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PubMed2006

Highly activated vinyl hydrogen in a significantly twisted styrene.

The novel example of a vinylic hydrogen more reactive than a benzylic hydrogen was found by treatment of a twisted styrene derivative with a strong base followed by D(2)O quenching. In this paper, the full details of the examples of the highly activated vinyl hydrogens in twisted styrene derivatives are described, with a discussion on the correlation between the reactivity of the vinyl hydrogens and the magnitude of the twist. The highly reactive vinyl hydrogens could be rationalized by considering the novel orbital interaction between the pi(*) orbital of the benzene ring and the pi(*) orbital of the vinylic C-H bond in the twisted styrene derivatives.

Journal Article↗

PubMed2004

Molecular-scale observation of formation of nuclei in soap-free polymerization of styrene.

To clarify the mechanism of the nucleation process in the soap-free polymerization of styrene in water, the polymerization process of styrene mainly at a temperature 46 degrees C was investigated on a molecular scale using an atomic force microscope (AFM) as well as a scanning electron microscope (SEM) and a dynamic light scattering apparatus (DLS). A cationic initiator was employed to make polymerized styrene adsorb electrostatically on the negatively charged mica plate with molecular-scale smoothness, and the mechanism was estimated from their AFM measurements in situ in water. The following was found. There exist two streams to produce PSL particles in the polymerization: one is the polymerization in monomer droplets fragmented by mixing from the main monomer reservoir floating above the solution, and the other is the polymerization of monomers dissolved in the solution by initiators. The former is normally neglected or not recognized because of the small contribution. The latter is the main production process of PSL particle, which is investigated in detail on a molecular scale, and a possible mechanism was proposed.

Journal Article↗

PubMed2006

Comparative study on reactions and self-directed growth mechanisms of styrene molecules on H-terminated Si(111) and Si(100): combining quantum chemistry and molecular mechanics simulations.

A comparative study on mechanisms of radical initiated self-directed growth of styrene molecules on the H-terminated Si(111) and Si(100) has been carried out by using quantum chemical and molecular mechanics methods. Several possible H-abstraction pathways through formations of transition states containing five-, six-, and even eight-membered ring structures are investigated with the aid of surface cluster models and density functional theory calculations. It has been demonstrated by employing periodic surface models and molecular mechanics simulations that the surface pattern and intermolecular interactions between phenyl groups play important roles in the self-directed growth processes. The formation of cluster-shaped aggregation of styrene molecules on H-Si(111) results from the undirectional chain reactions, due to the isotropic hexagonal arrangement of surface sites. On the contrary, the anisotropic style of H-Si(100) induces a strong directional preference for H-abstractions, following an order of the inter Si-Si dimer > the intra Si-Si dimer >> the inter Si-Si dimer row. The one-dimensionally ordered structures of single and double lines along the Si-Si dimer row are thus formed on H-Si(100). The self-directed growths of styrene molecules on both H-Si(111) and H-Si(100) are revealed to be stage-dependent.

Journal Article↗

PubMed2006

Regioselectivity in aqueous palladium catalysed hydroxycarbonylation of styrene: a catalytic and mechanistic study.

Regioselectivity control was studied in palladium catalysed hydroxycarbonylation of styrene in neat water with water-soluble phosphines, mostly trisulfonated triphenylphosphine, TPPTS, but also N-bis(N',N'-diethyl-2-aminoethyl)-4-aminomethylphenyl-diphenylphosphine, N3P. The factor giving the highest changes in regioselectivity in the TPPTS system, under similar reaction conditions, is the temperature. In the N3P case, only a minor variation in the n/i ratio as a function of temperature is observed. Insitu normal- and high-pressure NMR experiments were performed to obtain further information about the catalytic cycle and the reaction intermediates. Two palladium hydride intermediates, a palladium eta3-benzylic complex and both the branched and linear palladium acyl complexes were identified in the HP NMR experiments. The hydroxycarbonylation in water using styrene as a substrate operates using a hydride mechanism for pathways leading to both linear and branched product. Insertion of styrene in the palladium-hydride bond gives an eta3-benzyl compound. A high CO pressure gives a kinetic preference for the iso-acyl in the next step. In the TPPTS system, at moderate temperatures, the hydrolysis of the iso-acyl is faster than its conversion to the thermodynamically more stable n-acyl. A low n/i therefore requires high pressures and reasonably low temperatures. The N3P ligand always favours the linear product since isomerisation of the iso-acyl to the n-acyl in this system is fast under all conditions investigated.

Journal Article↗

PubMed1989

O6-substituted-2'-deoxyguanosine-3'-phosphate adducts detected by 32P post-labeling of styrene oxide treated DNA.

32P post-labeling of DNA reacted with styrene oxide resulted in the detection of six adducts. In order to determine which of these corresponded to modification at the O6 position of guanine, O6-substituted styrene oxide-deoxyguanosine-3'-monophosphate derivatives were synthesized. The two synthetic isomers were purified by HPLC and the structures were confirmed by mass spectrometry and 1H NMR. 32P post-labeling and co-chromatography with the DNA-styrene-7,8-oxide reaction products resulted in the assignment of adduct number 4 as O6-(2-hydroxy-2-phenylethyl)-2'--deoxyguanosine-3',5'-bisphosphate and adduct number 5 as O6-(2-hydroxy-1-phenylethyl)-2'-deoxyguanosine-3',5'-bisphosphate.

Chemical Phenomena↗

PubMed1983

Reactions of methylnitrosourea, epichlorohydrin, styrene oxide and acetoxyacetylaminofluorene with polyamino acids.

Radioactive methylnitrosourea, epichlorohydrin, styrene oxide, and N-acetoxy-2-acetylaminofluorene were reacted with 14 different polyamino acids in vitro, to determine the relative reactivity of the functional groups in amino acids. All the carcinogens reacted preferentially with polycysteine and much less with polyhistidine. Reaction was also noted with polylysine, polymethionine and polyarginine, as well as with DNA. Epichlorohydrin and styrene oxide reacted also with polyserine. Methylnitrosourea and N-acetoxy-2-acetylamino-fluorene reacted relatively more with polyhistidine as compared with the epoxides. Polycysteine, polyhistidine and polylysine were more reactive towards styrene oxide at pH 8 than at pH 6.

2-Acetylaminofluorene↗

PubMed1999

A new biocatalyst for production of optically pure aryl epoxides by styrene monooxygenase from Pseudomonas fluorescens ST.

We developed a biocatalyst by cloning the styrene monooxygenase genes (styA and styB) from Pseudomonas fluorescens ST responsible for the oxidation of styrene to its corresponding epoxide. Recombinant Escherichia coli was able to oxidize different aryl vinyl and aryl ethenyl compounds to their corresponding optically pure epoxides. The results of bioconversions indicate the broad substrate preference of styrene monooxygenase and its potential for the production of several fine chemicals.

Catalysis↗

PubMed1988

Conjugation of styrene oxide by the basic and acidic forms of glutathione transferase in the human fetal liver.

Two forms of glutathione transferase were isolated by means of isoelectric focusing of human fetal liver cytosol preparations. The enzyme activity was measured with 1-chloro-2,4-dinitrobenzene as the electrophilic substrate. One peak focused at pH 9-10 (basic form) and the other at pH 4-5 (acidic form). The basic and the acidic forms are representatives of glutathione transferase classes alpha and tau, respectively. These classes constitute two of the three classes defined for cytosolic forms of the enzyme in several mammalian species [Mannervik et al., Proc. natn. Acad. Sci. USA 82: 7202-7206, 1985]. Only the basic fraction isolated from human fetal liver catalyzed the conjugation of styrene oxide with glutathione at a significant rate. The kinetics of this form were studied keeping the concentration of styrene oxide constant (6 mM) and varying the glutathione concentration from 0.05 to 25 mM. The enzyme activity displayed non-Michaelis-Menten kinetics. The basic and acidic forms of glutathione transferase from a fetal liver were purified to homogeneity. Both purified forms catalyzed the conjugation of glutathione with styrene oxide. The kinetics were studied at varying glutathione concentrations and for both forms, it was found to be of a non-Michaelis-Menten type. The results are consistent with previous findings in the cytosolic fraction [Pacifici et al., Biochem. Pharmac. 30: 3367-3371, 1981] and show that the non-Michaelian kinetics observed with glutathione in human fetal liver cytosol are reflections of the intrinsic properties of the basic as well as the acid form of this enzyme and not primarily depending on the simultaneous catalytic action of the two forms.

Cytosol↗

PubMed2000

Reductive metabolism of stilbene oxide and styrene oxide to the olefins in rats.

The present study provides the first evidence that stilbene oxide and styrene oxide are reductively metabolized to the corresponding olefins in rats. When cis- or trans-stilbene oxide was given orally to rats, both cis- and trans-stilbene were isolated from the urine and feces. Styrene was also isolated from the urine and feces of rats given styrene oxide. These metabolites were identified unequivocally by UV and mass spectral comparison with authentic samples, and on the basis of their TLC and HPLC behavior. However, these olefins were not detected in the urine or feces of antibiotics-treated rats dosed with cis- or trans-stilbene oxide. Cecal contents of the untreated rats exhibited olefin oxide reductase activities toward cis- and trans-stilbene oxides under anaerobic conditions. The results suggest that intestinal bacteria play an important role in the reduction of olefin oxides to the corresponding olefins in the animal body.

Alkenes↗

PubMed2006

Fast and robust method for the determination of microstructure and composition in butadiene, styrene-butadiene, and isoprene rubber by near-infrared spectroscopy.

In the tire industry, synthetic styrene-butadiene rubber (SBR), butadiene rubber (BR), and isoprene rubber (IR) elastomers are essential for conferring to the product its properties of grip and rolling resistance. Their physical properties depend on their chemical composition, i. e., their microstructure and styrene content, which must be accurately controlled. This paper describes a fast, robust, and highly reproducible near-infrared analytical method for the quantitative determination of the microstructure and styrene content. The quantitative models are calculated with the help of pure spectral profiles estimated from a partial least squares (PLS) regression, using (13)C nuclear magnetic resonance (NMR) as the reference method. This versatile approach allows the models to be applied over a large range of compositions, from a single BR to an SBR-IR blend. The resulting quantitative predictions are independent of the sample path length. As a consequence, the sample preparation is solvent free and simplified with a very fast (five minutes) hot filming step of a bulk polymer piece. No precise thickness control is required. Thus, the operator effect becomes negligible and the method is easily transferable. The root mean square error of prediction, depending on the rubber composition, is between 0.7% and 1.3%. The reproducibility standard error is less than 0.2% in every case.

Journal Article↗

PubMed1989

Characterization of structural xenobiotic modifications in proteins by high sensitivity tandem mass spectrometry. Human hemoglobin treated in vitro with styrene 7,8-oxide.

Alkylation of DNA by xenobiotic agents, or their electrophilic metabolites, is believed to be the major initiating process that may result ultimately in carcinogenesis. The study of hemoglobin alkylated in vivo by chemical carcinogens has previously been proposed as an indicator for DNA alkylation. Xenobiotically modified proteins, however, are not readily amenable to conventional methods for amino acid sequencing. Tandem mass spectrometry allows unambiguous structural elucidation of chemically modified proteins. Styrene is a widely used chemical in the plastics industry and its major metabolite, styrene 7,8-oxide, is both mutagenic and carcinogenic in rodents. Human hemoglobin was modified in vitro with styrene 7,8-oxide and digested with trypsin. Tryptic peptides from unmodified hemoglobin were isolated by high performance liquid chromatography, and their molecular weights were determined by liquid secondary ion mass spectrometry. This allowed confirmation of the known sequence of the protein and provided a reference for the identification of modified peptides. High performance tandem mass spectrometry of modified peptides allowed unambiguous assignment of specific residues modified. The externally accessible histidines were found to be the dominant sites for alkylation at high modification levels of the protein.

Alkylation↗

PubMed1986

Rat and mouse forestomach tumors induced by chronic oral administration of styrene oxide.

Styrene oxide (CAS: 96-09-3) was administered in corn oil by gavage three times a week at two dose levels to groups of 52 male and 52 female F344 rats and 52 male and 52 female B6C3F1 mice for 2 years, after which the surviving animals were killed and examined histopathologically. The doses given to rats were 550 and 275 mg/kg (body wt) per treatment; in mice the two doses were 750 and 375 mg/kg (body wt) per treatment. The main pathologic findings were high incidences of squamous cell carcinomas or papillomas of the forestomach in both sexes of both rats and mice. These neoplasms were virtually absent from the 52 controls of either sex of both species given parallel treatment with corn oil alone. There was a statistically significant increase in the incidence of hepatocellular neoplasms in male mice receiving 375 mg styrene oxide/kg. Styrene oxide is carcinogenic to both sexes of F344 rats and B6C3F1 mice when administered orally in corn oil.

Administration, Oral↗

PubMedDate not supplied

Metabolism of styrene oxide in the rat and guinea pig.

The metabolism of styrene oxide has been studied in the rat and guinea pig, with emphasis upon bivalent sulfur metabolites. Methylthio analogs of phenylethylene glycol, with the methylthio group in both possible positions, were found as urinary metabolites in both species. These compounds were present in more than trace amounts. The excretion of 2-hydroxy-1-methylthio-1-phenylethane amounted to about 7% of the administered dose in the guinea pig, and about 2% in the rat, in o-24 hr urine samples. The positional isomer 1-hydroxy-2-methylthio-1-phenylethane was excreted in lesser amounts in both species. Acidic urinary metabolites derived from glutathione conjugates are species dependent. In this study, the only products observed in the rat were the mercapturic acids expected as a result of reaction of the oxide with glutathione. In the guinea pig, the major bivalent sulfur acids were the corresponding mercaptoacetic acids. Other related metabolites included a mercaptolactic and a mercaptopyruvic acid, together with one of the mercapturic acids. These metabolites result from partial acetylation or acetylation/deacetylation of cysteine or cysteinylglycine adducts. The hitherto unobserved dihydrodiol formed via an arene oxide was found as a minor metabolite for both styrene and styrene oxide.

Animals↗

PubMedDate not supplied

Synthesis and elimination reactions of methylsulfonium ions formed from styrene oxide and methylthio compounds related to methionine and cysteine.

Methylsulfonium compounds were prepared through the nucleophilic addition of a number of methylthio reagents to styrene oxide. In the absence of water, methylsulfonium ions from styrene oxide were converted to 2-hydroxy-1-methylthio-1-phenylethane (I) and 1-hydroxy-2-methylthio-1-phenylethane (II) by brief heating. In the presence of water, the glycol 1,2- dihydroxyphenylethane (III) was obtained along with I and II. The addition and elimination reactions were combined in sequences that were carried out in an organic solvent (acetone) or in aqueous solutions containing acetone or methanol. With L-methionine as the reagent, both reactions proceeded in sequence at 37 degrees C in water/methanol (80:20) to give I, II, and III as reaction products. These methods can be used to prepare the methylthio metabolites of styrene oxide.

Chemical Phenomena↗

PubMed1985

An analysis of exposure to styrene in the reinforced plastic boat-making industry.

To evaluate patterns of occupational exposure to styrene monomer in the boat-building industry, we conducted industrial hygiene surveys in seven fiberglass-reinforced plastic boat-fabrication plants. A total of 397 personal breathing zone air samples were collected on workers in four key job categories: gel coating and hull, deck, and small-parts lamination. We found that exposure to styrene in 234 (59%) of the personal samples exceeded the NIOSH-recommended time-weighted average (TWA) standard of 50 parts per million (ppm), and 96 (24%) of these samples exceeded the OSHA eight-hour TWA permissible exposure limit of 100 ppm. From highest to lowest average exposure potential, the job categories ranked in the following order: hull lamination (range 2-183 ppm, mean 78 ppm), deck lamination (range 12-160 ppm, mean 73 ppm), gel coating (range 5-94 ppm, mean 48 ppm), and small-parts lamination (range 9-130 ppm, mean 45 ppm). The former two categories composed a higher-exposure group, and the latter two tended to form a lower-exposure group. Exposures in these jobs appear to be proportional to resin consumption. Statistical analyses indicated that the parameter that most affects exposure potential is job category. Within a job category, part size, configuration, and surface area are important determinants of exposure. The principal reason for high exposures was the absence of control technologies and, in particular, the absence of adequate ventilation.

Air Pollutants, Occupational↗

PubMed1991

Single-strand breaks, chromosome aberrations, sister-chromatid exchanges, and micronuclei in blood lymphocytes of workers exposed to styrene during the production of reinforced plastics.

Chromosome aberrations (CA), micronuclei (MN, cytokinesis-block [CB] method), and sister-chromatid exchanges (SCE) were analysed in blood lymphocytes of 17 workers and 17 control subjects. The mean urinary mandelic acid level (average 9.4 mmol/l) and styrene glycol in blood (average 2.5 mumol/l) implied exposure to about 300 mg/m3 of styrene in the plant. The number of CA was significantly higher in non-smoking workers compared with nonsmoking controls. A significant correlation was observed between duration of exposure and individual CA level of all workers. No significant effects were observed in MN or SCE. Single-strand breaks (SSB) in DNA of isolated lymphocytes were studied in nine of the workers and eight of the controls by the DNA-unwinding technique. The results showed an increase in SSB among the exposed workers. The present findings support earlier reports on the increase of structural CA in blood lymphocytes of workers in the reinforced plastic industry, and also show that SSBs are elevated in such workers.

Chromosome Aberrations↗

PubMed1986

Sister chromatid exchange and chromosome aberration analyses in mice after in vivo exposure to acrylonitrile, styrene, or butadiene monoxide.

The use of polymers in plastic and rubber products has generated concern that monomers potentially active in biological systems may be eluted from these substances. We have evaluated two such monomers, acrylonitrile and styrene, for the induction of chromosome damage in mice. Butadiene monoxide, a presumed metabolite of a third important monomer, 1,3-butadiene, was also tested. These chemicals were administered as a single intraperitoneal injection; sister chromatid exchanges and chromosome aberrations were analyzed in bone marrow cells. Acrylonitrile and styrene were largely negative for these endpoints when tested at doses ranging to 60 mg/kg and 1,000 mg/kg, respectively. Butadiene monoxide, which previously has not been tested in a mammalian system, was determined to be a very effective inducer of sister chromatid exchanges and chromosome aberrations. Both endpoints showed a clear dose response and a greater than ten-fold increase over control levels at high doses. These studies represent an initial step in our efforts to evaluate genetic risk associated with exposure to common polymeric chemicals.

Acrylonitrile↗

PubMed1985

Stereometabolism of styrene in man: gas chromatographic determination of phenylethyleneglycol enantiomers and phenylethanol isomers in the urine of occupationally-exposed persons.

A gas chromatographic procedure for the determination of phenylethyleneglycol enantiomers and phenylethanol isomers is described and applied to the investigation of urine samples from occupationally styrene-exposed workers (11 males, six females) and an unexposed control group. Phenylethyleneglycol enantiomers and 2-phenylethanol were present in the urine samples of exposed and unexposed individuals whereas 1-DL-phenylethanol was not found in control urine. The L/D enantiomer ratio of phenylethyleneglycol was found to be approximately 3 in the exposed group and 1.5 in the control group. Because of the close structural relation of these metabolites to the primarily formed epoxide, the results give further insight into the stereotoxicity of styrene in man.

Animals↗