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Title: Carbene-based Difluoromethylation of Bisphenols: Application to the Instantaneous Tagging of Bisphenol A in Spiked Soil for Its Detection and Identification by Electron Ionization Gas Chromatography-Mass Spectrometry

Abstract

The rapid and efficient difluoromethylation of a panel of eleven bisphenols (BPs) for their enhanced detection and identification by Electron-Ionization Gas Chromatography-Mass Spectrometry (EI-GC-MS) is presented. The derivatization employs the inexpensive, environmentally benign agent diethyl (bromodifluoromethyl) phosphonate (DBDFP) as a difluorocarbene-generating species that converts the BPs into bis-difluoromethylated ethers that can be detected and identified by GC-MS means. Key attributes of the protocol include its extreme rapidity (30 seconds) at ambient temperature, high specificity for BPs amidst other alcohol-containing analytes, and its biphasic nature that allows for its convenient adaptation to the analysis of BPs in organic as well as aqueous matrices. The protocol furnishes stable, novel BP ethers armed with a total of four fluorine atoms for their subsequent analysis by EI-GC-MS. Furthermore, each derivatized bisphenol exhibits unique retention times vastly different from their native counterparts leading to their unequivocal identification. The effectiveness and robustness of the developed methodology was applied to the tagging of the most famous member of this family of compounds, bisphenol-A (BPA), when spiked (at 1 μg.g–1 concentration) in the physically and compositionally complex Nebraska EPA standard soil. The method detection limit (MDL) for the bis-difluoromethylated BPA was determined to be 0.01 μg.mL–1. The bis-difluoromethylatedmore » BPA was conveniently detected on the organic layers from the biphasic, derivatized mixtures, highlighting the protocol’s practicality and utility in the rapid, qualitative detection of this endocrine disruptor during environmental analysis.« less

Authors:
 [1];  [1];  [1]
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  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Publication Date:
Research Org.:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1601564
Report Number(s):
LLNL-JRNL-779157
Journal ID: ISSN 2045-2322; 972724
Grant/Contract Number:  
AC52-07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; bisphenol; bisphenol A; GC-MS; difluoromethylation; endocrine disruptor

Citation Formats

Valdez, Carlos A., Leif, Roald N., and Hok, Saphon. Carbene-based Difluoromethylation of Bisphenols: Application to the Instantaneous Tagging of Bisphenol A in Spiked Soil for Its Detection and Identification by Electron Ionization Gas Chromatography-Mass Spectrometry. United States: N. p., 2019. Web. doi:10.1038/s41598-019-53735-9.
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Valdez, Carlos A., Leif, Roald N., & Hok, Saphon. Carbene-based Difluoromethylation of Bisphenols: Application to the Instantaneous Tagging of Bisphenol A in Spiked Soil for Its Detection and Identification by Electron Ionization Gas Chromatography-Mass Spectrometry. United States. https://doi.org/10.1038/s41598-019-53735-9
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Valdez, Carlos A., Leif, Roald N., and Hok, Saphon. Fri . "Carbene-based Difluoromethylation of Bisphenols: Application to the Instantaneous Tagging of Bisphenol A in Spiked Soil for Its Detection and Identification by Electron Ionization Gas Chromatography-Mass Spectrometry". United States. https://doi.org/10.1038/s41598-019-53735-9. https://www.osti.gov/servlets/purl/1601564.
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@article{osti_1601564,
title = {Carbene-based Difluoromethylation of Bisphenols: Application to the Instantaneous Tagging of Bisphenol A in Spiked Soil for Its Detection and Identification by Electron Ionization Gas Chromatography-Mass Spectrometry},
author = {Valdez, Carlos A. and Leif, Roald N. and Hok, Saphon},
abstractNote = {The rapid and efficient difluoromethylation of a panel of eleven bisphenols (BPs) for their enhanced detection and identification by Electron-Ionization Gas Chromatography-Mass Spectrometry (EI-GC-MS) is presented. The derivatization employs the inexpensive, environmentally benign agent diethyl (bromodifluoromethyl) phosphonate (DBDFP) as a difluorocarbene-generating species that converts the BPs into bis-difluoromethylated ethers that can be detected and identified by GC-MS means. Key attributes of the protocol include its extreme rapidity (30 seconds) at ambient temperature, high specificity for BPs amidst other alcohol-containing analytes, and its biphasic nature that allows for its convenient adaptation to the analysis of BPs in organic as well as aqueous matrices. The protocol furnishes stable, novel BP ethers armed with a total of four fluorine atoms for their subsequent analysis by EI-GC-MS. Furthermore, each derivatized bisphenol exhibits unique retention times vastly different from their native counterparts leading to their unequivocal identification. The effectiveness and robustness of the developed methodology was applied to the tagging of the most famous member of this family of compounds, bisphenol-A (BPA), when spiked (at 1 μg.g–1 concentration) in the physically and compositionally complex Nebraska EPA standard soil. The method detection limit (MDL) for the bis-difluoromethylated BPA was determined to be 0.01 μg.mL–1. The bis-difluoromethylated BPA was conveniently detected on the organic layers from the biphasic, derivatized mixtures, highlighting the protocol’s practicality and utility in the rapid, qualitative detection of this endocrine disruptor during environmental analysis.},
doi = {10.1038/s41598-019-53735-9},
journal = {Scientific Reports},
number = 1,
volume = 9,
place = {United States},
year = {Fri Nov 22 00:00:00 EST 2019},
month = {Fri Nov 22 00:00:00 EST 2019}
}
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https://doi.org/10.1038/s41598-019-53735-9
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A new chapter in the bisphenol A story: bisphenol S and bisphenol F are not safe alternatives to this compound
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New halogen-free fire retardant for engineering plastic applications
journal, June 2001

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  • Journal of Vinyl and Additive Technology, Vol. 7, Issue 2
  • DOI: 10.1002/vnl.10274

UHPLC–MS/MS method for the determination of bisphenol A and its chlorinated derivatives, bisphenol S, parabens, and benzophenones in human urine samples
journal, April 2014

  • Vela-Soria, F.; Ballesteros, O.; Zafra-Gómez, A.
  • Analytical and Bioanalytical Chemistry, Vol. 406, Issue 15
  • DOI: 10.1007/s00216-014-7785-9

Improvement of bisphenol A quantitation from urine by LCMS
journal, February 2015

Chemical tagging of chlorinated phenols for their facile detection and analysis by NMR spectroscopy
journal, March 2015

  • Valdez, Carlos A.; Leif, Roald N.
  • Analytical and Bioanalytical Chemistry, Vol. 407, Issue 13
  • DOI: 10.1007/s00216-015-8625-2

Determination of tetrabromobisphenol-A, tetrachlorobisphenol-A and bisphenol-A in soil by ultrasonic assisted extraction and gas chromatography–mass spectrometry
journal, July 2009

  • Sánchez-Brunete, Consuelo; Miguel, Ester; Tadeo, José L.
  • Journal of Chromatography A, Vol. 1216, Issue 29
  • DOI: 10.1016/j.chroma.2009.05.065

Ubiquity of bisphenol A in the atmosphere
journal, October 2010

In vivo effects of bisphenol A in laboratory rodent studies
journal, August 2007

An evaluation of evidence for the carcinogenic activity of bisphenol A
journal, August 2007

Bisphenol A and human health: A review of the literature
journal, December 2013

Diethyl bromodifluoromethylphosphonate: a highly efficient and environmentally benign difluorocarbene precursor
journal, July 2009

Derivatisation reactions in the chromatographic analysis of chemical warfare agents and their degradation products
journal, June 2003

Gas chromatographic–mass spectrometric method for the determination of bisphenol A and its chlorinated derivatives in urban wastewater
journal, February 2003

Silyl Derivatization of Alkylphenols, Chlorophenols, and Bisphenol A for Simultaneous GC/MS Determination
journal, July 2001

  • Li, Donghao; Park, Jongman; Oh, Jae-Ryoung
  • Analytical Chemistry, Vol. 73, Issue 13
  • DOI: 10.1021/ac001494l

Simultaneous Determination of 4-Nonylphenol and Bisphenol A in Sewage Sludge
journal, July 2002

  • Meesters, Roland J. W.; Schröder, Horst Fr.
  • Analytical Chemistry, Vol. 74, Issue 14
  • DOI: 10.1021/ac011258q

Water Analysis:  Emerging Contaminants and Current Issues
journal, May 2003

  • Richardson, Susan D.
  • Analytical Chemistry, Vol. 75, Issue 12
  • DOI: 10.1021/ac0301301

The Trifluoromethyl Group in Medical Chemistry
journal, April 1959

  • Yale, Harry L.
  • Journal of Medicinal and Pharmaceutical Chemistry, Vol. 1, Issue 2
  • DOI: 10.1021/jm50003a001

Bisphenol-A and the Great Divide: A Review of Controversies in the Field of Endocrine Disruption
journal, February 2009

  • Vandenberg, Laura N.; Maffini, Maricel V.; Sonnenschein, Carlos
  • Endocrine Reviews, Vol. 30, Issue 1
  • DOI: 10.1210/er.2008-0021

Parent Bisphenol A Accumulation in the Human Maternal-Fetal-Placental Unit
journal, October 2002

  • Schönfelder, Gilbert; Wittfoht, Werner; Hopp, Hartmut
  • Environmental Health Perspectives, Vol. 110, Issue 11
  • DOI: 10.1289/ehp.021100703

Exposure of the U.S. Population to Bisphenol A and 4- tertiary -Octylphenol: 2003–2004
journal, January 2008

  • Calafat, Antonia M.; Ye, Xiaoyun; Wong, Lee-Yang
  • Environmental Health Perspectives, Vol. 116, Issue 1
  • DOI: 10.1289/ehp.10753

Bisphenol S and F: A Systematic Review and Comparison of the Hormonal Activity of Bisphenol A Substitutes
journal, July 2015

  • Rochester, Johanna R.; Bolden, Ashley L.
  • Environmental Health Perspectives, Vol. 123, Issue 7
  • DOI: 10.1289/ehp.1408989

Xenoestrogens released from lacquer coatings in food cans.
journal, June 1995

  • Brotons, J. A.; Olea-Serrano, M. F.; Villalobos, M.
  • Environmental Health Perspectives, Vol. 103, Issue 6
  • DOI: 10.1289/ehp.95103608
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