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Biomedical subjects

A Kettrup

Publications and source records attributed to A Kettrup.

At least 19 recordsLinked to original sources

Effects of a branched p-nonylphenol isomer (4(3',6'-dimethyl-3'-heptyl)-phenol) on embryogenesis in Lymnae stagnalis L.

The tertiary branched alkyl-chain isomers of p-nonylphenol (NP) are perceived to have more estrogenic potency than its constituent secondary and primary straight alkyl-chain isomers. Investigations with single tertiary branched isomers of NP can therefore contribute toward the elucidation of the mechanisms of toxicity and estrogenicity of NP. A single tertiary branched alkyl-chain isomer (4(3',6'-dimethyl-3'-heptyl)-phenol) was used in studies to determine its effects on embryonic growth and mortality in Lymnaea stagnalis L. Egg masses were exposed to the test compound for 20 days in a static waterborne-exposure regime with an average NP concentration of 105 microg/L and water temperature range of 18-20 degrees C. Observations were made under a microscope and pictures were taken with a digital camera to determine the various developmental stages of growth, the duration of growth in each stage, embryo hatchability, and embryo mortality. The isomer was found to cause significant delay in all stages of growth and more significantly in the Morula and Veliger stages. An increase in embryo mortality, from the third day until the end of the experiment, was observed in exposed egg masses compared to controls. The hatching success of embryos was also significantly reduced by exposure, with 81% hatchability in exposed egg masses compared to 93% in the controls, after 18 days of continuous exposure. The encapsulating jelly strand that completely covers the rows of egg masses may have prevented the isomer residues from effectively penetrating into the embryos as shown by the observed low bioconcentration factors of the isomer in egg masses during exposure, resulting in unexpectedly lower observed estrogenic effects. However, this factor was not investigated. In vivo biotransformation of some of the residues of the isomer into catechol metabolites by the embryos during exposure could also result in the reduction of its estrogenic potential. To understand more fully the extent of toxicity and estrogenicity of this isomer, in vitro estrogenic assays are recommended. It would also be necessary to investigate its estrogenic effects on embryo development after in vivo maternal exposure.

Animals↗

Detection of royal jelly adulteration using carbon and nitrogen stable isotope ratio analysis.

Stable isotope ratios ((13)C/(12)C and (15)N/(14)N) were measured in royal jelly (RJ) samples by isotope ratio mass spectrometry (IRMS) to evaluate authenticity and adulteration. Carbon and nitrogen isotope contents (given as delta values relative to a standard, delta(13)C, delta(15)N) of RJ samples from various European origins and samples from commercial sources were analyzed. Uniform delta(13)C values from -26.7 to -24.9 per thousand were observed for authentic RJ from European origins. Values of delta(15)N ranged from -1.1 to 5.8 per thousand depending on the plant sources of nectars and pollen. High delta(13)C values of several commercial RJ samples from -20.8 to -13.3 per thousand indicated adulteration with high fructose corn syrup (HFCS) as a sugar source. Use of biotechnologically produced yeast powder as protein source for the adulterated samples was assumed as delta(15)N values were lower, as described for C(4) or CAM plant sources. RJ samples from authentic and from adulterated production were distinguished. The rapid and reliable method is suitable for urgent actual requirements in food monitoring.

Animals↗

Oxidant denuder sampling for analysis of polycyclic aromatic hydrocarbons and their oxygenated derivates in ambient aerosol: evaluation of sampling artefact.

The concentrations of some polycyclic aromatic hydrocarbons (PAH) and oxygenated PAH (O-PAH) can be changed by oxidation reactions during sampling. This can lead to an over- or underestimation of the corresponding adverse health effects. The aim of this study was the evaluation of these sampling artefacts. The potential of using an oxidant denuder was shown by parallel low-volume sampling with and without MnO(2) ozone denuder. Twenty-three PAH and 11 O-PAH in ambient air were analysed, both in the vapour and particulate phase. The denuder was proven to be highly efficient for stripping ozone from air while causing no significant particle losses. In general, the concentrations of 5- to 7-ring PAH, which are predominantly associated with particles, were underestimated in non-denuded samples. The highest losses due to reaction with ozone and other atmospheric oxidants were observed for benzo[a]pyrene and perylene. Concurrently, the concentrations of most of the mainly particle-associated 4- to 5-ring O-PAH were higher in the non-denuded samples. The denuder did not only remove ozone, moreover other gaseous species such as more volatile PAH and O-PAH were partially oxidized on the catalytic surface, too. Degradation of PAH and concurrent degradation/formation reactions of O-PAH occurred. The corresponding reactivities of selected PAH and O-PAH are discussed.

Air Pollutants↗

Predicting gas chromatographic retention times of 209 polybrominated diphenyls (PBBs) for different temperature programs.

A method has been developed to predict the retention times of 209 individual polybrominated diphenyl congeners for different temperature programs. The retention equations lnk'=A+B/T of five PBBs in gas chromatography (GC) were used to evaluate the properties of the regression coefficients A and B, which are widely accepted as being highly reliable chromatographic retentions. The quantitative relationships between the A and B values of PCBs and those of PBBs were found. The regression equations derived have coefficients of determination greater than 0.999. The A, B values of any PBB can be predicted by using the A, B values of the PCB according to these relationships. Using these predicted A and B values, the retention times of all PBBs can be predicted. This is an important advance in the identification of PBBs because at present there are only a few PBB standards available.

Chromatography, Gas↗

Suppressive effects of caraway (Carum carvi) extracts on 2, 3, 7, 8-tetrachloro-dibenzo-p-dioxin-dependent gene expression of cytochrome P450 1A1 in the rat H4IIE cells.

Cytochrome P450 1A1 (CYP1A1) is among the cytochrome P450 classes known to convert xenobiotics and endogenous compounds to toxic and/or carcinogenic metabolites. Suppression of CYP1A1 over expression by certain compounds is implicated in prevention of cancer caused by chemical carcinogens. Chemopreventive agents containing high levels of flavonoids and steroids-like compounds are known to suppress CYP1A1. This study was carried out for assessment of the genomic and proteomic effects of caraway (Carum carvi) extracts containing high levels of both flavonoids and steroid-like substances on ethoxy resorufin dealkylation (EROD) activity and CYP1A1 at mRNA levels. Rat hepatoma cells co-treated with a CYP1A1 inducer i.e. TCDD (2, 3, 7, 8-tetrachlorodibenzo-p-dioxin) and different preparations of caraway extracts at concentrations of 0, 0.13, 1.3, and 13 microM in culture medium. After incubation (37 degrees C and 7% CO2 for 20 h), changes in EROD specific activity recorded and compared in cells under different treatments. The results show that caraway seed extract prepared in three different organic solvents suppressed the enzyme activity in hepatoma cells in a dose-dependent manner. The extracts added above 0.13 microM could significantly inhibit EROD activity and higher levels of each extract (1.3 and 13 microM) caused approximately 10-fold suppression in the enzyme activity. Accordingly, data obtained from the RT-PCR (TaqMan) clearly showed the suppressive effects of plant extract on CYP1A1-related mRNA expression. These data clearly show that substances in caraway seeds extractable in organic solvents can potentially reverse the TCDD-dependent induction in cytochrome P450 1A1.

Animals↗

LC-MS/MS method for the confirmatory determination of aromatic amines and its application in textile analysis.

A confirmation method for the determination of 18 aromatic amines originating from azo dyes after reductive cleavage was developed. The method is based on the use of high-performance liquid chromatography/tandem mass spectrometry with atmospheric-pressure chemical ionization. For the identification of the analytes one precursor ion and two daughter ions (multi-reaction monitoring, MRM) were selected and the LC-MS/MS parameters optimized to obtain high sensitivity and selectivity. The linear ranges varied from 0.1-1 to 30-50 microg mL(-1) with correlation coefficients of 0.99 or better. The applicability of the method to determine o-tolidine (3,3'-dimethylbenzidine) and 3,3'-dimethoxybenzidine in textiles following reductive cleavage of acid red 114, trypan blue, and Chicago sky blue 6B was demonstrated.

Journal Article↗

MMSPE-RP-HPLC method for the simultaneous determination of methimazole and selected metabolites in fish homogenates.

A simple and rapid high-performance liquid chromatography method with ultraviolet detection was developed for the determination of the thyreostatic compound methimazole (1-methyl-2-mercaptoimidazole, MET) and metabolites 2-mercaptoimidazol (SHMET), N-methylthiourea (MTU) and N-methylhydantoin (MEH) from zebrafish (D. rerio) whole body homogenates using mixed mode solid phase extraction technique for sample pre-treatment. The highly polar compounds were separated on a difunctionally bonded silica based reverse phase column using gradient elution. Retention factors ranged between 1.53 and 5.66. The method was linear between 0.1 and 30 microg/ml, the detection limits were 0.4 ng for MET and SHMET, 0.6 ng for MTU and 2.6 ng for MEH. Extraction method was exhibited average recovery rates of 85.2-97.6%.

Animals↗

A potentiometric and 113Cd NMR study of cadmium complexation by natural organic matter at two different magnetic field strengths.

The binding of cadmium to Suwannee River natural organic matter (NOM) has been investigated across a broad range of Cd/C ratios (0.00056-0.0056) and pH values (3.5-11) by (113)Cd NMR spectroscopy at two magnetic field strengths (B(0) = 9.4 and 11.7 T). Caused by the very peculiar and highly complex nature of the Cd-NOM exchanging system, these (113)Cd NMR spectra are characterized by a pH- and concentration-dependent superposition of slow, intermediate, and fast chemical exchange. The complex interplay of solution chemistry and chemical exchange requires a thorough mapping of this Cd-NOM chemically exchanging system through NMR acquisition at two magnetic field strengths and a systematic variation of Cd/C ratios and pH values. The interpretation of (113)Cd NMR spectra is greatly facilitated and constrained by simultaneous measurements of pH and pCd, which allows a model-independent calculation of organically bound Cd(2+) under all experimental conditions. Within the range of chemical conditions applied in this study, (113)Cd NMR spectrometric evidence is consistent with coordination of cadmium by oxygen, nitrogen, and sulfur ligands in NOM. Under all experimental conditions, cadmium is primarily coordinated to oxygen; however, several lines of evidence point to the participation of nitrogen ligands, even in acidic solutions where nitrogen ligands are primarily bound to protons. Under alkaline conditions, up to one-third of cadmium may be coordinated to nitrogen, and a small, but unquantifiable, percentage of cadmium is coordinated to sulfur ligands, as evidenced by far-low-field (113)Cd NMR resonances.

Journal Article↗

Resonance-enhanced multiphoton ionization and VUV-single photon ionization as soft and selective laser ionization methods for on-line time-of-flight mass spectrometry: investigation of the pyrolysis of typical organic contaminants in the steel recycling process.

A newly conceived compact and mobile time-of flight mass spectrometer (TOFMS) for real-time monitoring of highly complex gas mixtures is presented. The device utilizes two selective and sensitive soft ionization techniques, viz., resonance-enhanced multiphoton ionization (REMPI) and single-photon ionization (SPI) in a (quasi)-simultaneous mode. Both methods allow a fragmentationless ionization. The REMPI method selectively addresses aromatic species, while with SPI applying vacuum ultaviolet light (118 nm) in principle all compounds with an ionization potential below 10.5 eV are accessible. This provides comprehensive information of the chemical composition of complex matrixes. The combustion and pyrolysis behavior of five organic materials typically used in steel processing in China was studied. The trace amounts of organic compounds in the gas phase during combustion and pyrolysis were monitored selectively and sensitively by real-time SPI/REMPI-TOFMS. The measurements were carried out at several constant temperatures in the range from 300 to 1190 degrees C in both synthetic air and nitrogen. Timely resolved mass spectra reveal the formation and subsequent growth of aromatic molecules. At lower temperatures, highly alkylated PAHs predominate, while at temperatures above 800 degrees C, the more stable benzene and PAHs without side chains prevail. Potential hyphenation of SPI/REMPI-TOFMS to methods of thermal analysis is discussed.

Journal Article↗

Speciation of Pt(II) and Pt(IV) in spiked extracts from road dust using on-line liquid chromatography-inductively coupled plasma mass spectrometry.

The emission of platinum from automobile catalytic exhaust converters is well known and the accumulation of Pt in road dust has been studied by the analysis of total Pt contents. However, there are few studies on the speciation of the emitted Pt-compounds in the environment. A separation method with HPLC-UV has been developed by Nachtigall et al. [Chromatogr. A 775 (1997) 197] with aqueous standards of Pt(II)- and Pt(IV)-chloro complexes. Due to the limited selectivity and sensitivity of the UV-detection this method is not suitable for Pt-speciation in road dust extracts. Therefore, in this study the method of Nachtigall et al. was modified to realize an on-line coupling to ICP-MS with the advantage of Pt-specific detection. Calibration was performed with aqueous standards and spiked road dust extracts. Calibration curves were linear with low residual standard deviation (1.3-3.1% for the aqueous standards) and approximately 10-times lower detection limits compared to the HPLC-UV-method. Moreover, the stability of the model species was investigated using isocratic as well as gradient separation. Isotopic ratios of 194Pt, 195Pt, 196Pt and 198Pt were determined for quality control. A new mathematical correction method for the HfO-interference on the 195Pt-signal was developed. Additionally, the elution pattern of further elements in the road dust extracts was monitored and total element contents were determined in unspiked road dust extracts.

Calibration↗

QSPR models for physicochemical properties of polychlorinated diphenyl ethers.

Partial least squares regression together with 17 theoretical molecular structural descriptors was successfully used to develop QSPR models on sub-cooled liquid vapor pressures (P(L)), n-octanol/water partition coefficients (K(OW)) and sub-cooled liquid water solubilities (S(W,L)) of polychlorinated diphenyl ethers (PCDEs). Only a few theoretical molecular descriptors were included in the QSPR models, including average molecular polarizability, molecular weight, total energy and standard heat of formation, which implies that intermolecular dispersive forces play an important role in governing the magnitude of P(L) and K(OW). The models were tested as acceptable for prediction of P(L) and K(OW) by validation set. The consistency between observed and predicted values for P(L) is the best, followed by K(OW) and S(W,L). The Q(2)(cum) values of the PLS models obtained are higher than 0.95, indicating high robustness of the models. Since P(L), K(OW) and S(W,L) values for many PCDE congeners are not available, the developed models can be used for estimation.

Halogenated Diphenyl Ethers↗

In vivo metabolism and organ distribution of a branched 14C-nonylphenol isomer in pond snails, Lymnaea stagnalis L.

The branched isomers of p-nonylphenol (NP) are perceived to be more resistant to biodegradation in aquatic environments as well as to have more estrogen-like toxicity than the straight chain isomers. By use of GC-MS, some of them have been identified and found to exist in higher concentrations in the isomeric compound mixture than the straight chain isomers. The investigations of the distribution and metabolism of these branched isomers in aquatic organisms are therefore considered to be important in understanding the mechanisms of toxicity of NP. A single tertiary isomer of NP, 4(3'-,6'-dimethyl-3'-heptyl)-phenol, was synthesized in the laboratory and used in in vivo studies of its organ distribution and metabolism in Lymnaea stagnalis L., following a constant exposure of the organisms to 14C-NP isomer in water over a period of 8 days at an average exposure concentration of 105 ppb (range: 93-116 ppb). The results obtained clearly showed the distribution and bioconcentration of the isomer residues in various internal organs of Lymnaea after uptake in water and food. Analysis of the extracts of the organ tissues and faeces by HPLC and GC-MS after digestion with Pankreatin/beta-glucuronidase and nitric acid, respectively, showed that the isomer was metabolized by conjugation to glucuronic acid and hydroxylation to a catechol. The findings from these studies and their implications in the biotransformation and estrogenicity of NP in Lymnaea stagnalis L. are further discussed in detail in this paper.

Animals↗

Photodegradation of PCDD/Fs adsorbed on spruce (Picea abies (L.) Karst.) needles under sunlight irradiation.

Spruce (Picea abies (L.) Karst.) needles were exposed to exhaust gas containing polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) generated by combustion of polyvinyl chloride, wood, high-density polyethylene, and styrene. Photodegradation of PCDD/Fs adsorbed on spruce needles under sunlight irradiation was studied. The photodegradation of PCDD/Fs follows pseudo-first-order reaction kinetics, with photolysis half-lives ranging between 40 and 100 h. The photolysis rates of PCDF congeners are higher than PCDD congeners with the same chlorinated substitutions. Higher chlorinated PCDD/Fs tend to photolyze slowly. The wax components in spruce needles may act as proton donors and accelerate the photolysis rate. C-Cl cleavage through the addition of protons to PCDD/F molecules may be an important route for PCDD/Fs photodegradation.

Adsorption↗

Quantitative predictive models for octanol-air partition coefficients of polybrominated diphenyl ethers at different temperatures.

Quantitative predictive models for octanol-air partition coefficients of polybrominated diphenyl ethers at different environmental temperatures (T) were developed. Partial least squares (PLS) regression was used for model development. A list of 18 theoretical molecular structural descriptors was screened by PLS analysis. The optimal model was selected from the one containing nine theoretical molecular descriptors and 1/T as predictor variables. The cross-validated Q(2)(cum) value for the optimal model is 0.975, indicating a good predictive ability and stability of the model. Intermolecular dispersive interactions play a leading role in governing the magnitude of logK(OA). The lower the E(LUMO) (the energy of the lowest unoccupied molecular orbital), the greater the intermolecular interactions between octanol and PCB molecules, and thus the greater the logK(OA) values.

Environmental Pollutants↗

Ecotoxicological and chemical characterization of selected treatment process effluents of municipal sewage treatment plant.

The triolein-containing semipermeable membrane devices (SPMDs) were deployed for 4 weeks in a sewage treatment plant in Beijing, China, to sample and concentrate priority hydrophobic organic pollutants in a sewage treatment process. The chemical analyses and ecotoxicities of the residuals of SPMDs dialysate were examined. The data from the chemical analyses by gas chromatography-mass spectrometry selected ion monitoring mode indicated the lower removal for polychlorinated biphenyls (PCB) congeners and polycyclic aromatic hydrocarbons (PAHs) coincided with the persistence of them in the environment. The acute toxicity examined by bioluminescence test with Vibrio fischeri revealed approximately only 20% decrease in the overall toxicity of the influent after the activate sludge treatment process. The ethoxy resorufin-O-deethylase (EROD) induction with a micro-EROD assay in vitro using H4-IIE rat hepatoma cell cultures demonstrated the presence of persistent organics in influent and sequency effluents. Results obtained suggested that integration of the SPMD technique and chemical analyses and bioassay might be a valuable approach for the risk assessment of hydrophobic organic pollutants in water ecosystem. It revealed the necessity for organic pollutants monitoring and ecotoxicities examining of sewage treatment plants.

Animals↗

The dissipation, distribution and fate of a branched 14C-nonylphenol isomer in lake water/sediment systems.

A single tertiary isomer which is believed to be one of the major branched isomers of the isomeric nonylphenol was synthesized for use in investigations on its metabolism and estrogenicity in aquatic organisms. The physico-chemical properties of the isomer were determined to enable the prediction of its behaviour in aquatic environments. From laboratory investigations on its dissipation and distribution in lake water, which are reported in this paper, it was found that it had a half-life of dissipation of 38.1 days and 20.1 days in an open lake water and in an open lake water/ sediment system, respectively, and to be rapidly partitioned in to sediment giving a high concentration factor of 1.76 after 28 days with an initial dose concentration of 2.52 ppm. The main dissipation route was found to occur through volatilization and co-distillation. The isomer was, however, found to be resistant to biodegradation in both the lake water and sediment, showing only a slight 9% loss (after 56 days) and 4.2% loss (after 28 days), of the 14C-residues in lake water and lake water/sediment systems, respectively, by microbial activity. Transformation to other more polar metabolites possibly by hydroxylation was also found to be minimal in both lake water and sediment samples after 14 days by HPLC analysis. After 7 days, only 2.25 and 7.4% transformation to a more polar metabolite was detected in lake water and sediment samples, respectively.

Biodegradation, Environmental↗

Quantitative relationships between molecular structures, environmental temperatures and octanol-air partition coefficients of polychlorinated biphenyls.

A quantitative model that incorporates information on both environmental temperatures (T) and molecular structures, for logarithm of octanol-air partition coefficient to base 10 (logK(OA)) of polychlorinated biphenyls (PCBs) was developed. Partial least squares (PLS) analysis together with 16 theoretical molecular structural descriptors was used to develop the Quantitative relationships between structures, environmental temperatures and properties (QRSETP) model. The cross-validated Q(cum)(2) value for the optimal QRSETP model is 0.976, indicating a good predictive ability for logK(OA) of PCBs at different environmental temperatures. T, E(LUMO) (the energy of the lowest unoccupied molecular orbital), molecular size or average molecular polarizability (alpha), and the net atomic charges on chlorine, hydrogen and carbon atoms of PCB molecules, are major factors governing logK(OA). The lower the E(LUMO), the greater the intermolecular interactions between octanol and PCB molecules, and thus the greater the logK(OA) values. Because of intermolecular dispersive forces, the more chlorine atoms in PCB molecules, the greater the molecular size or alpha, the greater the logK(OA). The largest negative net atomic charge on a carbon atom (q(C)(-)) and molecular size or average molecular polarizability (alpha) are major factors governing temperature dependence of logK(OA). PCB molecules with low q(C)(-) values and more chlorines (big size or alpha) tend to have strong temperature dependence, due to intermolecular electrostatic interactions and dispersive forces, respectively.

Journal Article↗

Quantitative structure-property relationships for vapor pressures of polybrominated diphenyl ethers.

Based on quantum chemical descriptors, by the use of partial least squares regression, quantitative structure-property relationship models for subcooled liquid vapor pressures (PL) of polybrominated diphenyl ether (PBDE) congeners were developed. The Q2cum value of the optimal model obtained is as high as 0.993, indicating a good predictive ability and robustness of the model. Although disagreements were observed between the predicted log PL values and log PL values of validation set, the model obtained can still be used for estimating PL of other PBDE congeners, considering the fact that accurate PL values for compounds with low volatility are extremely difficult to determine experimentally. Intermolecular dispersive interactions play a leading role in governing the values of PL, followed by electrostatic, dipole-dipole and dipole-induced dipole interactions. Intermolecular dispersive interactions also govern the values of enthalpies of vaporization.

Chemical Phenomena↗