Contribution to the Structural Elucidation of 10 Isomers of Technical <i>p</i>-Nonylphenol

Thiele, Bjoern; Heinke, Volkmar; Kleist, E.; Guenther, Klaus

doi:10.1021/es040026g

Cited by 93 publications

(49 citation statements)

References 16 publications

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“…The presence of these isomers were good agreement with previous reports. 17,18,25,26) These NP isomers showed lower estrogenic activities than the commercial NP. The other NP isomers in the commercial NP were suggested to possess much higher estrogenic activities compared with the NP isomers synthesized in this study.…”

Section: Estrogenic Activity Of Synthesized Np Isomers In Commercial Npmentioning

confidence: 89%

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Estrogenic Activity of Branched 4-Nonylphenol Isomers Examined by Yeast Two-Hybrid Assay

Shioji

Tsunoi

Kobayashi

et al. 2006

JOURNAL OF HEALTH SCIENCE

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Various branched isomers of 4-nonylphenol (NP) and, in addition, the other 4-alkylphenols (APs) were synthesized and their estrogenic activities were assessed using the yeast two-hybrid system. We investigated the relationships between the structure of the nonyl group of NP isomers and their estrogenic activities based on the following five factors: the length of the main alkyl chain, the degree of branching on the α-carbon, the degree of bulkiness, the position of the branch, and the cyclic structure in the nonyl group. An appropriate length of the main alkyl chain was essential for the estrogenic activity. A small effect of the branching on the α-carbon was observed. The importance of the bulkiness and position of the branch in the nonyl group was suggested from the results of the synthesized NP isomers possessing the high estrogenic activities. The bulkiness on the β-carbon was the most important factor for the high estrogenic activity. The investigation of the cyclic structure also indicated the significance of the bulkiness around the β-carbon. The bulkiness on the γ-carbon was also suggested to be an important factor. The metabolic effect of the synthesized APs on the estrogenic activity was also examined using a liver S9. The estrogenic activities of the selected APs were either reduced or lost. In addition, GC-MS analyses of the commercial NP and synthesized NP isomers revealed that the nine synthesized NP isomers were included in the commercial NP.

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Section: Estrogenic Activity Of Synthesized Np Isomers In Commercial Npmentioning

confidence: 89%

“…15,16) Gas chromatographic analysis indicated that more than 21 isomers were included in commercial NP. 17) Some NP isomers were fractionated by HPLC and their estrogenic activities were measured by recombinant yeast screen assay.…”

Section: Introductionmentioning

confidence: 99%

Estrogenic Activity of Branched 4-Nonylphenol Isomers Examined by Yeast Two-Hybrid Assay

Shioji

Tsunoi

Kobayashi

et al. 2006

JOURNAL OF HEALTH SCIENCE

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“…NP is used as part of a technical mixture which consists of more than 20 branched isomers of the nonyl chain (23,28). Although some studies report an easy degradation of the NP with a linear alkyl chain (4-n-NP) through oxidation of the side chain, the situation is different for branched isomers of NP (2,25,26).…”

mentioning

confidence: 99%

“…It is important to note that all compounds synthesized with 3,5-dimethyl-3-heptanol, such as p353NP and o353NHQ, are found as four diastereomers due to the pres- ence of two asymmetric carbon atoms in the nonyl chain. They give rise to only two characteristic diastereomeric peaks in all GC analyses, and both peaks display the same mass spectrum (23,27). To allow better comprehension of the GC-MS analyses, only fragment ions of the first diastereomeric peak of the metabolites and o353NHQ are presented in Table 1.…”

mentioning

confidence: 99%

Degradation of a Nonylphenol Single Isomer by Sphingomonas sp. Strain TTNP3 Leads to a Hydroxylation-Induced Migration Product

Corvini

Meesters

Schäffer

et al. 2004

Appl Environ Microbiol

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Sphingomonas sp. strain TTNP3 degrades 4(3,5-dimethyl-3-heptyl)-phenol and unidentified metabolites that were described previously. The chromatographic analyses of the synthesized reference compound and the metabolites led to their identification as 2(3,5-dimethyl-3-heptyl)-1,4-benzenediol. This finding indicates that the nonylphenol metabolism of this bacterium involves unconventional degradation pathways where an NIH shift mechanism occurs.Nonylphenol (NP) is a ubiquitous pollutant which mainly results from the biodegradation of widely used NP polyethoxylate surfactants, and it is well known for its endocrine systemdisrupting potential (5,8,11,13,20,21). NP is used as part of a technical mixture which consists of more than 20 branched isomers of the nonyl chain (23, 28). Although some studies report an easy degradation of the NP with a linear alkyl chain (4-n-NP) through oxidation of the side chain, the situation is different for branched isomers of NP (2,25,26). The main reason for the poor degradability of NP is a quaternary carbon atom (␣-carbon) of the branched alkyl chain, which is involved in the attachment of the nonyl group to the phenol moiety. More than 85% of the isomers of the technical mixture contain such quaternary ␣-carbon atoms (26, 28). Some strains belonging to the genera Sphingomonas, Sphingobium, and Pseudomonas have been reported to be able to degrade the branched isomers of NP, but the catabolic pathways in these bacteria remain poorly characterized (6,7,18,19,21,24).Previously, it was proven that the dead-end product of the degradation of 4(3Ј,5Ј-dimethyl-3Ј-heptyl)-phenol (p353NP) diastereomers is 3,5-dimethyl-3-heptanol (nonanol). This metabolite corresponds to the nonyl chain of p353NP, where the aromatic ring has been replaced by a hydroxyl group (3). It remains to be elucidated how the very stable quaternary C atom structure of NP can lead to the formation of nonanol. Nonanol has been found only in cultures of Sphingomonas sp. strain TTNP3 and Sphingomonas cloacae, so these bacteria seem to possess particular degradation pathways for NP (3,6,21). Recently, it was reported that neither 4-n-NP nor shortchain alkylphenols were degraded by Sphingomonas sp. strain TTNP3, whereas the diastereomers of the branched single isomer p353NP (Fig. 1) led to the formation of ring-oxidized metabolites (4). Ring-oxidized metabolites were detected only in the intracellular fraction and were shown to be different from 4(3Ј,5Ј-dimethyl-3Ј-heptyl)-catechol (Fig. 1b) and 4(3Ј,5Ј-dimethyl-3Ј-heptyl)-resorcinol (Fig. 1c), hydroxylated at positions C-2 and C-3 (Fig. 1), respectively. We hypothesize the formation of metabolites which undergo either hydroxylation with an alkyl chain internal rearrangement, as is the case for bisphenol A (14), or hydroxylation-induced migration of the alkyl chain immediately after hydroxylation at position C-4. The latter process would lead to the formation of 2(3Ј,5Ј-dimethyl-3Ј-heptyl)-1,4-benzenediol (o353NHQ) (Fig. 1d). In order to identify definitively these metabolites ...

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“…The final technical mixtures of NP contain more than 22 isomers of 4-substituted monoalkylphenols (Thiele et al 2004;Wheeler et al 1997).…”

Section: Np and Npeosmentioning

confidence: 99%

Application of the GREAT-ER model for environmental risk assessment of nonylphenol and nonylphenol ethoxylates in China

Zhang

Yan

Hao

et al. 2015

Environ Sci Pollut Res

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The environmental risk presented by Bdown-thedrain^chemicals to receiving rivers in large urban areas has received increasing attention in recent years. Geo-referenced Regional Environmental Assessment Tool for European Rivers (GREAT-ER) is a typical river catchment model that has been specifically developed for the risk assessment of these chemicals and applied in many European rivers. By utilizing the new version of the model, GREAT-ER 3.0, which is the first completely open source software for worldwide application, this study represents the first attempt to conduct an application of GREAT-ER in the Wenyu River of China. Aquatic exposure simulation and an environmental risk assessment of nonylphenol (NP) and its environmental precursor nonylphenol ethoxylates (NPEOs) were conducted effectively by GREAT-ER model, since NP is one of typical endocrine disrupting chemicals (EDCs) and its environmental precursor NPEOs as a Bdown-the-drain^chemical are extensively used in China. In the result, the predicted environmental concentrations (PECs) of NP and NPEOs in the water of Wenyu River were 538 and 4320 ng/L, respectively, at the regional scale, and 1210 and 8990 ng/L, respectively, at the local scale. From the results profile of the RCR, the combination of high emissions from large STPs with insufficient dilution of the river caused the high RCR. The PECs of NP in the sediment were in the range of 216.8-8218.3 ng/g (dry weight), which was consistent with the available monitoring data. The study showed the worldwide applicability and reliability of GREAT-ER as a river catchment model for the risk assessment of these chemicals and also revealed the general environmental risks presented by NP and NPEOs in the Wenyu River catchment in Beijing due to the extensive use of these chemicals. The results suggest that specific control or treatment measures are probably warranted for these chemicals to reduce their discharge in major cities.

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Contribution to the Structural Elucidation of 10 Isomers of Technical p-Nonylphenol

Cited by 93 publications

References 16 publications

Estrogenic Activity of Branched 4-Nonylphenol Isomers Examined by Yeast Two-Hybrid Assay

Estrogenic Activity of Branched 4-Nonylphenol Isomers Examined by Yeast Two-Hybrid Assay

Degradation of a Nonylphenol Single Isomer by Sphingomonas sp. Strain TTNP3 Leads to a Hydroxylation-Induced Migration Product

Application of the GREAT-ER model for environmental risk assessment of nonylphenol and nonylphenol ethoxylates in China

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