Biomedical subjects

Heinrich Hühnerfuss

Publications and source records attributed to Heinrich Hühnerfuss.

10 recordsLinked to original sources

PubMed2007

Methylsulfonyl PCB and DDE metabolites and their enantioselective gas chromatographic separation in human adipose tissues, seal blubber and pelican muscle.

In the present investigation, eleven human adipose tissue samples, two seal blubber samples and two pelican muscles samples were analyzed with regard to their concentrations of PCB parent compounds as well as to the respective chiral methylsulfonyl metabolites 3-MeSO2-CB 91, 4-MeSO2-CB 91, 3-MeSO2-CB 95, 4-MeSO2-CB 95, 3-MeSO2-CB 149, 4-MeSO2-CB 149, 3-MeSO2-CB 132, 4-MeSO2-CB 132, 3-MeSO2-CB 174, and 4-MeSO2-CB 174 and the achiral metabolites 3-MeSO2-CB 49, 4-MeSO2-CB 49, 3-MeSO2-CB 101, 4-MeSO2-CB 101, 3-MeSO2-CB 110, 4-MeSO2-CB 110 and 3-MeSO2-DDE. In order to verify enantioselective transformation processes and to compare the different enzymatic transformation pathways in birds and mammals, the enantioselective excesses of the chiral PCB-metabolites were determined by enantioselective gas chromatography with electron capture and mass spectrometric detection using modified cyclodextrin phases, including heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl-)-beta-cyclodextrin/OV1701 (1:1) for the parent PCBs and heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl-)-beta-cyclodextrin/SE52 (1:4) for the metabolites, respectively.

Adipose Tissue↗

PubMed2005

Temporal trend of bis(4-chlorophenyl) sulfone, methylsulfonyl-DDE and -PCBs in Baltic guillemot (Uria aalge) egg 1971-2001--a comparison to 4,4'-DDE and PCB trends.

The dynamics of organohalogen contaminants and their metabolites are best studied over time by analysis of biota at high trophic levels. In this study, time trends, 1971-2001, of bis(4-chlorophenyl) sulfone (BCPS) and of methylsulfonyl-substituted metabolites of PCBs and 4,4'-DDE, were investigated in eggs of guillemot (Uria aalge) hatching in the Baltic Proper. Temporal trends of PCBs, trans-nonachlor, beta-HCH, 4,4'-DDT, and 4,4'-DDE were also assessed. Tris(4-chlorophenyl) methane (TCPMe), a 4,4'-DDT by-product, was detected in the eggs. The concentration of BCPS ranged between 2.6-0.76 microg/g on a lipid weight basis over the three decades and showed a significant 1.6% annual decrease. Three metabolites of PCBs, i.e. 3'-MeSO2-CB101, 4'-MeSO2-CB101 and 4-MeSO2-CB149, were quantified in all samples over time and showed an annual decrease of approximately 3% compared to MeSO2-DDE with a decrease of 8.9%. The methylsulfonyl-PCB and -DDE metabolites are eliminated more slowly than the persistent PCB congeners and 4,4'-DDE. Trans-nonachlor decreases by 16% compared to 19% and 9% for 4,4'-DDT and beta-HCH, respectively. The concentration of TCPMe in guillemot decreased by 8.2% per year. A linear relationship was found between TCPMe and 4,4'-DDE concentrations which supports the theory that TCPMe has an origin as a contaminant in commercial 4,4'-DDT products. The very slow decrease in BCPS concentrations is notable and remains to be explained. BCPS is still present at rather high concentrations in the guillemot eggs. The enantiomeric fraction varied between 0.27 and 0.67 which indicates less of a specific retention of the chiral MeSO2-PCBs in guillemot eggs than in grey seal tissues, for example. Independent of meta- or para-substitution of the sulfone group, the most accumulative atropisomer of each of four MeSO2-PCB pairs has been assigned an absolute R structure.

Animals↗

PubMed2005

Enantioselective semipreparative HPLC separation of PCB metabolites and their absolute structure elucidation using electronic and vibrational circular dichroism.

Polychlorinated biphenyls (PCBs) remain one of the most important groups of environmental contaminants. The fate (transformation) as well as the toxicological implications of the different metabolism steps are subject to considerable debate. The aim of this study is to start a comprehensive investigation of atropisomeric PCB metabolites, i.e., hydroxy, methoxy, methylthionyl, and methylsulfonyl PCBs in different biota. For this purpose, enantioselective semipreparative liquid chromatography is used to obtain pure enantiomers of PCB metabolites. Electronic circular dichroism (UV-CD) and vibrational circular dichroism (VCD) in combination with computational techniques were applied to determine their absolute structures. Approximately 18-25 mg of each enantiomer of the following metabolites were obtained using semipreparative HPLC on beta-cyclodextrin-based columns: 4-MeO-CB149, 4-MeS-CB149, 4-MeSO2-CB149, 3-MeS-CB149, and 3-MeSO2-CB149. The enantiomeric purity of the separated enantiomers was in the range of 95.0-99.9%. Rotational angles and absolute configurations were also determined. This study establishes a sound method for future preparation and absolute structure determination of compounds belonging to the same class.

Chromatography↗

PubMed2005

Appearance and disappearance of dendritic and chiral patterns in domains of Langmuir monolayers observed with Brewster angle microscopy.

Investigations on the aggregation behavior and morphology of Langmuir films of enantiomeric (L) and racemic (DL) N-acyl amino acids on pure aqueous as well as metal cation containing subphases were carried out at the mesoscale level with the help of Brewster angle microscopy (BAM). In the case of N-hexadecanoyl alanine on a pure aqueous subphase at 298 K the L-enantiomer forms crystal platelets, while the irregular fractal-like shape of the domains of the racemic mixture can be explained by a diffusion limited aggregation (DLA) growth mechanism. At 303 K the L-enantiomer shows a dendritic growth pattern, which leads to explicitly chiral domain shapes that correspond with the chirality of the film-forming molecules and for which hydrogen bridges as directed attractive forces are assumed to be responsible. The compression of the L-enantiomer on a zinc ion containing subphase is accompanied by a remarkable metamorphosis of the condensed structure. Starting from torus-like domains they were at first converted into strongly wound S-shaped domains, finally turning into a seahorse-like appearance. The origin of these chiral shapes can be explained on the basis of an electrostatic growth model. The enantiomer of N-hexadecanoyl alanine methyl ester shows three different asymmetric dendritic growth patterns. The domains of the racemic mixture are dendritic too, but in contrast they are symmetric and have a notably low branching density. On a pure aqueous subphase the L-enantiomer of N-octadecanoyl valine exhibits dendritic growth as well, but the overall outer shape of the domains is not explicitly chiral.

Alanine↗

PubMed2004

Identification and quantification of pesticides, industrial chemicals, and organobromine compounds of medium to high polarity in the North Sea.

Solid-phase extraction of 20 L seawater samples enabled the enrichment and determination of a wide array of organic substances, including compounds of medium to high polarity, in the pg/L-range. A number of contaminants was detected and quantified throughout the North Sea, among them the pesticides dichlobenil (2,6-dichlorobenzonitrile), metolachlor and terbuthylazine as well as the industrial chemicals dichloropyridines (DCPy, 4 isomers) and nitrobenzene. Concentrations attained values up to 1.4 ng/L for dichlobenil, 0.83 ng/L for terbuthylazine, 0.61 ng/L for metolachlor, 0.13 ng/L for 2,6-DCPy, 4.37 ng/L for nitrobenzene and 1-8 ng/L for tris(chloropropyl)phosphates (TCPP). A number of North Sea water samples was screened for non-target compounds, revealing the presence of further contaminants, e.g., lindane and TCPP, as well as several biogenic and/or anthropogenic organobromine substances, among which bromoindols, -phenols and -anisoles were identified.

Bromine Compounds↗

PubMed2004

Simultaneous solid-phase extraction of acidic, neutral and basic pharmaceuticals from aqueous samples at ambient (neutral) pH and their determination by gas chromatography-mass spectrometry.

Seven polymeric solid-phase extraction (SPE) sorbents were evaluated with regard to their ability to extract acidic, neutral and basic pharmaceuticals and estrogens simultaneously from water at neutral pH. Highest recoveries (70-100%) for the majority of the analytes were obtained with styrene-methacrylate and styrene-N-vinylpyrrolidone co-polymers. The latter one (Oasis HLB) was chosen for further refinement of an extraction method for the quantitative determination of acidic and neutral drugs in surface water samples at detection limits below 1 ng/l. A sequential elution protocol was applied for clean-up and separation of the extracted analytes into fractions suitable for further compound specific processing. The neutral analytes as well as the acidic compounds after derivatisation were quantified by GC-MS. Caffeine, ibuprofen, its metabolites and diclofenac were detected in river water samples in the 1-100 ng/l range.

Chromatography, High Pressure Liquid↗

PubMed2004

Determination of selected pharmaceuticals and caffeine in sewage and seawater from Tromsø/Norway with emphasis on ibuprofen and its metabolites.

Selected pharmaceuticals, among them analgesics, ss-blockers and anti-depressants as well as caffeine, the anti-bacterial triclosan and the insect repellent N,N-diethyl-3-toluamide (DEET) were determined in different sewage samples (sewage treatment plants, hospital effluents) from Tromsø/Norway and in seawater from Tromsø-Sound, into which the sewage is discharged. While caffeine, triclosan, ibuprofen and its major metabolites hydroxy- and carboxy-ibuprofen were present in all sewage samples, additional pharmaceuticals were observed in sewage containing hospital effluents. Concentrations were in the range of 20-293 microg/l (caffeine), 0.2-2.4 microg/l (triclosan) and 0.1-20 microg/l (sum ibuprofen + metabolites). In seawater, only caffeine (7-87 ng/l), DEET (0.4-13 ng/l) and ibuprofen + metabolites (sum concentration < LOQ-7.7 ng/l) were detected. Ibuprofen and its metabolites hydroxy- and carboxy-ibuprofen were quantified individually by use of the respective reference compounds. Relative amounts of the three compounds were determined in different types of water showing characteristic patterns, with hydroxy-ibuprofen being the major component in sewage whereas carboxy-ibuprofen was dominant in seawater samples. The patterns which were compared to those observed in similar samples from Germany indicated different transformation behaviour under limnic and marine conditions.

Caffeine↗

PubMed2004

Genotoxic and teratogenic potential of marine sediment extracts investigated with comet assay and zebrafish test.

Organic extracts of marine sediments from the North Sea and the Baltic Sea were investigated with two toxicity assays. The comet assay based on the fish cell line Epithelioma papulosum cyprini (EPC) was applied to determine the genotoxic potential; zebrafish embryos (Danio rerio) were used to quantify the teratogenic potential of the samples. EC(50) values were calculated from dose-response curves for both test systems. Highest teratogenic and genotoxic effects normalised to total organic carbon (TOC) content were detected in sediment samples of different origins. Polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) are not likely to be the causes of the observed effects, as demonstrated by a two-step fractionation procedure of selected extracts. The toxic potential was more pronounced in fractions having polarity higher than those possessed by PAHs and PCBs. The suitability of the two in vitro test systems for assessing genotoxic and teratogenic effects of marine sediment extracts could be demonstrated.

Animals↗

PubMed2002

Drugs and personal care products as ubiquitous pollutants: occurrence and distribution of clofibric acid, caffeine and DEET in the North Sea.

An analytical method is presented, which allows the simultaneous extraction of neutral and acidic compounds from 20-L seawater samples at ambient pH (approximately 8.3). It is based on a solid-phase extraction by means of a polystyrene-divinylbenzene sorbent and gas chromatographic-mass spectrometric detection, and provides detection limits in the lower pg/L range. The method was applied to the screening of samples from different North Sea areas for clofibric acid, diclofenac, ibuprofen, ketoprofen, propyphenazone, caffeine and N,N-diethyl-3-toluamide (DEET). Whereas clofibric acid, caffeine and DEET showed to be present throughout the North Sea in concentrations of up to 1.3, 16 and 1.1 ng/L, respectively, propyphenazone could only be detected after further clean-up. Diclofenac and ibuprofen were found in the estuary of the river Elbe (6.2 and 0.6 ng/L, respectively) but in none of the marine samples. Ketoprofen was below the detection limit in all samples.

Caffeine↗

PubMed2002

Chiral PCB methyl sulfones in rat tissues after exposure to technical PCBs.

PCB methyl sulfones (MeSO2-PCBs) are lipophilic PCB metabolites known to exhibit selective tissue retention properties in wildlife and humans. The aim of this study was to investigate the presence of atropisomers of MeSO2-PCB congeners in tissues of rats exposed to a technical PCB product, Clophen A50. Changes in the enantiomer fractions (EFs) of the MeSO2-PCB atropisomers after exposure were also determined. Liver, lung, and adipose tissue from rats dosed with Clophen A50 were analyzed for the MeSO2-PCB atropisomers of 3-methylsulfonyl-2,2',4',5,6-pentachlorobiphenyl (5-MeSO2-CB91), 4-methylsulfonyl-2,2',3,4',6-pentachlorobiphenyl (4-MeSO2-CB91), 3-methylsulfonyl-2,2',3',4',5,6-hexachlorobiphenyl (5'-MeSO2-CB132), 4-methylsulfonyl-2,2',3,3',4',6-hexachlorobiphenyl (4'-MeSO2-CB132), 3-methylsulfonyl-2,2',4',5,5',6-hexachlorobiphenyl (5-MeSO2-CB149), and 4-methylsulfonyl-2,2',3,4',5',6-hexachlorobiphenyl (4-MeSO2-CB149). In all tissues analyzed, especially lung, the para-MeSO2-PCBs were more abundant than the meta-MeSO2-PCBs. The concentration ratio was higher for 4-MeSO2-CB149 versus 5-MeSO2-CB149 than for the corresponding ratio 4-/5-MeSO2-CB91 and 4'-/5'-MeSO2-CB132. Enantioselective MeSO2-PCB analysis of the lung samples showed an excess and dominance of the second eluting atropisomer of 4-MeSO2-CB149. In both lung and adipose tissues, small amounts of the first eluting atropisomer of 5-MeSO2-CB149 was present, but this atropisomer was not detected in the liver. No significant time-dependent changes in the EFs of 4-MeSO2-CB91, 5'-MeSO2-CB132, 4'-MeSO2-CB132, 5-MeSO2-CB149, and 4-MeSO2-CB149 atropisomers were found for either lung, liver, or adipose tissue. The results of the present study suggest that enantioselective formation occur for both meta- and para-MeSO2-PCBs.

Adipose Tissue↗