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Host-guest interaction between cyclen based macrotricyclic ligands and phosphate anions. A potentiometric investigation.

The host-guest interaction between orthophosphate, pyrophosphate and triphosphate anions and three cyclen based macrotricyclic ligands possessing ortho- (TOC), meta- (TMC) and para-xylenyl (TPC) linkers was investigated by potentiometric measurements. The ternary species present in solution and their stability constants have been determined. The different behaviours are explained in terms of hydrogen bond formation and coulombic attraction between the organic host and the inorganic guest. The selectivity, illustrated with species distribution diagrams, is discussed. The results unambiguously showed the importance of the distance between the two cyclen cores and emphasized the increasing of the triphosphate species selectivity together with the cavity size of the ligand. A comparison of the present results with those obtained with their mono-bridged homologues is also discussed.

Anions↗

Effects of inhaled municipal refuse incinerator fly ash in the guinea pig.

Fly ash was collected from two municipal refuse incinerators. It was analyzed for heavy metals, elements, and a wide range of toxic organics. It was resuspended in air for inhalation exposure of guinea pigs. These animals were exposed at high concentrations of each ash 6 h/d for 5 d, and tissues were taken 45 d after the exposure. Following the first exposure and after each daily exposure the ventilatory response of these animals upon challenge with CO2 was found to be depressed. Recovery occurred following exposure. Heavy metals, cadmium, lead, zinc, and mercury were elevated in the lungs of these animals. Histologic evaluation of pulmonary tissue revealed multifocal pneumoconiosis. Interstitial infiltration by macrophages and smooth muscle hypertrophy of blood vessels and bronchioles were also observed. There was no evidence of a dioxinlike toxic effect following inhalation of these ashes.

Air Pollutants↗

Pheromones.

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Acetates↗

Characterization of polycyclic aromatic hydrocarbons and carbonyl compounds in diesel exhaust emissions.

Exhaust emissions from a recent model heavy-duty diesel vehicle (city bus) in a chassis dynamometer were measured during a transient driving cycle. Particle-bound polycyclic aromatic hydrocarbons (PAHs) and gaseous carbonyls, substances that create health hazards and are, as yet, unregulated were collected, the former on filters and the latter on dinitrophenylhydrazine (DNPH)-coated silica cartridges and analysed by GC-MS and HPLC, respectively. PAH emission rates decreased with the number of benzene fused rings. They averaged 0.2 mg km(-1) for a total of 11 PAHs ranging from fluoranthene to benzo(ghi)perylene. Fluoranthene and pyrene accounted for 90% of total PAHs. The sum of emission rates of C1 approximately C6 carbonyls averaged 174 mg km(-1), even if formaldehyde alone represented approximately 70% of the total carbonyl mass, followed by acetaldehyde (13%). Results obtained were compared with emission data reported in previous studies.

Air Pollutants↗

Organic contaminants in direct coal liquefaction--a preliminary assessment.

Area samples taken at two coal liquefaction facilities were analyzed by either gas chromatography or gas chromatography/mass spectrometry to identify the types of organic contaminants to which workers may be exposed. Results indicate that the contaminants consisted primarily of one or two ring low-molecular weight aromatic compounds.

Coal↗

Aerosol-bound emissions of polycyclic aromatic hydrocarbons and sterols from aeration tanks of a municipal waste water treatment plant.

Aeration tanks of wastewater treatment plants (WWTP) are a potential source of atmospheric aerosol particles. Several groups of organic compounds (sterols, polycyclic aromatic hydrocarbons, estrogens) were analyzed in aerosol particles sampled at a municipal WWTP, and the particle size distribution was measured directly with optical particle counters. Aerosol emissions from an activated treatment tank equipped with fine bubble diffusers were low; however, at the preaeration tank equipped with coarse bubble diffusers, sterol concentrations up to 14 ng m(-3) were measured. Directly next to the tank, sterols were associated mainly to particles with aerodynamic diameter >1.35 microm. The results suggest that coprostanol could be a useful tracer for monitoring the emission of aerosol particles from WWTPs. Moreover, wastewater treatment could contribute substantially to the atmospheric concentrations of cholesterol and 24-ethylcholesterol. Aeration tanks with fine bubble diffusers are no major source of atmospheric aerosol particles, whereas coarse bubbling devices seem to emit considerable amounts of aerosol particles.

Aerosols↗

Assessment of bioavailability and effects of chemicals due to remediation actions with caging mussels (Anodonta anatina) at a creosote-contaminated lake sediment site.

A study was conducted at Lake Jämsänvesi in Central Finland, to identify the potential ecotoxicological risks of the remediation operation of a creosote-/PAH-contaminated lake sediment, made by capping during the years 1998-1999. Mussels (Anodonta anatina) were deployed to the lake at the same time as the remediation operation was started in November 1998. The contaminated area (0.5 ha) was covered by a filter geotextile (polypropylene), gravel and sand (1-1.5m) which were spread out on the ice and let to sink onto the bottom of the lake when the ice melted in May 1999. The possible impacts of capping to the adjacent environment were assessed from mussels exposed and particulate material settled (SPM) to collectors placed on the lake bottom. Mussel tissue, SPM, the water inside the collector were analyzed for polycyclic aromatic compounds (PAH)-compounds. Biological endpoints included body condition, glycogen and protein contents of adductor muscle. Mussels and SPM exposed downstream to the contaminated site (Site 3) contained the highest total PAH concentrations. Biota-sediment accumulation factors of acenaphthene, phenanthrene, anthracene, fluoranthene, pyrene and benzo(a)anthracene of mussels varied from 0.79 to 1.45. The glycogen and protein concentrations were lowest in adductor muscle from mussels exposed to conditions at Site 3. Concentrations of some PAH-compounds were found distinctly increased adjacent to the remediated area, possibly due to the agitation of contaminated sediment due to the capping. It is also possible that resuspension of sediment around remediated area (containing some PAHs) spread the deposited PAH-compounds.

Animals↗

Inactivation of the human papillomavirus-16 E6 oncoprotein by organic disulfides.

We are investigating compounds that could be useful in the treatment of neoplastic lesions of the cervix by acting on the oncoprotein E6 of human papillomavirus-16. The E6 protein contains two potential zinc-binding domains that are required for most of its functions. We have published tests that measure (i) the release of zinc ions after chemical alteration of the cysteine groups of these zinc-binding domains (TSQ assay), (ii) the interaction of E6 with the cellular proteins E6AP and E6BP (BIACORE assay), and (iii) the viability of tumor cell lines that require the continuous expression of HPV oncoproteins (WST1 assay). Based on these tests, we identified 4.4'-dithiodimorpholine as a potential lead compound. In this study we examined whether the dithiobisamine moiety of 4,4'-dithiodimorpholine may be an important molecular prerequisite for further drug development in this system. We have evaluated 59 new substances including organic disulfides and those containing the dithiobisamine moiety, as well as structural analogues. The compounds with significant reactivity in all three assays were observed only for dithiobisamine derivatives with saturated cyclic amines and aryl substituted piperazines. The identity of these substances suggests that the N-S-S-N moiety is necessary but not sufficient for reactivity in our assays, and that dithiobisamine based substances are useful as lead compounds that target the cysteine groups of HPV-16 E6 zinc fingers.

Antiviral Agents↗

Polypyrrole-coated capillary coupled to HPLC for in-tube solid-phase microextraction and analysis of aromatic compounds in aqueous samples.

In-tube solid-phase microextraction (SPME) based on a polypyrrole (PPY)-coated capillary was investigated for the extraction of aromatic compounds from aqueous solutions. The PPY-coated capillary was coupled on-line to HPLC that was programmed with an autosampler to achieve automated in-tube SPME and HPLC analysis. Three groups of aromatics, including both polar and nonpolar compounds, were examined. The results demonstrated that the PPY coating had a higher extraction efficiency than the currently used commercial capillary coatings, especially for polycyclic aromatic compounds and polar aromatics due to the increasing pi-pi interactions, interactions by polar functional groups, and hydrophobic interactions between the polymer and the analytes. In addition to the functional groups in the PPY coating, which contributed to the higher extraction efficiency and selectivity toward analytes, the coating's porous surface structure,which was revealed by electron microscopy experiments, provided a high surface area that allowed for high extraction efficiency. It was found that the extraction efficiency and selectivity could be tuned by changing the coating thickness. The preliminary study of the extraction mechanism indicated that analytes were extracted onto the PPY coating mainly by an adsorption mechanism. The method was used for the extraction and analysis of both polar and nonpolar aromatics in aqueous samples.

Journal Article↗

Comparative in vitro activities of retapamulin (SB-275833) against 141 clinical isolates of Propionibacterium spp., including 117 P. acnes isolates.

Using the NCCLS agar dilution method, we studied the in vitro activity of retapamulin (SB-275833) against 141 clinical isolates of Propionibacterium species, including seven multiresistant strains, and found retapamulin to be the most active agent among those tested with MICs of < or = 1 microg/ml against all isolates.

Anti-Bacterial Agents↗

Effects of Aconitum alkaloid kobusine and pseudokobusine derivatives on cutaneous blood flow in mice; II.

Aconitum alkaloids of the C20-diterpenoid type, kobusine (1) and pseudokobusine (2), their anisoyl, veratroyl, p-nitrobenzoyl, nicotinoyl or pivaloyl derivatives, and dehydrokobusine and N,6-seco-6-dehydropseudokobusine derivatives were examined for their peripheral vaso-activities by laser-flowmetrical measurement of the cutaneous blood flow in the hind foot of mice after intravenous administration. Kobusine 15-anisoate (4), 11-veratroate (5), 15-veratroate (6), 11-pivaloate (9) and 15-pivaloate (10) were significantly effective at a low dose of 0.5 or 0.05 mg/kg. Pseudokobusine derivatives were all active at 1, 0.5 or 0.05 mg/kg, and the effects of pseudokobusine 15-anisoate (13), 15-veratroate (16) and 15-p-nitrobenzoate (19) at 0.1 mg/kg were remarkable. Yesoline (26) and alkaloid (28) were significantly effective at a low dose of 1 mg/kg, whereas yesonine (25) and N-acetyl-N,6-seco-6-dehydropseudokobusine (27) were inactive. Dehydrokobusine derivatives (29, 30) were significantly effective at a low dose of 0.5 or 0.1 mg/kg. It is thought that the hydroxyl groups of alkaloids, especially a free OH group of 2 at C-6, are important for action on the peripheral vasculature leading to dilatation, and the results indicated that esterification of the hydroxyl group at C-15 with either anisoate, veratroate orp-nitrobenzoate may contribute to enhancement of the activity of the parent alkaloids.

Animals↗