole transfer from CdSe nanoparticles to TQ1 polymer in hybrid solar cell device

Science.gov (United States)

Sohail, Muhammad; Shah, Zawar Hussain; Saeed, Shomaila; Bibi, Nasreen; Shahbaz, Sadia; Ahmed, Safeer; Shabbir, Saima; Siddiq, Muhammad; Iqbal, Azhar

2018-05-01

In view of realizing the economic viability, we fabricate a solar cell device containing low band gap and easily processable polymer 5-yl-8-(thiophene-2,5-diyl)-2,3-bis(3-(octyloxy)phenyl) quinoxaline (TQ1) and CdSe nanoparticles (NPs) and investigate its charge transport properties. When the TQ1 is combined with the CdSe NPs a strong photoluminescence quenching and shortening of photoluminescence lifetime of the TQ1 is observed indicating exciton transfer from TQ1 to the CdSe NPs. The time-resolved photoluminescence further reveals that the exciton transfer from the polymer to CdSe NPs is very efficient (68%) and it occurs in solar cell as compared to polymer only device. These observations suggest the importance of other II-VI semiconductor NPs to achieve higher efficiency for photovoltaic devices containing TQ1 polymer.

Persistence of TBT and copper in excess on leisure boat hulls around the Baltic Sea.

Science.gov (United States)

Eklund, Britta; Watermann, Burkard

2018-05-01

A handheld XRF-analyzer specially calibrated for measurements of metals on plastic boat hulls has been used on leisure boats in Denmark (DK), Finland (FI), and Germany (DE). The results on tin and copper are presented as μg metal/cm 2 . Tin is a proxy for the occurrence of organotin compounds on the boat. Two or three sites were visited in each country and between 25 and 90 boats were measured at each site. Every boat was measured at six to eight places, and the results are presented both as mean and median values. Linear regression of mean to median values of the 377 data pairs shows high relationship with R 2  = 0.9566 for tin and R 2 of 0.9724 for copper and thus both ways of calculation may be used. However, for regulative use, it is suggested that all individual measurements on each boat should be presented and used for decisions of removal or sealing of boat hulls. The results are compared with published data from different parts of Sweden, i.e., boats in fresh water, brackish water, and salt water. The results show that tin with mean values > 50 μg Sn/cm 2 is still found on 42, 24, and 23% of the boats in DK, FI, and DE, respectively. The corresponding percentages based on median values are 38, 22, and 18% for DK, FI, and DE, respectively. The variation among boats is high with a maximum mean value of 2000 μg Sn/cm 2 . As comparison, one layer of an old TBT antifouling paint Hempels Hard racing superior, corresponds to 300 μg Sn/cm 2 . The percentage of boats with tin > 400 μg Sn/cm 2 content based on mean values was 10% in DK, 5% in FI, and 1% in DE. The corresponding median values were 9, 6, and 1% for DK, FI, and DE. Copper, > 100 μg Cu/cm 2 , was detected on all measured boats in DK and in DE and on all but 3% of the FI boats. One layer of Hempels MilleXtra corresponds to ̴ 4000 μg Cu/cm 2 . The recommendation on the can is to apply two layers. The proportion of boats with higher mean copper values than 8000 μg Cu/cm 2

Effects of antifouling biocides to the germination and growth of the marine macroalga, Hormosira banksii (Turner) Desicaine

Energy Technology Data Exchange (ETDEWEB)

Myers, Jackie H. [School of Ecology and Environment, Deakin University, P.O. Box 423, Warrnambool, Victoria 3280 (Australia) and Department of Primary Industries Research Victoria, Queenscliff, P.O. Box 114 Queenscliff, Victoria 3225 (Australia) and School of Biological Sciences, Monash University, Clayton Campus, Clayton, Victoria 3800 (Australia)]. E-mail jhmyers@deakin.edu.au; Gunthorpe, Leanne [Department of Primary Industries Research Victoria, Queenscliff, P.O. Box 114 Queenscliff, Victoria 3225 (Australia)]. E-mail Leanne.Gunthorpe@dpi.vic.gov.au; Allinson, Graeme [School of Ecology and Environment, Deakin University, P.O. Box 423, Warrnambool, Victoria 3280 (Australia)]. E-mail graemea@deakin.edu.au; Duda, Susan [Department of Primary Industries Research Victoria, Queenscliff, P.O. Box 114 Queenscliff, Victoria 3225 (Australia)]. E-mail Susan.Duda@dpi.vic.gov.au

2006-09-15

The International Maritime Organisation's (IMO) ban on the use of tributyltin in antifouling paints has inevitability increased the use of old fashioned antifoulants and/or the development of new paints containing 'booster biocides'. These newer paints are intended to be environmentally less harmful, however the broader environmental effects of these 'booster biocides' are poorly known. Germination and growth inhibition tests using the marine macroalga, Hormosira banksii (Turner) Desicaine were conducted to evaluate the toxicity of four new antifouling biocides in relation to tributyltin-oxide (TBTO). Each of the biocides significantly inhibited germination and growth of Hormosira banksii spores. Toxicity was in increasing order: diuron < zineb < seanine 211 < zinc pyrithione < TBTO. However, the lack of knowledge on partitioning in the environment makes it difficult to make a full assessment on whether the four biocides tested offer an advantage over organotin paints in terms of environmental impact.

Butyltin compounds in a sediment core from the old Tilbury basin, London,

International Nuclear Information System (INIS)

Scrimshaw, M.D.; Wahlen, R.; Catterick, T.; Lester, J.N.

2005-01-01

Sections from a sediment core taken from the River Thames were analysed for butyltin species using gas chromatography with species-specific isotope dilution mass spectrometry. Results demonstrated that in most samples tributyltin concentrations of 20-60 ng/g accounted for <10% of the total butyltin species present, which is in agreement with data from other sediment samples which were historically contaminated with tributyltin. Vertical distribution of the organotin residues with depth throughout the core, with data on organochlorine compounds and heavy metals allowed for the construction of a consistent hypothesis on historical deposition of contaminated sediments. From this it was possible to infer that the concentrations of tributyltin in sediments deposited during the early 1960s were in the order of 400-600 μg/g by using degradation rate constants derived by other workers. Such values fall well within the range quoted for harbour sediments in the literature

Effects of antifouling biocides to the germination and growth of the marine macroalga, Hormosira banksii (Turner) Desicaine

International Nuclear Information System (INIS)

Myers, Jackie H. . E-mail jhmyers@deakin.edu.au; Gunthorpe, Leanne . E-mail Leanne.Gunthorpe@dpi.vic.gov.au; Allinson, Graeme . E-mail graemea@deakin.edu.au; Duda, Susan . E-mail Susan.Duda@dpi.vic.gov.au

2006-01-01

The International Maritime Organisation's (IMO) ban on the use of tributyltin in antifouling paints has inevitability increased the use of old fashioned antifoulants and/or the development of new paints containing 'booster biocides'. These newer paints are intended to be environmentally less harmful, however the broader environmental effects of these 'booster biocides' are poorly known. Germination and growth inhibition tests using the marine macroalga, Hormosira banksii (Turner) Desicaine were conducted to evaluate the toxicity of four new antifouling biocides in relation to tributyltin-oxide (TBTO). Each of the biocides significantly inhibited germination and growth of Hormosira banksii spores. Toxicity was in increasing order: diuron < zineb < seanine 211 < zinc pyrithione < TBTO. However, the lack of knowledge on partitioning in the environment makes it difficult to make a full assessment on whether the four biocides tested offer an advantage over organotin paints in terms of environmental impact

Butyltin compounds in a sediment core from the old Tilbury basin, London,

Energy Technology Data Exchange (ETDEWEB)

Scrimshaw, M.D. [Department of Environmental Science and Technology, Faculty of Life Sciences, Imperial College London, London SW7 2AZ (United Kingdom); Wahlen, R. [LGC Ltd., Queens Road, Teddington, Middlesex TW11 0LY (United Kingdom); Catterick, T. [LGC Ltd., Queens Road, Teddington, Middlesex TW11 0LY (United Kingdom); Lester, J.N. [Department of Environmental Science and Technology, Faculty of Life Sciences, Imperial College London, London SW7 2AZ (United Kingdom)]. E-mail: j.lester@imperial.ac.uk

2005-12-15

Sections from a sediment core taken from the River Thames were analysed for butyltin species using gas chromatography with species-specific isotope dilution mass spectrometry. Results demonstrated that in most samples tributyltin concentrations of 20-60 ng/g accounted for <10% of the total butyltin species present, which is in agreement with data from other sediment samples which were historically contaminated with tributyltin. Vertical distribution of the organotin residues with depth throughout the core, with data on organochlorine compounds and heavy metals allowed for the construction of a consistent hypothesis on historical deposition of contaminated sediments. From this it was possible to infer that the concentrations of tributyltin in sediments deposited during the early 1960s were in the order of 400-600 {mu}g/g by using degradation rate constants derived by other workers. Such values fall well within the range quoted for harbour sediments in the literature.

Aeromonas veronii, a tributyltin (TBT)-degrading bacterium isolated from an estuarine environment, Ria de Aveiro in Portugal.

Science.gov (United States)

Cruz, Andreia; Caetano, Tânia; Suzuki, Satoru; Mendo, Sónia

2007-12-01

Organotin compounds are used in a variety of industrial processes therefore their subsequent discharge into the environment is widespread. Bacteria play an important role in biogeochemical transformations acting as natural decontamination agents. Therefore, screening for tributyltin (TBT)-resistant and -degrading bacteria is relevant for the selection of isolates with decontamination ability of these polluted areas. With this purpose, 50 strains were isolated from sediment and water from Ria de Aveiro and their tolerance to TBT, up to 3mM, was evaluated. Generally, occurrence of highly TBT-resistant bacteria was observed, and Gram negative bacteria exhibited more tolerance to TBT than Gram positive bacteria. A memory response was observed when bacteria were progressively exposed to increasingly higher TBT concentrations. One isolate, Aeromonas veronii Av27, highly resistant to TBT (3mM) uses this compound as carbon source and degrades it to less toxic compounds.

Tributyltin (TBT) induces oxidative stress and modifies lipid profile in the filamentous fungus Cunninghamella elegans.

Science.gov (United States)

Bernat, Przemysław; Gajewska, Ewa; Szewczyk, Rafał; Słaba, Mirosława; Długoński, Jerzy

2014-03-01

To investigate the response of the tributyltin-degrading fungal strain Cunninghamella elegans to the organotin, a comparative lipidomics strategy was employed using an LC/MS-MS technique. A total of 49 lipid species were identified. Individual phospholipids were then quantified using a multiple reaction monitoring method. Tributyltin (TBT) caused a decline in the amounts of many molecular species of phosphatidylethanolamine or phosphatidylserine and an increase in the levels of phosphatidic acid, phosphatidylinositol and phosphatidylcholine. In the presence of TBT, it was observed that overall unsaturation was lower than in the control. Lipidome data were analyzed using principal component analysis, which confirmed the compositional changes in membrane lipids in response to TBT. Additionally, treatment of fungal biomass with butyltin led to a significant increase in lipid peroxidation. It is suggested that modification of the phospholipids profile and lipids peroxidation may reflect damage to mycelium caused by TBT.

Simultaneous determination of butyltin and phenyltin species in sediments using ultrasound-assisted leaching

Energy Technology Data Exchange (ETDEWEB)

Carpinteiro, J.; Rodriguez, I.; Cela, R. [Dpto. Quimica Analitica, Nutricion y Bromatologia, Universidad de Santiago de Compostela (Spain)

2001-08-01

A fast and simple procedure is presented for the simultaneous leaching of butyl (mono, di and tributyl) and phenyl organotin species from sediment samples. Leached compounds are further ethylated with sodium tetraethylborate in aqueous medium, and analyzed by gas chromatography. After testing the stability of triphenyltin under different extraction conditions, ultrasound-assisted leaching at room temperature in the presence of acetic acid was been proposed as an extraction procedure compatible with the simultaneous determination of phenyl- and butyltin compounds in sediments. Recoveries between 70 and 90% were obtained for phenyl species in spiked samples prepared in the laboratory. Results for butyltin species were validated by use of the reference material PACS-2. Quantification limits, using GC-MIP-AES as measurement technique, were approximately 5-10 ng g{sup -1}. Precision in the consecutive analysis of three sediment samples varied between 3 and 10%. (orig.)

Chemistry of tin compounds and environment

International Nuclear Information System (INIS)

Ali, S.; Mazhar, M.; Mahmood, S.; Bhatti, M.H.; Chaudhary, M.A.

1997-01-01

Of the large volume of tin compounds reported in the literature, possible only 100 are commercially important. Tin compounds are a wide variety of purposes such as catalysts, stabilizers for many materials including polymer, biocidal agents, bactericides, insecticides, fungicides, wood preservatives, acaricides and anti fouling agents in paints, anticancer and antitumour agents, ceramic opacifiers, as textile additives, in metal finishing operations, as food additives and in electro conductive coating. All these applications make the environment much exposed to tin contamination. The application of organotin compounds as biocides account for about 30% of total tin consumption suggesting that the main environmental effects are likely to originate from this sector. Diorgano tins and mono-organo tins are used mainly in plastic industry which is the next big source for environmental pollution. In this presentation all environmental aspects of the use of tin compounds and the recommended preventive measures are discussed. (author)

Total and species-specific quantitative analyses of trace elements in sediment by isotope dilution inductively coupled plasma mass spectrometry

International Nuclear Information System (INIS)

Inagaki, Kazumi; Takatsu, Akiko; Yarita, Takashi; Okamoto, Kensaku; Chiba, Koichi

2009-01-01

Isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS) is one of the reliable methods for total and species-specific quantitative analysis of trace elements. However, several technical problems (e.g. spectral interference caused from sample constituents) should be overcome to obtain reliable analytical results when environmental samples are analyzed by ID-ICP-MS. In our laboratory, various methods based on ID-ICP-MS have been investigated for reliable quantitative analyses of trace elements in environmental samples. In this paper, coprecipitate separation/ID-ICP-MS for the determination of trace elements in sediment, cation exchange disk filtration/ID-ICP-MS for the determination of selenium in sediment, species-specific ID-ICP-MS using 118 Sn/labeled organotin compounds for the determination of butyltins and phenyltins, and the application of the ID-ICP-MS methods to the certification of sediment reference materials are described. (author)

Analytical study of endocrine-disrupting chemicals in leachate treatment process of municipal solid waste (MSW) landfill sites.

Science.gov (United States)

Asakura, Hiroshi; Matsuto, Toshihiko; Tanaka, Nobutoshi

2007-01-01

Influent and processed water were sampled at different points in the leachate treatment facilities of five municipal solid waste (MSW) landfill sites. Then, the concentrations of endocrine-disrupting chemicals (EDCs), namely, alkylphenols (APs), bisphenol A (BPA), phthalic acid esters (PAEs) and organotin compounds (OTs), in the treated leachate samples were determined and the behavior of the EDCs in the treatment processes was discussed. The concentrations of APs were as low as those in surface waters, and no OTs were detected (detection limit: 0.01 microg/L). Meanwhile, diethylhexyl phthalate (DEHP), which was the most abundant of the four substances measured as PAEs, and BPA were found in all of the influent samples. BPA was considerably degraded by aeration, except when the water temperature was low and the total organic carbon (TOC) was high. By contrast, aeration, biological treatment, and coagulation/sedimentation removed only a small amount of DEHP.

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

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

Synthesis, Antibacterial and Antifungal Activity of Some New Pyrazoline and Pyrazole Derivatives

Directory of Open Access Journals (Sweden)

Seham Y. Hassan

2013-02-01

Full Text Available A series of 2-pyrazolines 5–9 have been synthesized from α,β-unsaturated ketones 2–4. New 2-pyrazoline derivatives 13–15 bearing benzenesulfonamide moieties were then synthesized by condensing the appropriate chalcones 2–4 with 4-hydrazinyl benzenesulfonamide hydrochloride. Ethyl [1,2,4] triazolo[3,4-c][1,2,4]triazino[5,6-b]-5H-indole-5-ethanoate (26 and 1-(5H-[1,2,4]triazino[5,6-b] indol-3-yl-3-methyl-1H-pyrazol-5(4H-one (32 were synthesized from 3-hydrazinyl-5H-[1,2,4]triazino[5,6-b]indole (24. On the other hand ethyl[1,2,4]triazolo[3,4-c][1,2,4]triazino[5,6-b]-5,10-dihydroquinoxaline- 5-ethanoate (27 and 1-(5,10-dihydro-[1,2,4]triazino[5,6-b]quinoxalin-3-yl-3-methyl-1H-pyrazol-5(4H-one (33 were synthesized from 3-hydrazinyl-5,10-dihydro-[1,2,4]triazino[5,6-b]quinoxaline (25 by reaction with diethyl malonate or ethyl acetoacetate, respectively. Condensation of 6,6-dimethyl-4-oxo-4,5,6,7-tetrahydro-1H-indole-2-carbaldehyde (1' with compound 24 or 25 afforded the corresponding Schiff's bases 36 and 37, respectively. Reaction of the Schiff's base 37 with benzoyl hydrazine or acetic anhydride afforded benzohydrazide derivative 39 and the cyclized compound 40, respectively. Furthermore, the pyrazole derivatives 42–44 were synthesized by cyclization of hydrazine derivative 25 with the prepared chalcones 2–4. All the newly synthesized compounds have been characterized on the basis of IR and 1H-NMR spectral data as well as physical data. Antimicrobial activity against the organisms E. coli ATCC8739 and P. aeruginosa ATCC 9027 as examples of Gram-negative bacteria, S. aureus ATCC 6583P as an example of Gram-positive bacteria and C. albicans ATCC 2091 as an example of a yeast-like fungus have been studied using the Nutrient Agar (NA and Sabouraud Dextrose Agar (SDA diffusion methods. The best performance was found for the compounds 16, 17, 19 and 20.

Heterocyclic N-oxides - A Promising Class of Agents Against Tuberculosis, Malaria and Neglected Tropical Diseases.

Science.gov (United States)

Dos Santos Fernandes, Guilherme Felipe; Pavan, Aline Renata; Dos Santos, Jean Leandro

2018-04-17

Heterocyclic N-oxides have emerged as promising agents against a number of diseases and disorders, especially infectious diseases. This review analyzes the emergence and development of this scaffold in the medicinal chemistry, focusing mainly on the discovery of new heterocyclic N-oxide compounds with potent activity against tuberculosis, malaria and neglected tropical diseases (i.e. leishmaniasis and Chagas disease). A number of heterocyclic N-oxide are described herein, nevertheless, the following chemical classes deserve to be highlighted due to the large number of reports in the literature about their promising pharmacological effects: furoxan, benzofuroxan, quinoxaline 1,4-di-N-oxide, indolone N-oxide and benzimidazole N-oxide. In order to describe those most promising compounds, we included in this review only those most biologically active heterocyclic N-oxide published since 2000. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Arbutus unedo induces endothelium-dependent relaxation of the isolated rat aorta.

Science.gov (United States)

Ziyyat, Abderrahim; Mekhfi, Hassane; Bnouham, Mohamed; Tahri, Abdelhafid; Legssyer, Abdelkhaleq; Hoerter, Jacqueline; Fischmeister, Rodolphe

2002-09-01

Arbutus unedo L. (Ericaceae) is used in oriental Morocco to treat arterial hypertension. We studied its vasodilator effect and mechanisms of action in vitro. The root aqueous extract of Arbutus (0.25 mg/mL) produced a relaxation of noradrenaline-precontracted ring preparations of rat aorta with intact endothelium. Relaxation by Arbutus did not occur in specimens without endothelium and was inhibited by pretreatment with 100 microM N(G)-methyl-L-arginine (L-NMA), 10 microM methylene blue or 50 microM 1H-[1,2,4] oxadiazolo [4,3-a] quinoxaline-1-one (ODQ) but not by 10 microM atropine. These results suggest that Arbutus produces an endothelium-dependent relaxation of the isolated rat aorta which may be mediated mainly by a stimulation of the endothelial nitric oxide synthase by mechanisms other than activation of muscarinic receptors. Copyright 2002 John Wiley & Sons, Ltd.

Effects of met-enkephalin on GABAergic spontaneous miniature IPSPs in organotypic slice cultures of the rat hippocampus

DEFF Research Database (Denmark)

Rekling, J C

1993-01-01

The action of met-enkephalin on GABAergic spontaneous miniature IPSPs (smIPSPs) was investigated in CA1 neurons from hippocampal slice cultures. In the presence of excitatory amino acid blockers (2,3-dihydroxy-6-nitro-7-sulphamoyl-benzo(F)quinoxaline, DL-2-amino-5-phosphonovaleric acid) and TTX...... the amplitude distribution of the smIPSPs. The proportion of "large" smIPSPs was reduced, but a loss of "small" smIPSPs also contributed to the reduction in smIPSP frequency. The selective mu-receptor agonist DAGO mimicked the effect of met-enkephalin and naloxone blocked the effect of DAGO. Hyperpolarization......IPSP frequency, nor did it block the effect of DAGO. These results suggest that CA1 pyramidal cells of hippocampal organotypic cultures are tonically inhibited by spontaneous release of GABA, through a release mechanism that is independent of propagated sodium action potentials. Met-enkephalin and DAGO reduce...

Emission characteristics in solution-processed asymmetric white alternating current field-induced polymer electroluminescent devices

Science.gov (United States)

Chen, Yonghua; Xia, Yingdong; Smith, Gregory M.; Gu, Yu; Yang, Chuluo; Carroll, David L.

2013-01-01

In this work, the emission characteristics of a blue fluorophor poly(9, 9-dioctylfluorene) (PFO) combined with a red emitting dye: Bis(2-methyl-dibenzo[f,h]quinoxaline)(acetylacetonate)iridium (III) [Ir(MDQ)2(acac)], are examined in two different asymmetric white alternating current field-induced polymer electroluminescent (FIPEL) device structures. The first is a top-contact device in which the triplet transfer is observed resulting in the concentration-dependence of the emission similar to the standard organic light-emitting diode (OLED) structure. The second is a bottom-contact device which, however, exhibits concentration-independence of emission. Specifically, both dye emission and polymer emission are found for the concentrations as high as 10% by weight of the dye in the emitter. We attribute this to the significant different carrier injection characteristics of the two FIPEL devices. Our results suggest a simple and easy way to realize high-quality white emission.

3-[2-(5H-Indolo[2,3-b]quinoxalin-5-ylethyl]-1,3-oxazolidin-2-one

Directory of Open Access Journals (Sweden)

Abdussalam Alsubari

2010-09-01

Full Text Available The title compound, C19H16N4O2, has an almost planar fused N-heterocyclic system (r.m.s. deviation = 0.031 Å and an almost planar five-membered 1,3-oxazolidine ring (r.m.s. deviation = 0.015 Å at the ends of an ethylene chain [N—C—C—N torsion angle = −65.6 (2°]. The ring systems are inclined at 38.1 (1° to one another.

Structural and biochemical studies of a fluoroacetyl-CoA-specific thioesterase reveal a molecular basis for fluorine selectivity.

Science.gov (United States)

Weeks, Amy M; Coyle, Scott M; Jinek, Martin; Doudna, Jennifer A; Chang, Michelle C Y

2010-11-02

We have initiated a broad-based program aimed at understanding the molecular basis of fluorine specificity in enzymatic systems, and in this context, we report crystallographic and biochemical studies on a fluoroacetyl-coenzyme A (CoA) specific thioesterase (FlK) from Streptomyces cattleya. Our data establish that FlK is competent to protect its host from fluoroacetate toxicity in vivo and demonstrate a 10(6)-fold discrimination between fluoroacetyl-CoA (k(cat)/K(M) = 5 × 10⁷ M⁻¹ s⁻¹) and acetyl-CoA (k(cat)/K(M) = 30 M⁻¹ s⁻¹) based on a single fluorine substitution that originates from differences in both substrate reactivity and binding. We show that Thr 42, Glu 50, and His 76 are key catalytic residues and identify several factors that influence substrate selectivity. We propose that FlK minimizes interaction with the thioester carbonyl, leading to selection against acetyl-CoA binding that can be recovered in part by new C═O interactions in the T42S and T42C mutants. We hypothesize that the loss of these interactions is compensated by the entropic driving force for fluorinated substrate binding in a hydrophobic binding pocket created by a lid structure, containing Val 23, Leu 26, Phe 33, and Phe 36, that is not found in other structurally characterized members of this superfamily. We further suggest that water plays a critical role in fluorine specificity based on biochemical and structural studies focused on the unique Phe 36 "gate" residue, which functions to exclude water from the active site. Taken together, the findings from these studies offer molecular insights into organofluorine recognition and design of fluorine-specific enzymes.

Mechanism of immunotoxicological effects of tributyltin chloride on murine thymocytes.

Science.gov (United States)

Sharma, Neelima; Kumar, Anoop

2014-04-01

Tributyltin-chloride, a well-known organotin compound, is a widespread environmental toxicant. The immunotoxic effects of tributyltin-chloride on mammalian system and its mechanism is still unclear. This study is designed to explore the mode of action of tributyltin-induced apoptosis and other parallel apoptotic pathways in murine thymocytes. The earliest response in oxidative stress followed by mitochondrial membrane depolarization and caspase-3 activation has been observed. Pre-treatment with N-acetyl cysteine and buthionine sulfoximine effectively inhibited the tributyltin-induced apoptotic DNA and elevated the sub G1 population, respectively. Caspase inhibitors pretreatment prevent tributyltin-induced apoptosis. Western blot and flow cytometry indicate no translocation of apoptosis-inducing factor and endonuclease G in the nuclear fraction from mitochondria. Intracellular Ca(2+) levels are significantly raised by tributyltin chloride. These results clearly demonstrate caspase-dependent apoptotic pathway and support the role of oxidative stress, mitochondrial membrane depolarization, caspase-3 activation, and calcium during tributyltin-chloride (TBTC)-induced thymic apoptosis.

Cell-selective determination of trace elements in testis by SR-XRF analysis with nanoprobe

International Nuclear Information System (INIS)

Homma-Takeda, Shino; Nishimura, Yoshikazu; Watanabe, Yoshito; Yukawa, Masae; Ueno, Shunji; Terada, Yasuko

2005-01-01

Organotin compounds are widely used in industry and its environmental contamination by these compounds has recently become a concern. It is known that they act as endocrine disruptors but details of the dynamics of Sn in reproductive organs are still unknown. In the present study, we attempted to determine Sn in the testis of rats exposed to tributyltin chloride (TBTC) cell-selectively by synchrotron radiation X-ray florescence analysis with nanoprobe. TBTC was orally administered to rats at a dose of 45 μmol/kg per day for 3 days. One day later, Sn was detected in spermatozoa at the stage VIII seminiferous tubule, which are the final step of spermatogenesis in the testis. Sn levels in the microdissectioned seminiferous tubules determined by inductively coupled argon plasma-mass spectrometry were approximately equivalent to that in the testis. These data indicate that Sn accumulates in germ cells as well as in spermatozoa in a short period of TBTC exposure. (author)

Occurrence of tributyltin (TBT)-resistant bacteria is not related to TBT pollution in Mekong River and coastal sediment: with a hypothesis of selective pressure from suspended solid.

Science.gov (United States)

Suehiro, Fujiyo; Mochizuki, Hiroko; Nakamura, Shinji; Iwata, Hisato; Kobayashi, Takeshi; Tanabe, Shinsuke; Fujimori, Yoshifumi; Nishimura, Fumitake; Tuyen, Bui Cach; Tana, Touch Seang; Suzuki, Satoru

2007-07-01

Tributyltin (TBT) is organotin compound that is toxic to aquatic life ranging from bacteria to mammals. This study examined the concentration of TBT in sediment from and near the Mekong River and the distribution of TBT-resistant bacteria. TBT concentrations ranged from TBT-resistant bacteria ranged TBT-resistant bacteria ranged from TBT in the sediment and of TBT-resistant bacteria were unrelated, and chemicals other than TBT might induce TBT resistance. TBT-resistant bacteria were more abundant in the dry season than in the rainy season. Differences in the selection process of TBT-resistant bacteria between dry and rainy seasons were examined using an advection-diffusion model of a suspended solid (SS) that conveys chemicals. The estimated dilution-diffusion time over a distance of 120 km downstream from a release site was 20 days during dry season and 5 days during rainy season, suggesting that bacteria at the sediment surface could be exposed to SS for longer periods during dry season.

Effects of Organoboron Antifoulants on Oyster and Sea Urchin Embryo Development

Directory of Open Access Journals (Sweden)

Noritaka Tsunemasa

2012-12-01

Full Text Available Prohibition of Ot (organotin compounds was introduced in Japan in 1997 and worldwide from September 2008. This meant that the production of paints containing TBT compounds was stopped and alternatives to the available Ot antifoulants had to be developed. It has been claimed that the degradation by-products of these alternative antifoulants were less toxic than those of Ot compounds. Since the introduction of the alternative antifoulants, the accumulation of these compounds has been reported in many countries. However, the toxicity of these compounds was still largely unreported. In this research, the toxicity of the alternative Ot antifoulants TPBP (triphenylborane pyridine and TPBOA (triphenylborane octadecylamine and their degradation products on Crassostea gigas and Hemicentrotus pulcherrimus were tested. The results showed that toxic effects in Crassostea gigas was higher for each antifouling biocide than that in Hemicentrotus pulcherrimus. Also, while the toxicity of the Organoboron antifoulants and the Ots were the same, the former’s degradation products were much less harmful.

Dibutylammonium bis(hydrogen methylphosphonato-κOtriphenylstannate(IV

Directory of Open Access Journals (Sweden)

Tidiane Diop

2012-10-01

Full Text Available The asymmetric unit of the title organotin salt, (C8H20N[Sn(C6H53(CH4O3P2], contains two dibutylammonium cations and two stannate(IV anions consisting each of two monodentately bonding methyl hydrogenphosphate groups attached to an Sn(C6H5 unit. The overall coordination environment of the two SnIV atoms is trigonal–bipyramidal defined by three phenyl C atoms in equatorial positions and two methyl hydrogenphosphate O atoms at the apical sites. In the crystal, the stannate(IV anions are linked to each other via pairs of short O—H...O hydrogen bonds, leading to an infinite chain extending parallel to the b-axis direction. Neighbouring chains are linked by N—H...O hydrogen bonds involving the butylammonium cations, giving a two-dimensional structure parallel to the ab plane. The crystal under investigation was found to be twinned by reticular merohedry with twin fractions of 0.5342 (7:0.4658 (7.

A model compound study: the ecotoxicological evaluation of five organic contaminants employing a battery of marine bioassays.

Science.gov (United States)

Macken, Ailbhe; Giltrap, Michelle; Foley, Barry; McGovern, Evin; McHugh, Brendan; Davoren, Maria

2008-06-01

This paper describes the ecotoxicological evaluation of five organic contaminants frequently detected in marine sediments (tributyltin, triphenyltin, benzo[a]pyrene, fluoranthene, and PCB 153) using three marine species (Vibrio fischeri, Tetraselmis suecica, and Tisbe battagliai). The sensitivity of each species varied for all compounds. The triorganotins were consistently the most toxic to all species. The applicability of each test system to assess the acute toxicity of environmental contaminants and their use in Toxicity Identification Evaluation (TIE) is discussed. Suitability of the Microtox and T. battagliai tests for employment in TIE studies were further assessed through spiking experiments with tributyltin. Results demonstrated that the most effective treatment to remove organotin toxicity from the sample was the C18 resin. The results of this study have important implications for risk assessment in estuarine and coastal waters in Ireland, where, at present the monitoring of sediment and water quality is predominantly reliant on chemical analysis alone.

Pilot survey of a broad range of priority pollutants in sediment and fish from the Ebro river basin (NE Spain)

International Nuclear Information System (INIS)

Lacorte, Silvia; Raldua, Demetrio; Martinez, Elena; Navarro, Alicia; Diez, Sergi; Bayona, Josep M.; Barcelo, Damia

2006-01-01

Priority organic pollutants were investigated in sediments and fish collected along the Ebro river basin (NE Spain) to evaluate their occurrence, transport and bioavailability. Sediments were collected in 18 sites and two species of fish were captured in nine sites according to the availability in each area. The sampling sites covered industrial, urban and agricultural areas. Four methods were used to detect 20 organochlorine compounds (OCs), 8 polycyclic aromatic hydrocarbons, 3 organotin compounds, 2 alkylphenols and 40 polybrominated diphenyl ethers (PBDEs) from purified extracts. The contamination pattern was site specific and no downstream increase in concentration of pollutants was observed but rather a generalized low level diffuse pollution. Target compounds were detected in sediments at 0.01 to 2331 μg/kg dry weight, and only OCs and PBDEs were accumulated in benthopelagic fish. Toxicological assessment was performed according to predicted environmental levels and revealed sites where adverse effects could occur. - Organic pollutants were monitored in sediments and fish from the Ebro river basin (NE Spain)

Structural optimization and evaluation of butenolides as potent antifouling agents: modification of the side chain affects the biological activities of compounds

KAUST Repository

Li, Yongxin

2012-09-01

A recent global ban on the use of organotin compounds as antifouling agents has increased the need for safe and effective antifouling compounds. In this study, a series of new butenolide derivatives with various amine side chains was synthesized and evaluated for their anti-larval settlement activities in the barnacle, Balanus amphitrite. Side chain modification of butenolide resulted in butenolides 3c-3d, which possessed desirable physico-chemical properties and demonstrated highly effective non-toxic anti-larval settlement efficacy. A structure-activity relationship analysis revealed that varying the alkyl side chain had a notable effect on anti-larval settlement activity and that seven to eight carbon alkyl side chains with a tert-butyloxycarbonyl (Boc) substituent on an amine terminal were optimal in terms of bioactivity. Analysis of the physico-chemical profile of butenolide analogues indicated that lipophilicity is a very important physico-chemical parameter contributing to bioactivity. © 2012 Copyright Taylor and Francis Group, LLC.

Distribution of butyltins in the waters and sediments along the coast of India.

Science.gov (United States)

Garg, Anita; Meena, Ram M; Jadhav, Sangeeta; Bhosle, Narayan B

2011-02-01

Water and surface sediment samples were analyzed for butyltins (TBT, DBT, MBT) from various ports along the east and west coast of India. The total butyltin (TB) in water samples varied between ~1.7 and 342 ng S nl⁻¹, whereas for sediments it varied between below detection limit to 14861 ng S ng⁻¹ dry weight of sediment. On an average Chennai port recorded the highest level of butyltins in the sediments while Paradip recorded the highest level of butylins in the waters. A fairly good relationship between the TB in the sediment and overlying water samples, as well as between organic carbon and TB, implicates the importance of adsorption/desorption process in controlling the levels of TBT in these port areas. In India the data on organotin pollution is very sparse; most of the port areas have been surveyed for butyltins for the first time during this study. Copyright © 2010 Elsevier Ltd. All rights reserved.

Potent antifouling compounds produced by marine Streptomyces

KAUST Repository

Xu, Ying

2010-02-01

Biofouling causes huge economic loss and a recent global ban on organotin compounds as antifouling agents has increased the need for safe and effective antifouling compounds. Five structurally similar compounds were isolated from the crude extract of a marine Streptomyces strain obtained from deep-sea sediments. Antifouling activities of these five compounds and four other structurally-related compounds isolated from a North Sea Streptomyces strain against major fouling organisms were compared to probe structure-activity relationships of compounds. The functional moiety responsible for antifouling activity lies in the 2-furanone ring and that the lipophilicity of compounds substantially affects their antifouling activities. Based on these findings, a compound with a straight alkyl side-chain was synthesized and proved itself as a very effective non-toxic, anti-larval settlement agent against three major fouling organisms. The strong antifouling activity, relatively low toxicity, and simple structures of these compounds make them promising candidates for new antifouling additives. © 2009 Elsevier Ltd. All rights reserved.

Persistent toxic substances: sources, fates and effects.

Science.gov (United States)

Wong, Ming H; Armour, Margaret-Ann; Naidu, Ravi; Man, Ming

2012-01-01

Persistent toxic substances (PTS) include the Stockholm persistent organic pollutants, like dichlorodiphenyltrichloroethane, polychlorinated biphenyls, dioxin/furan, etc., and organometallic compounds, like organomercury, organotin, and organolead, which all share the same characteristics of being persistent, toxic, bioaccumulative, and able to travel long distances through different media. The adverse health effects of some of the emerging chemicals like pentabromodiphenyl ether, bisphenol A, and di(2-ethylhexyl)phthalate, which are widely used in daily appliances (e.g., TVs, computers, mobile phones, plastic baby bottles), have become a public health concern due to more evidence now available showing their adverse effects like disturbance of the endocrine system and cancer. This article is an attempt to review the current status of PTS in our environment, citing case studies in China and North America, and whether our existing drinking water treatment and wastewater treatment processes are adequate in removing them from water. Some management issues of these emerging chemicals of concern are also discussed.

Results of bulk sediment analysis and bioassay testing on selected sediments from Oakland Inner Harbor and Alcatraz disposal site, San Francisco, California

International Nuclear Information System (INIS)

Word, J.Q.; Ward, J.A.; Woodruff, D.L.

1990-09-01

The Battelle/Marine Sciences Laboratory (MSL) was contracted by the US Army Corps of Engineers, San Francisco District, to perform bulk sediment analysis and oyster larvae bioassays (elutriate) on sediments from Inner Oakland Harbor, California. Analysis of sediment characteristics by MSL indicated elevated priority pollutants, PAHs, pesticides, metals, organotins, and oil and grease concentrations, when compared to Alcatraz Island Dredged Material Disposal Site sediment concentrations. Larvae of the Pacific oyster, Crassostrea gigas, were exposed to seawater collected from the Alcatraz Island Site water, and a series of controls using water and sediments collected from Sequim Bay, Washington. Exposure of larvae to the Alcatraz seawater and the 50% and 100% elutriate concentrations from each Oakland sediment resulted in low survival and a high proportion of abnormal larvae compared to Sequim Bay control exposures. MSL identified that field sample collection, preservation, and storage protocols used by Port of Oakland contractors were inconsistent with standard accepted practices. 23 refs., 10 figs., 40 tabs

Triphenyltin alters lipid homeostasis in females of the ramshorn snail Marisa cornuarietis.

Science.gov (United States)

Lyssimachou, Angeliki; Navarro, Juan Carlos; Bachmann, Jean; Porte, Cinta

2009-05-01

Molluscs are sensitive species to the toxic effects of organotin compounds, particularly to masculinisation. Both tributyltin (TBT) and triphenyltin (TPT) have been recently shown to bind to mollusc retinoid X receptor (RXR). If RXR is involved in lipid homeostasis, exposure to TPT would have an immediate effect on endogenous lipids. To test this hypothesis, the ramshorn snail Marisa cornuarietis was exposed to environmentally relevant concentrations of TPT (30, 125, 500 ng/L as Sn) in a semi-static water regime for 7 days. Percentage of lipids and total fatty acid content decreased significantly in TPT-exposed females while the activity of peroxisomal acyl-CoA oxidase, involved in fatty acid catabolism, increased. In addition, fatty acid profiles (carbon chain length and unsaturation degree) were significantly altered in exposed females but not in males. This work highlights the ability of TPT to disrupt lipid metabolism in M. cornuarietis at environmentally realistic concentrations and the higher susceptibility of females in comparison to males.

Structural optimization and evaluation of butenolides as potent antifouling agents: modification of the side chain affects the biological activities of compounds

KAUST Repository

Li, Yongxin; Zhang, Fengying; Xu, Ying; Matsumura, Kiyotaka; Han, Zhuang; Liu, Lingli; Lin, Wenhan; Jia, Yanxing; Qian, Pei Yuan

2012-01-01

A recent global ban on the use of organotin compounds as antifouling agents has increased the need for safe and effective antifouling compounds. In this study, a series of new butenolide derivatives with various amine side chains was synthesized and evaluated for their anti-larval settlement activities in the barnacle, Balanus amphitrite. Side chain modification of butenolide resulted in butenolides 3c-3d, which possessed desirable physico-chemical properties and demonstrated highly effective non-toxic anti-larval settlement efficacy. A structure-activity relationship analysis revealed that varying the alkyl side chain had a notable effect on anti-larval settlement activity and that seven to eight carbon alkyl side chains with a tert-butyloxycarbonyl (Boc) substituent on an amine terminal were optimal in terms of bioactivity. Analysis of the physico-chemical profile of butenolide analogues indicated that lipophilicity is a very important physico-chemical parameter contributing to bioactivity. © 2012 Copyright Taylor and Francis Group, LLC.

Degradation and toxicity of phenyltin compounds in soil

International Nuclear Information System (INIS)

Paton, G.I.; Cheewasedtham, W.; Marr, I.L.; Dawson, J.J.C.

2006-01-01

Although the fate of organotins has been widely studied in the marine environment, fewer studies have considered their impact in terrestrial systems. The degradation and toxicity of triphenyltin in autoclaved, autoclaved-reinoculated and non-sterilised soil was studied in a 231 day incubation experiment following a single application. Degradation and toxicity of phenyltin compounds in soil was monitored using both chemical and microbial (lux-based bacterial biosensors) methods. Degradation was significantly slower in the sterile soil when compared to non-sterilised soils. In the non-sterilised treatment, the half-life of triphenyltin was 27 and 33 days at amendments of 10 and 20 mg Sn kg -1 , respectively. As initial triphenyltin degradation occurred, there was a commensurate increase in toxicity, reflecting the fact that metabolites produced may be both more bioavailable and toxic to the target receptor. Over time, the toxicity reduced as degradation proceeded. The toxicity impact on non-target receptors for these compounds may be significant. - Triphenyltin degradative metabolites cause toxic responses to biosensors

Thermochemical study of chloropyrazines and chloroquinoxalines

International Nuclear Information System (INIS)

Morais, Victor M.F.; Miranda, Margarida S.; Matos, M. Agostinha R.

2004-01-01

The standard (p 0 =0.1 MPa) molar enthalpies of formation for liquid 2-chloropyrazine and crystalline 2,6-dichloropyrazine, 2,3-dichloroquinoxaline and 2,3,6,7-tetrachloroquinoxaline were derived from the standard molar enthalpies of combustion, in oxygen, to yield CO 2 (g), N 2 (g), and HCl · 600H 2 O(l), at the temperature T=298.15 K, measured by rotating-bomb combustion calorimetry. The standard molar enthalpies of vaporization or of sublimation, at T=298.15 K, were measured by Calvet microcalorimetry. Density functional theory with the B3LYP functional and two different basis sets, 6-31G* and 6-311G**, was used to optimize the geometries of all chloro-substituted pyrazines and some chloro-substituted quinoxalines. The calculation of the energy of isodesmic reactions allowed the estimation of the standard molar enthalpies of formation in the gas phase for all compounds including some not studied experimentally

The Prevalence of the OqxAB Multidrug Efflux Pump amongst Olaquindox-Resistant Escherichia coli in Pigs

DEFF Research Database (Denmark)

Hansen, Lars Hestbjerg; Sørensen, Søren Johannes; Jørgensen, Helle S.

2005-01-01

The quinoxaline olaquindox has been used extensively as a growth promoter for pigs. Recently, we isolated a plasmid (pOLA52) conferring resistance to olaquindox from swine manure. On this plasmid, the oqxA and oqxB genes encode an RND-family multidrug efflux pump, OqxAB. It facilitates resistance...... to olaquindox as well as resistance to other antimicrobials like chloramphenicol. In this study, 10 of the 556 (1.8%) previously isolated Escherichia coli strains were shown to have an MIC = 64 µg/ml olaquindox. In nine of the ten strains, the oqxA gene was detected. Sequencing of an internal fragment of oqx......A from the oqxA-positive strains showed no variation, indicating highly conserved oqxA genes. All of the oqxA-positive strains contain plasmids with replicons similar to that of pOLA52. It was verified by Southern hybridization that the oqxAB operon was situated on plasmids in most, if not all, resistant...

The prevalence of the OqxAB amongst olaquindox-resistant multidrug efflux pump Escherichia coli in pigs

DEFF Research Database (Denmark)

Hansen, L.H.; Sørensen, S.J.; Jørgensen, H.S.

2005-01-01

The quinoxaline olaquindox has been used extensively as a growth promoter for pigs. Recently, we isolated a plasmid (pOLA52) conferring resistance to olaquindox from swine manure. On this plasmid, the oqxA and oqxB genes encode an RND-family multidrug efflux pump, OqxAB. It facilitates resistance...... to olaquindox as well as resistance to other antimicrobials like chloramphenicol. In this study, 10 of the 556 (1.8%) previously isolated Escherichia coli strains were shown to have an MIC >= 64 mu g/ml olaquindox. In nine of the ten strains, the oqxA gene was detected. Sequencing of an internal fragment of oqx......A from the oqxA-positive strains showed no variation, indicating highly conserved oqxA genes. All of the oqxA-positive strains contain plasmids with replicons similar to that of pOLA52. It was verified by Southern hybridization that the oqxAB operon was situated on plasmids in most, if not all, resistant...