Bis 4-chlorophenyl Sulfone Research Articles

Bis(4-chlorophenyl) sulfone (BCPS) concentrations found in Austrian freshwater fish and cormorants (Phalacrocorax carbo sinensis) indicating trophic transport and biomagnification – A screening pilot-study

Bis(4-chlorophenyl) sulfone (BCPS, CAS No. 80-07-9) is used as monomer for the production of several groups of polymers like polysulphones and polyethersulphones. Residual amounts of monomer remain in the polymer matrix and might migrate out from the polymer matrix. In the present study, freshwater fish and fish-eating birds were examined. Following fish species (top predators) were collected at two Austrian locations: Sander lucioperca, Silurus glanis, and Lota lota. Whole fish samples were analysed for BCPS. Levels in freshwater fish ranged between 1.3 and 9.3 ng/g fat. In addition, breast muscle and liver samples from six cormorants (Phalacrocorax carbo sinensis) were investigated. BCPS levels in cormorants breast muscle were in the range of 4.3–40 ng/g fat (mean: 16.3 ng/g fat, n = 6) and 28–86 ng/g fat (mean: 53.5 ng/g fat, n = 6) in the liver samples. BCPS concentration in liver was 3.3-fold higher than in muscle tissue. One of the cormorants had ingested fish with a BCPS level of 5.5 ng/g fat; BCPS levels in the cormorant were 23 ng/g fat (breast muscle) and 28 ng/g fat (liver), suggesting biomagnification values (BMF) of 4.2 (fish/breast muscle) and 5.1 (fish/liver), respectively. A BMF value higher than 1 can be considered as an indication for very high biomagnification. Comparing the BCPS concentrations of cormorants’ breast muscle from 2019 (mean: 16 ng/g fat) to the concentrations from 2001 to 2005 (mean: 8.9 ng/g fat), indicates that BCPS levels might be increasing in Europe.

Final report: Testing a procedure for the identification of emerging chemical risks in the food chain. External Scientific Report. OC/EFSA/SCER/2014/03

Final report: Testing a procedure for the identification of emerging chemical risks in the food chain. External Scientific Report. OC/EFSA/SCER/2014/03

Synthesis and Characterization of Novel Copoly(aryl ether sulfone) Containing Phthalazinone and Biphenyl Moieties

A series of poly(ether sulfone)s copolymers (BP-COPPESs) based on phthalazinone and biphenyl moieties were synthesized by nucleophilic displacement reaction from 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one (DHPZ), biphenol (BP) and bis(4-chlorophenyl) sulfone (BCS). The experimental results indicated that the higher initial concentration of the polymerization reaction resulted in lower cyclics content and narrower molecular weight distribution of resultant copolymers. Moreover, the molecular weight decreased with increasing content of phthalazinone moiety of the main chain. These copolymers showed high glass transition temperatures ( Tg values) together with superior thermal properties. These copolymers were soluble in various aprotic solvents and were amorphous as evidenced by wide-angle X-ray diffraction. The molecular weights of BP-COPPES64 (60% phthalazinone moiety) could be controlled by utilizing excess molar content of BCS monomer. The rheological property test of copolymers indicated that the torque values decreased with increasing biphenyl group and ether linkage content.

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, β-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 μg/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′-MeSO 2-CB101, 4′-MeSO 2-CB101 and 4-MeSO 2-CB149, were quantified in all samples over time and showed an annual decrease of approximately 3% compared to MeSO 2-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 β-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 MeSO 2-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 MeSO 2-PCB pairs has been assigned an absolute R structure.

Enantiomeric Specificity of Methylsulfonyl-PCBs and Distribution of Bis(4-chlorophenyl) Sulfone, PCB, and DDE Methyl Sulfones in Grey Seal Tissues

PCB methyl sulfones (MeSO2-PCBs) are lipophilic PCB metabolites of which five of the environmentally relevant meta/para pairs are chiral (i.e., exist as atropisomeric pairs). Methylsulfonyl-DDE (MeSO2-DDE) is a DDE metabolite, while bis(4-chlorophenyl) sulfone (BCPS) is a commercial monomer used for thermoplastic production. All these sulfones are well-known environmental contaminants. In this study, liver, lung, and adipose tissue in grey seals (Halichoerus grypus) from the Baltic Sea, naturally exposed to organochlorines via their food, were analyzed for the compounds mentioned. MeSO2-PCBs, 3-MeSO2-DDE, and BCPS were all found in significantly higher concentrations in the liver than in lung and blubber. Their strong liver retention, represented by a median of 42 microg/g l.w. of sigmaMeSO2-PCBs, has previously been mainly neglected in assessments of exposure. The highest concentrations of PCBs and DDE were still found in the grey seal blubber. The atropisomeric composition of MeSO2-PCB congeners was determined, and their enantiomeric fractions were calculated and compared in blubber, liver, and lung tissues. The enantiomeric specificity was equal in all tissues. A notably high abundance (>94%) was observed for one atropisomer in each chiral MeSO2-PCB pair. The first eluting atropisomer (A1) was dominating for all para-substituted MeSO2-PCBs studied, while the second eluting atropisomers (A2) were as dominant in all meta-substituted MeSO2-PCBs in all samples analyzed. In the liver, as much as 50% of sigmaMeSO2-PCBs consisted of the second eluting atropisomer (A2) of 5-MeSO2-CB149. The results imply that the sulfone group is crucial for the specific liver retention of MeSO2-PCBs, 3-MeSO2-DDE, and BCPS.

Bis(4-chlorophenyl) sulfone (BCPS) in Swedish marine and fresh water wildlife–a screening study

Bis(4-chlorophenyl) sulfone (BCPS) is a high production volume chemical (HPVC) applied in thermostable polymers. BCPS has been detected as an environmental contaminant both in Europe and in North America but it is still not a commonly studied pollutant. In this study, three Baltic Sea fish species; herring (Clupea harengus), salmon (Salmo salar) and perch (Perca fluviatilis) from the Swedish coast, and one inland fish species, arctic char (Salvelinus alpinus), were analysed to screen for the occurrence and distribution of BCPS. Salmon and arctic char, were sampled in the early 1970s as well as the late 1990s. Fish eating grey seal (Halichoerus gryphus) and guillemot (Uria aalge) from the Baltic Sea were included to screen for whether BCPS biomagnify or not. The representativeness of the analysed samples for studying bioaccumulation of environmental pollutants was compared through analysis of two well known persistent and bioaccumulating compounds, 2,2′,4,4′,5,5′-hexachlorobiphenyl (CB-153), and 4,4′-DDE. Pooled muscle and blubber samples based on 4–10 individuals were used for analysis, as well as individual samples of grey seal blubber. 2,4,4′-Trichlorodiphenyl sulfone, was synthesised and applied as an internal standard. BCPS was detected in all marine samples but in only one of the fresh water fish samples. The highest BCPS concentrations detected, 1600 and 1900 ng/g lipid weighet (l.w.), were found in muscle from Baltic guillemot. The results indicate that BCPS is bioaccumulated in both grey seal and guillemot, and that the guillemot has higher concentrations of BCPS than the grey seal (50–500 ng/g l.w.). The concentrations found in different species of fish from the Baltic Sea ranged between 15–37 ng/g l.w. and lower concentrations were found in freshwater species (n.d.−1.8 ng/g l.w.). The present study shows that BCPS is found in all investigated species of wildlife but, in most species, still at low concentrations. However, the guillemot has levels in the low ppm range indicating a considerable biomagnification of BCPS in this species.

35 Cl NQR and 2 H NMR analysis of the critical dynamics by approaching from above the normal-incommensurate phase transition of Bis-(4-chlorophenyl)-sulfone (BCPS)

The inverse of the NQR or NMR spin lattice relaxation time of BCPS exhibits a Landau like critical behaviour on approaching the Normal/Incommensurate phase transition from above. This critical behaviour is interpreted as the contribution from the central peak observed in neutron experiments within the framework of the model of a coupling of the soft mode to pure relaxation modes. This result would be consistent with a central peak of dynamical nature.

Halogenated environmental contaminants in perch ( Perca fluviatilis) from Latvian coastal areas

The environmental contamination situation in coastal areas of the former Soviet Union has up to now been more or less unknown. This study on perch ( Perca fluviatilis), collected at three locations along the coast of Latvia during 1994 and 1995, provides concentrations of several ubiquitous environmental contaminants (PCBs, HCB, HCHs, 4,4′-DDT, 4,4′-DDE, 4,4′-DDD, trans-Nonachlor, 2,2′,4,4′-tetrabromodiphenyl ether). The concentrations of total PCB were similar at all study locations [0.7–1.4 ppm on a lipid weight (l.w.) basis], although a site close to the City of Riga indicated the presence of a local PCB contamination source. The contamination source was identified mainly by a higher relative content of lower chlorinated PCB congeners in the samples. Local pollution sources were also indicated for HCH and DDT. A large variation in the HCH isomer composition between 1994 and 1995 at one location demonstrates short half-lives of HCHs in the environment. The brominated flame retardant compound 2,2′,4,4′-tetrabromdiphenyl ether was present in the range of 6.4–10 ng/g l.w. in the perch. The clean-up method applied in this study allowed for quantification of two semi-polar contaminants frequently overlooked in Baltic biota, namely Dieldrin and bis(4-chlorophenyl) sulfone (BCPS). Concentrations of BCPS were remarkably high, i.e. in the same magnitude as the most abundant PCB congeners. The results presented shows that the contamination of, e.g. PCB in an area of the former Soviet Union, the Gulf of Riga, is similar to that observed in other parts of the Baltic area.

EFFECTS OF BIS(4-CHLOROPHENYL) SULFONE ON RATS FOLLOWING 28-DAY DIETARY EXPOSURE

The short-term oral toxicity of a recently identified environmental pollutant, bis(4-chlorophenyl) sulfone (BCPS), was studied. Groups of male Sprague-Dawley rats (n = 6) were administered BCPS via the diet at 0 (control), 10, 100, or 1000 ppm for 4 wk. Additional control and 1000 ppm groups were also treated for 1, 2, and 3 wk. At termination, highdose animals showed depressed growth rate and food consumption, and 1 high dose animal in each of the wk-1, -3, and-4 groups had marked hematuria. Increased liver to body weight ratio was present at 100 ppm and increased kidney to body weight ratio at 1000 ppm. Marked increases in hepatic benzoylresorufin O -dealkylase (BROD) and pentoxyresorufin O-dealkylase (PROD) activities were detected starting at 10 ppm. There was a significant decrease in methoxyresorufin O-dealkylase (MROD) activity at 1000 ppm. Hepatic UDP-glucuronosyltransferase (UDPGT) and glutathione S-transferase (GST) activities also increased starting at 100 ppm. A marked increase in urinary excretion of ascorbic acid was apparent starting at 10 ppm, while there were no changes in urinary N-acetylglucosaminidase (NAG) activity and protein levels. A threefold increase in serum cholesterol and a 30% increase in platelet counts were observed in the 1000 ppm group. Levels of thiobarbituric acid-reactive substances (TBARS) were increased by threefold in the liver of the highdose animals but were not significantly altered in the serum. Tissue BCPS concentrations were dose dependent and followed the order: adipose tissue >> liver > kidneys > brain, spleen, lungs. In the time-course study involving the control and high-dose groups, most of the treatment effects were clearly present in wk 1, and the severity of the effects remained at more or less the same levels thereafter. The exceptions were hepatic BROD and PROD activities, which showed a trend toward further increases with time of treatment. Liver and adipose tissue concentrations of BCPS remained unchanged from wk 1 to wk 4, while kidney concentrations increased with time. The results indicated that BCPS produced hepatic effects at the lowest dose level tested (10 ppm in the diet or 0.8 mg/kg/d).

Lattice Dynamics and Structural Instabilities in Biphenyl Sulfone Derivatives

Bis(4-chlorophenyl)sulfone (BClPS) is one of the few organic molecular solids which exhibits a displacive normal-incommensurate phase transition involving spatial modulations of conformational parameters. In the present work, the room temperature phase of BClPS was taken as a prototype, in order to investigate the structural stability of a group of related solids. Lattice dynamics calculations were performed in order to detect possible soft mode instabilities in the phonon dispersion branches. An atomistic semiempirical approach was adopted in lattice calculations, in addition to a semirigid molecular model considering the possibility of coupling between lattice and low lying internal degrees of freedom. Also, free-molecule equilibrium structure and dynamics calculations were performed using ab initio 3-21G * methods, to evaluate the extent of conformational distortions of the molecule in solid phase. The contribution of the internal potential and the molecular packing on the lattice instability of BClPS ...

NMR structural analysis of incommensurate modulated systems with multiple active symmetry modes: A case study of deuterated bis-(4-chlorophenyl)-sulfone

We report single-crystal deuteron NMR measurements both in the normal (N) and the incommensurate (IC) phase of bis-(4-chlorophenyl)-sulfone (BCPS). From the quadrupole splitting data obtained in the N phase, the quadrupole coupling (QC) tensors of all deuterons in BCPS are derived. The central part of the paper is concerned with the analysis of the deuteron NMR frequency distributions observed in the IC phase as a function of the orientation of the applied magnetic field relative to the BCPS crystal. This analysis is carried out in terms of the amplitudes and phases of the rotational symmetry modes that contribute to the fundamental IC modulation wave in BCPS, i.e., directly in terms of the structural changes associated with the IC phase transition. Both a semiquantitative graphical, and a fully quantitative numerical approach are given. The former is used to identify particularly simple and therefore particularly informative crystal orientations. The latter uses as an input the deuteron QC tensors measured in the N phase. Quantitative and complete structural information about the rotational displacements that atoms experience in an N--IC phase transition is deduced from NMR spectra. Our results are in full agreement with corresponding data of an x-ray-diffraction study. We also report on measurements of the spin-lattice relaxation time ${T}_{1}$ across the deuteron NMR frequency distributions. The results are at variance with the established theory and this is traced back to the fact that multiple rotational modes are contributing to the IC modulation wave in BCPS.

Synthesis and characterization of ran-copoly (p-phenylene sulfide sulfone/ketone)s

Random copoly(p-phenylene sulfide sulfone/ketone)s (PPSS/K) [PhSO 2 PhS] m [PhCOPhS] n are prepared in high yield by the polycondensation of sodium hydrosulfide (NaSH) with bis (4-chlorophenyl) sulfone (BCPS) and 4,4'-dichlorobenzophenone (DCBP). The copolymers with sulfone/ketone mole ratios (S:K)> 25:75 are amorphous, while the copolymers with S:K ratios ≤ 25:75 are crystalline. These materials form tough, creaseable films and exhibit a linear increase in the T g with increasing sulfone content

Raman and Birefringence Studies on the Incommensurate Phase Transition of Bis(4-chlorophenyl)sulfone Crystal*

Temperature dependences of polarized Raman spectra and birefringence of bis(4-chlorophenyl)sulfone (BCPS) crystal were measured. Gas-phase Raman spectra of BCPS were also measured. Raman bands observed in the low-frequency region at room temperature were shown to have partial nature of intramolecular vibrations. The lowest-frequency Raman band observed at low temperatures softened as the temperature was raised up to T 1 =150 K. A gradual change of birefringence was also observed below T 1 . These are in harmony with previous reports on the normal-incommensurate phase transition of this crystal at T 1 . The critical exponents for the changes in the soft-mode frequency and the birefringence were compared with that for the previously reported intensity change of the satellite X-ray diffraction. These data were explained by assuming an incommensurate orientational modulation of the phenyl groups of BCPS molecules. However, the incommensurate-commensurate transition which has been expected to take place around 115 K was not detected by the present measurements.

Thermodynamic study of the incommensurate phase transitions in crystalline bis(4-chlorophenyl)sulfone

The temperature dependence of heat capacity of bis(4-chlorophenyl)sulfone (BCPS) was measured by AC calorimetry between liquid nitrogen and room temperatures. The existence was confirmed of the normal-incommensurate phase transition of the second-order at 146 K. Also detected at about 115 K was the anomaly probably due to another phase transition, which was predicted as a lock-in transition from the NQR experiments by Corbero et al. The nature of the transition(s) is discussed on the basis of the magnitude of the anomalies.