Abstract  BIOSIS COPYRIGHT: BIOL ABS. For the validation of the genotoxicity testing on stack gas condensates from waste incineration plants using bacterial short time tests (15), a modified UDS assay with the lung cell lines NCI-H 322 and 358 was developed. The UDS assay is more sensitive than the SOS chromotest and discriminates better between the negative or weakly positive and the clearly positive samples. It has a high sensitivity and specificity and also accuracy, is practicable in a comparatively simple, speedy and reasonably he two test cell lines. From three plants examined continuously in this period only two emitted stack gases with constantly low genotoxicity at the end of sampling. 5 clean gas condensates, that were taken in random samples from 3 other plants in the period 1994 to 1995, proved to be non-genotoxic in the UDS assay. However, one of these plants emitted stack gases with high cytotoxicity, which might have masked UDS-inducing single substances. It is not possible to make a statement

Abstract  Soluble methane monooxygenase (sMMO) from methane-oxidizing bacteria is a multicomponent nonheme oxygenase that naturally oxidizes methane to methanol and can also cooxidize a wide range of adventitious substrates, including mono- and diaromatic hydrocarbons. Leucine 110, at the mouth of the active site in the alpha subunit of the hydroxylase component of sMMO, has been suggested to act as a gate to control the access of substrates to the active site. Previous crystallography of the wild-type sMMO has indicated at least two conformations of the enzyme that have the "leucine gate" open to different extents, and mutagenesis of homologous enzymes has indicated a role for this residue in the control of substrate range and regioselectivity with aromatic substrates. By further refinement of the system for homologous expression of sMMO that we developed previously, we have been able to prepare a range of site-directed mutations at position 110 in the alpha subunit of sMMO. All the mutants (with Gly, Cys, Arg, and Tyr, respectively, at this position) showed relaxations of regioselectivity compared to the wild type with monoaromatic substrates and biphenyl, including the appearance of new products arising from hydroxylation at the 2- and 3- positions on the benzene ring. Mutants with the larger Arg and Trp residues at position 110 also showed shifts in regioselectivity during naphthalene hydroxylation from the 2- to the 1- position. No evidence that mutagenesis of Leu 110 could allow very large substrates to enter the active site was found, however, since the mutants (like the wild type) were inactive toward the triaromatic hydrocarbons anthracene and phenanthrene. Thus, our results indicate that the "leucine gate" in sMMO is more important in controlling the precision of regioselectivity than the sizes of substrates that can enter the active site.

Abstract  Separation and determination of thorium, uranium and mixed rare-earth elements (RE) as their 2-(2-arsenophenylazo)-1,8-dihydroxyl-7-(4-chloro-2,6-dibromophenylazo)-naphthalene-3,6-disulfonic acid (DBC-As) complexes by capillary electrophoresis is presented in this paper. The pre-column derivitization conditions are discussed. Some separation parameters such as pH value, type of carrier electrolyte, applied voltage, the concentration of ligand in buffer and the sample size are also optimized. Under the selected conditions, the complete separation of thorium and uranium from mixed RE was accomplished in 10 min. Quantitative analyses exhibited an excellent linear dynamic relationship in the range of over two orders of magnitude. Detection limits of 4.81x10(-8), 7.23x10(-8), and 59.4x10(-8) mol l(-1) for RE, Th and U were obtained, respectively. This method was applied to the determination of these metal ions in ore samples.

Abstract  In Africa, Mitragyna inermis (Willd.) O. Kuntze (Rubiaceae) is commonly used in traditional medicine to treat malaria. Antimalarial activity is mostly due to the hydromethanolic extract of M. inermis leaves and especially to the main alkaloids, uncarine D and isorhynchophilline. In the present study, we describe for the first time an HPLC method for the simultaneous quantification of uncarine D and isorhynchophylline in biological matrices. SPE was used to extract the components and the internal standard naphthalene from human and pig plasma samples. Chromatographic separation was performed on a C-18 reversed column at a flow rate of 1 mL/min, using methanol-phosphate buffer (10:90, pH 7), as a mobile phase. Good linearity was observed over the concentration ranges of 0.0662-3.31 microg/mL for uncarine D and 0.0476-2.38 microg/mL for isorynchophylline. The precision was less than 12% and the accuracy was from 86 to 107% without any discrepancy between the two species. Uncarine D and isorhynchophylline recoveries were over 80%. These results allowed the quantification of both uncarine D and isorhynchophylline in pig plasma after intravenous administration of M. inermis extract.

Abstract  The title anti-pyrine derivative, C(22)H(19)N(3)O(2), was synthesized by the reaction of 4-amino-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazol-3-one and 1-hy-droxy-naphthalene-2-carbaldehyde in methanol solution. As expected, the compound adopts a trans configuration about the central C=N bond. The N atom is involved in an intra-molecular O-H⋯N bond which stabilizes the mol-ecular configuration. In the crystal structure, adjacent mol-ecules stack with no short contacts.

Abstract  The authors of this article describe the determination of D/L-amino acid residues in peptides and proteins at microgram levels. They fluorescently tagged amino acid residues with naphthalene-2,3-dicarboxaldehyde and performed enantioseparation using β-cyclodextrin-modified micellar electrokinetic chromatography in the presence of methanol as an organic modifier. Their separation was coupled with laser-induced fluorescence detection for sensitive determination. The authors determined configurations of amino acid residues in peptides with 10 μg of hydrolyzed peptide material. They demonstrated the assessment of enantiomeric purity for synthetic peptides by their proposed method. They also applied the method to determining D-aspartic acid, free and bound in proteins in rat brains. Although they detected high levels of free D-aspartic acid, no D-aspartic acid was bound in proteins.

Abstract  BIOSIS COPYRIGHT: BIOL ABS. RRM POLLUTION CONTROL WASTE MANAGEMENT PLUMES PARTICLES RESIDUES PROPELLANTS EXPLOSIVES PYROTECHNICS

Abstract  BIOSIS COPYRIGHT: BIOL ABS. Natural organic matter (NOM) in nine water samples selected for the NOM typing project were characterized by pyrolysis in conjunction with gas chromatography and mass spectrometry (GC-MS). NOM samples both isolated by reverse osmosis and evaporation techniques were subjected to high temperature pyrolysis and the products obtained were assigned to one of the four main types: biopolymers carbohydrates, proteinaceous materials, N-acetylamino sugars, and polyhydroxy aromatics. These biopolymers in t verse osmosis technique.

Abstract  The dissociation constants of 45 substituted 1- and 2-naphthoic acids in six organic solvents (methanol, ethanol, acetonitrile, dimethylformamide, dimethyl sulfoxide, pyridine) have been used to evaluate the substituent effects in the naphthalene skeleton. The dissociation constants data have been treated traditionally by using Dewar-Grisdale equation and the Taft DSP equation, and the alternative interpretation of substituent effects (AISE) method. Quantitative comparison of substituent effects and their transmission from different positions, combination of inductive and resonance effects from various positions, and effects of solvents are discussed. Best results are predominantly provided by the AISE. Substituent effects are stronger in the case of substituents affecting from ring of the naphthalene skeleton bearing carboxylic group than from ring not bearing carboxylic group, and there are no substantial differences between the individual positions of this ring. The contribution of resonance effects at 4α and 8β positions distinctly changes with the medium. Special quality of substituent H was found in comparison with other substituents presumably due their bulkier character. The principal component analysis (PCA) has been also applied to treat the mean dissociation constants using the single substituent property approach. The dissociation together with reactivity data for other naphthalene derivatives have been tested for compre-hensive evaluation using PCA. There was found a large similarity of naphthalene reactivity data tested from the point of view of substituent effects.

Abstract  The photophysics and photochemistry of 1,1'-, 1,2'-, and 2,2'-dinaphthyl ketones and a related 2,3,5,6-dibenzofluorenone were studied by laser flash photolysis techniques in organic solvents. Their photochemistry is dominated by the triplet state, which has a pi,pi* character. This is consistent with their phosphorescence spectra, as is the high efficiency of the sensitization of singlet oxygen generation, Phi=0.9-0.96 in acetonitrile. Self-quenching plays an important role in determining triplet lifetimes in solution. The dinaphthyl ketone triplets are not photoreduced by 2-propanol, a common hydrogen donor toward n,pi* ketone triplets. The energies of dinaphthyl ketone triplets range from E-T=53.8 for rigid 2,3,5,6-dibenzofluorenone to 59.2 kcal mol(-1) for flexible 2,2'-dinaphthyl ketone, and reflect the degree of conjugation of the carbonyl group and naphthalene rings promoted by their ability to approach a coplanar conformation. The reactions of the dinaphthyl ketone triplets with 1,4-diazabicyclo[2.2.2] octane (DABCO), triethylamine, 1,4-cyclohexadiene and 2,4,6-trimethylphenol indicate their strong preference for electron transfer. For example, the electron transfer from DABCO to 2,3,5,6-dibenzofluorenone triplet in methanol occurs with k=9.9X10(8) M-1 s(-1), and is almost two orders of magnitude faster than H-atom abstraction from an excellent H-atom donor 1,4-cyclohexadiene (k=1.4X10(7) M-1 s(-1)). Hydrogen bonding between the reactants plays a major role in the reactions with 2,4,6-trimethylphenol. The reactivities in non-hydrogen bonding hexane, are considerably higher than in methanol, where the hydrogen bonds with the solvent hinder the interaction between the reactants. (C) 1997 Elsevier Science S.A.

Abstract  Combustion sampling for toxicological assessment often requires that large (greater than 100 mg) lots of complex organic mixtures of wide volatility range be rapidly recovered from high temperature gases without contamination. A new sampler, meeting these criteria for studies of public health interest, has been developed and demonstrated. The device provides high sampling rates and intimate contacting of the samples stream with large volumes of a well-cooled, liquid solvent, dichloromethane (DCM). This promotes rapid organics dissolution from carrier gas and particulates and prompt dilution and quenching of the resulting solution, resulting in high organics collection efficiencies with minimal DCM losses. Solvent separation then remits large quantities of concentrated organics for chemical analysis and toxicological testing. One- to seven-hour interrogations of in-flame, post-flame, and flue gas regions gave 50- to 250-mg yields of complex organic mixtures. In side-by-side sampling of combustion exhaust, the DCM sampler provided higher yields of DCM solubles (identified with complex organic mixtures) and of S. typhimuirim mutagens (active without exogenous metabolizing agents) than did a filter/polymeric sorbent bed sampling train. The new sampler also collects polar and high volatile hydrocarbons such as benzaheyde, pentadiyne, m- and p-diethynyl-benzene, and 1-hexen-3,5-diyne. Nitration of naphthalene and pyrene in DCM solution (1 mg/mL each) was less than 1 part in 10(7) after a 345-min exposure to a bubbling flow of moist N2/air mixture (1:1 v/v) containing 107 ppm NO and 1.5 ppm NO2, indicating that for these condition a DCM sampler should resist artifactual nitration of aromatics. However, because of the very high bacterial mutagenicity of some nitroaromatics and the wide range of sampling conditions of environmental interest, nitration and all artifacts must still be scrutinized when using the DCM sampler. The DCM sampler is expected to contribute to public health impact assessments by facilitating detailed determinations of the identities, compositions, concentrations, sources, formation mechanisms, and biological activity of environmental toxicants in gaseous atmospheres.

Abstract  The dichloromethane/methanol (1 : 1) extracts of the roots of Pentas longiflora and Pentas lanceolata showed low micromolar (IC₅₀= 0.9-3 µg/mL) IN VITRO antiplasmodial activity against chloroquine-resistant (W2) and chloroquine-sensitive (D6) strains of PLASMODIUM FALCIPARUM. Chromatographic separation of the extract of PENTAS LONGIFLORA led to the isolation of the pyranonaphthoquinones pentalongin (1) and psychorubrin (2) with IC₅₀ values below 1 µg/mL and the naphthalene derivative mollugin (3), which showed marginal activity. Similar treatment of Pentas lanceolata led to the isolation of eight anthraquinones ( 4-11, IC₅₀= 5-31 µg/mL) of which one is new (5,6-dihydroxydamnacanthol, 11), while three--nordamnacanthal (7), lucidin-ω-methyl ether (9), and damnacanthol (10)--are reported here for the first time from the genus Pentas. The compounds were identified by NMR and mass spectroscopic techniques.

Abstract  In the early 1980s, a series of limited special purpose investigations was initiated to determine whether certain chemicals were entering Wisconsin's groundwater and, if so, to determine their concentrations. Screening of 1174 community wells and 617 private wells showed that 65 community wells had detectable levels of volatile organic chemicals (VOCs) and that 5 community wells had concentrations above the recommended health advisory levels. Also 82 private wells had detectable levels of VOCs, 14 of which had concentrations above the health advisory. On the basis of these initial results, sampling near probable sources of contamination will be given more attention as contamination appears more site‐specific than widespread.

Abstract  The use of mercapturic acids (N-acetyl-L-cysteine S-conjugates, MAs) in the biological monitoring of human exposure to environmental and industrial chemicals is receiving more and more attention. Mercapturic acids (MAs) are formed from glutathione (GSH) S-conjugates via the MA-pathway. Although this pathway can lead to different end-products, the formation of MAs is the predominant route in most species, including man. Two GSH S-transferases (GSTs) show genetic polymorphisms in humans and this can have major consequences for individual susceptibility to toxic effects and for MA formation. In occupational toxicology, adducts to biomacromolecules are also used as biomarkers. DNA adducts are a measure for the effective dose, while protein adducts are related to the dose at critical site. Both type of adducts are normally determined in blood, while MAs are determined in urine. Most MAs are excreted with relatively short half-lifes, allowing a direct evaluation of the occupational circumstances. For many compounds similar (linear) dose-dependency was found for MA excretion, formation of macromolecular adducts, and for various biomarkers of toxic effects. These relations together with fact that MAs relate to the electrophilic character of compounds, allows for the conclusion that MAs are biomarkers of toxicologically relevant internal doses of chemicals or their metabolites. An overview will be given here of the use of MAs in the assessment of internal human exposure to electrophilic environmental and industrial chemicals. Additionally, the formation of GSH S-conjugates, their catabolism to MAs and several of the frequently used analytical approaches are discussed. When appropriate, the influence of genetic polymorphisms on formation of MAs and on susceptibility to toxicity will be discussed for different chemicals as well.

Abstract  BIOSIS COPYRIGHT: BIOL ABS. On the basis of 1776 descriptions of water transport accidents involving dangerous goods, environmental problems in connection with releases of this kind are described and discussed. It was found that most detailed descriptions of environmental consequences concerned oil accidents, although most of the consequences were described as reversible changes. It was shown that crude oil releases, on average, are approximately five times larger than releases of oil products and that oil product releases are approximately five times larger than other chemicals. Only 2% of the 1776 accidents described contained information on consequences to living organisms, and only 10% contained any information on consequences to ecosystems. A relationship was found between the minimum kilometers of shore polluted and the tonnes released in the case of shore pollution from oil accidents. Oil slicks were shown to be five times longer than broad. Gravity scales used to describe and evaluate env

Abstract  BIOSIS COPYRIGHT: BIOL ABS. The collection of whole air samples using SUMMA polished canisters has been a commonly used technique for over a decade. This technique has been examined for sample storage, analyte stability, and recovery for up to 45 compounds routinely detected in ambient air. However, this technique is often used for a more extended set of target analytes for which little or no published validation data exist. This paper reports the accuracy, precision, and storage stability results for 194 volatile organic compounds generated in humidified ambient air and collected in SUMMA polished canisters. In addition, instrument and method detection limits for the gas chromatography/multidetector (GC) analytical system were determined from the resulting data. A small percentage of the study compounds displayed high variability, low recovery, or poor storage stability for which qualitative only data can be generated with this technique. However, 168 of 194 (86%) compounds studied appear to be a

Abstract  BIOSIS COPYRIGHT: BIOL ABS. The environmental distribution of 29 organic chemicals was calculated according to the fugacity model level I. The results were graphically analyzed by means to correspondence factor analysis and minimum spanning tree method. These two complementary multivariate approaches allowed to find structure/environmental fate relationships. The heuristic potency of this approach was discussion in detail.

Abstract  Il y a environ 50 000 à 60 000 composés chimiques utilisés communément à des fins techniques. Certains d'entre eux sont toxiques et leur rejet dans l'environnement peut constituer une menace pour l'équilibre des écosystèmes aquatiques et pour la santé humaine. Plusieurs listes de substances dangereuses, appelées également polluants chimiques prioritaires, ont ainsi été établies par des organismes nationaux ou internationaux, notamment par l'EPA aux Etats-Unis, la CEE en Europe, l'Organisation Mondiale de la Santé (OMS). La nécessité de protéger les milieux aquatiques et la santé humaine a par ailleurs amené le développement de standards, de critères de qualité des eaux naturelles et des eaux potables, vis-à-vis de ces contaminants chimiques. Les sources de pollution sont diverses, se partageant entre les sources localisées comme les effluents urbains et industriels et les sources diffuses comme les eaux de ruissellement en zones rurales et en zones urbaines et les retombées atmosphériques. Différentes processus biogéochimiques déterminent les mécanismes de transport et de transformation des polluants organiques dans le milieu aquatique, et la bioaccumutation dans les organismes vivants représente un important aspect de ce comportement. Une première évaluation de la qualité des eaux continentales (rivières, lacs, eaux souterraines) est effectuée en examinant les données recueillies à travers le réseau de surveillance mondiale de la qualité de l'eau (GENS/EAUX) mis en place par deux organismes des Nations Unies, l'OMS et le PNUE. D'autres sources d'informations, publiées dans la littérature scientifique, ont été également utilisées pour évaluer les niveaux de concentrations observés pour différents groupes de polluants organiques dans les eaux naturelles et les eaux potables. La plupart des données disponibles proviennent d'un nombre limité de pays industriels d'Amérique du Nord, d'Europe et du Japon. Il y a une dramatique absence d'informations concernant la qualité chimique des eaux continentales dans les pays les moins développés d'Afrique, d'Amérique Latine et d'Asie. A l'heure actuelle, la stratégie de surveillance des polluants chimiques à l'échelle mondiale est donc loin d'être réellement satisfaisante.

Abstract  Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental contaminants generated as byproducts of natural and anthropogenic combustion processes. Despite significant public health concern, physiologically based pharmacokinetic (PBPK) modeling efforts for PAHs have so far been limited to naphthalene, plus simpler PK models for pyrene, nitropyrene, and benzo[a]pyrene (B[a]P). The dearth of published models is due in part to the high lipophilicity, low volatility, and myriad metabolic pathways for PAHs, all of which present analytical and experimental challenges. Our research efforts have focused upon experimental approaches and initial development of PBPK models for the prototypic PAH, B[a]P, and the more potent, albeit less studied transplacental carcinogen, dibenzo[def,p]chrysene (DBC). For both compounds, model compartments included arterial and venous blood, flow limited lung, liver, richly perfused and poorly perfused tissues, diffusion limited fat, and a two compartment theoretical gut (for oral exposures). Hepatic and pulmonary metabolism was described for both compounds, as were fractional binding in blood and fecal clearance. Partition coefficients for parent PAH along with their diol and tetraol metabolites were estimated using published algorithms and verified experimentally for the hydroxylated metabolites. The preliminary PBPK models were able to describe many, but not all, of the available data sets, comprising multiple routes of exposure (oral, intravenous) and nominal doses spanning several orders of magnitude.

Abstract  Cytochrome P450 (CYP) monooxygenase activities with different category of substrates namely, alkanes, alkane derivatives, alcohols, aromatic compounds, organic solvents, and steroids were detected in the cells of Aspergillus terreus. High CYP specific activity was observed when methanol (5.6+/-0.017 U mg(-1)), acetone (7.76+/-0.02 U mg(-1)), dimethylsulphoxide (DMSO) (9.70+/-0.005 U mg(-1)), n-hexadecane (4.39+/-0.02 U mg(-1)), or n-octadecane (4.23+/-0.01 U mg(-1)) were used as substrates. Significant CYP specific activity was also detected when naphthalene (3.80+/-0.002 U mg(-1)) was used as substrate. The CYP catalysis of n-hexadecane had followed both terminal and sub terminal oxidations. The activity was localized in the cytosol of n-hexadecane grown cells, while, it was apparently distributed in light mitochondrial fraction and microsomal fraction of glucose grown cells. The substrate specificities of CYP present in all the locations were similar irrespective of the substrates used for the growth. Heme staining of the microsomal fraction containing CYP and other proteins in SDS-PAGE showed single heme protein band with corresponding molecular weight of 110 kDa.

Abstract  Quantification of aspartic acid enantiomers in rat brain by using a chiral capillary electrophoresis procedure is described. Amino acids were pre-column derivatized with naphthalene-2,3-dialdehyde. Enantiomeric separation was achieved by micellar electrokinetic chromatography in the presence of methanol and beta-cyclodextrin as chiral selector. The chiral separation was coupled with laser-induced fluorescence detection. Contents of D- and L-aspartic acids in rats at different stages of growth (from 1 day before birth to 90 days after birth) were determined. D-Aspartic acid was detected in all the brain tissue samples tested, but at different levels. In the cerebrum of rats 1 day before birth, D-aspartic acid was found to be at the highest concentration of 81 nmol/g wet tissue. The level of D-aspartic acid in rat brain falls rapidly after birth, while the L-aspartic acid level increases with age.

Abstract  IPA COPYRIGHT: ASHP The synthesis of esters of 1-(dimethylamino)-1-indan methanols and 1,2,3,4-tetrahydro-1-naphthalene methanols and their pharmacological profile as antispasmodics, anti-ulcer drugs and local anesthetics are described.

Abstract  A method was developed for the quantification of 1-4 ring quinones in urine samples using liquid-liquid extraction followed by analysis with gas chromatography-mass spectrometry. Detection limits for the ten quinones analyzed are in the range 1-2 nmol dm(-3). The potential use of this approach to monitor urinary quinone levels was then evaluated in urine samples from both Sprague-Dawley rats and human subjects. Rats were exposed to 9,10-phenanthraquinone (PQ) by both injection and ingestion (mixed with solid food and dissolved in drinking water). Urinary levels of PQ were found to increase by up to a factor of ten compared to control samples, and the levels were found to depend on both the dose and duration of exposure. Samples were also collected and analyzed periodically from human subjects over the course of six months. Eight quinones were detected in the samples, with levels varying from below the detection limit up to 3 μmol dm(-3).

Abstract  We performed a cumulative risk assessment for people living in a hypothetical urban environment, called Urbania. The main aims of the study were to demonstrate how a cumulative risk assessment for a middle-sized European city can be performed and to identify the bottlenecks in terms of data availability and knowledge gaps. The assessment focused on five air pollutants (i.e., PM₁₀, benzene, toluene, nonane and naphthalene) and six food pesticides (i.e., acetamiprid, carbendazim, chlorpyrifos, diazinon, imidacloprid and permethrin). Exposure predictions showed that PM₁₀, benzene and naphthalene exposure frequently exceeded the standards, and that the indoor environment contributed more than the outdoor environment. Effect predictions showed that mixture and interaction effects were generally limited. However, model calculations indicated potential synergistic effects between naphthalene and benzene and between chlorpyrifos, diazinon and toluene. PM₁₀ dominated the health impact expressed in Disability Adjusted Life Years (DALYs). We conclude that measures to reduce the health impact of environmental pollution should focus on the improvement of indoor air quality and the reduction of PM₁₀ emissions. Cumulative risk assessment can be improved by (1) the development of person-oriented exposure models that can simulate the cumulative exposure history of individuals, (2) a better mechanistic understanding of the effects of cumulative stressors, and (3) the development of instruments to prioritize stressors for inclusion in cumulative risk assessments.