Determination of a flame retardant hydrolysis product in human urine by SPE and LC?MS. Comparison of molecularly imprinted solid-phase extraction with a mixed-mode anion exchanger

Möller, Kristina Ängeby; Crescenzi, Carlo; Nilsson, Ulrika

doi:10.1007/s00216-003-2267-5

Cited by 67 publications

(21 citation statements)

References 26 publications

(29 reference statements)

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“…Recently, quantified DAPs and MAPs in urine have been identified as biomarkers to assess human exposure. In total, DAPs of BDCIPP, BCIPP, BCEP, BBOEP, DBP, DPHP, DEHP and some MAPs of MEHP, MBP, MCIPP, MBOEP and MPHP have been quantified in human urine, with median concentrations in the ng ml À1 range (Butt et al, 2014;Cequier et al, 2014bCequier et al, , 2015Chu et al, 2011;Cooper et al, 2011;Dodson et al, 2014;Fromme et al, 2014;Hoffman et al, 2015;Meeker et al, 2013a,b;Moller et al, 2004;Petropoulou et al, 2016;Reemtsma et al, 2011;Schindler et al, 2009a,b;Van den Eede et al, 2015b;Van den Eede et al, 2013b) (SI Table S2). However, no information is available for DAPs and MAPs or other OPFR metabolites from internal exposure studies of wild animals.…”

Section: Internal Exposurementioning

confidence: 99%

Review of OPFRs in animals and humans: Absorption, bioaccumulation, metabolism, and internal exposure research

2016

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h i g h l i g h t sThe absorption, bioaccumulation, metabolism and internal exposure of OPFRs are reviewed. Inhalation, ingestion and dermal contact are the main OPFRs absorptionpathways for humans. General in vivo and in vitro metabolic pathways of three different types of OPFRs are proposed. DAPs and MAPs are considered as putative biomarkers for the assessment of internal exposure of OPFRs in humans. a r t i c l e i n f o t r a c tDue to their widespread use, organophosphate flame retardants (OPFRs) are commonly detected in various environmental matrices and have been identified as emerging contaminants. Considering the adverse effects of OPFRs, many researchers have paid their attention on the absorption, bioaccumulation, metabolism and internal exposure processes of OPFRs in animals and humans. In this article, we first review the diverse absorption routes of OPFRs by animals and humans (e.g., inhalation, ingestion, dermal absorption and gill absorption). Bioaccumulation and biomagnification potentials of OPFRs in different types of organisms and food webs are also summarized, based on quite limited available data and results. For metabolism, we review the Phase-I and Phase-II metabolic processes for each type of OPFRs (chlorinated OPFRs, alkyl-OPFRs and aryl-OPFRs) in the animals and humans, as well as toxicokinetic information and putative exposure biomarkers on OPFRs. Finally, we highlight gaps in our knowledge and critical directions for future internal exposure studies of OPFRs in animals and humans.

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Section: Internal Exposurementioning

confidence: 99%

Review of OPFRs in animals and humans: Absorption, bioaccumulation, metabolism, and internal exposure research

2016

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“…These metabolites in human biological fluids, such as urine, therefore, may serve as biomarkers of human exposure to their parent FRs. No methods currently exist to measure BDCPP in human biological fluids or tissues, however, there are a few published methods to measure DPP in human urine [17–19]. …”

Section: Introductionmentioning

confidence: 99%

Analysis of the flame retardant metabolites bis(1,3-dichloro-2-propyl) phosphate (BDCPP) and diphenyl phosphate (DPP) in urine using liquid chromatography–tandem mass spectrometry

et al. 2011

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Organophosphate triesters tris-(1,3-dichloro-2-propyl) phosphate (TDCPP) and triphenyl phosphate (TPP) are widely used flame retardants (FRs) present in many products common to human environments, yet understanding of human exposure, and health effects of these compounds is limited. Monitoring urinary metabolites as biomarkers of exposure can be a valuable aid for improving this understanding; however, no previously published method exists for the analysis of the primary TDCPP metabolite, bis (1,3-dichloro-2-propyl) phosphate (BDCPP), in human urine. Here we present a method to extract the metabolites BDCPP and diphenyl phosphate (DPP) in human urine using mixed-mode anion exchange solid phase extraction and mass-labeled internal standards with analysis by atmospheric pressure chemical ionization liquid chromatography tandem mass spectrometry (APCI-LC/MS-MS). The method detection limit was 8 pg mL−1 urine for BDCPP and 204 pg mL−1 for DPP. Recoveries of analytes spiked into urine ranged from 82 ± 10% to 91 ± 4% for BDCPP and from 72 ± 12% to 76 ± 8% for DPP. Analysis of a small number of urine samples (n=9) randomly collected from non occupationally exposed adults revealed the presence of both BDCPP and DPP in all samples. Non-normalized urinary concentrations ranged from 46–1662 pg BDCPP mL−1 and 287–7443 pg DPP mL−1, with geometric means of 147 pg BDCPP mL−1 and 1074 pg DPP mL−1. Levels of DPP were higher than those of BDCPP in 89% of samples. The presented method is simple and sufficiently sensitive to detect these FR metabolites in humans and may be applied to future studies to increase our understanding of exposure and potential health effects to FRs.

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“…2). Such MIPs are hence analogous to polyclonal antibodies and are sometimes "group-specific," that is, selective not only towards the original template but also to other structurally related compounds, which can be quite useful, for example, for the separation of a class of analytes [13]. After polymerization, the Fig.…”

Section: Imprinting Matricesmentioning

confidence: 99%

Molecularly Imprinted Polymers

Haupt

Linares

Bompart

et al. 2011

Topics in Current Chemistry

159

119

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Molecular imprinting is a process that allows for the synthesis of artificial receptors for a given target molecule based on synthetic polymers. The target molecule acts as a template around which interacting and cross-linking monomers are arranged and co-polymerized to form a cast-like shell. In essence, a molecular memory is imprinted in the polymer, which is now capable of selectively binding the target. Molecularly imprinted polymers (MIPs) thus possess the most important feature of biological antibodies - specific molecular recognition. They can thus be used in applications where selective binding events are of importance, such as immunoassays, affinity separation, biosensors, and directed synthesis and catalysis. Since its beginnings in the 1970s, the technique of molecular imprinting has greatly diversified during the last decade both from a materials point of view and from an application point of view. Still, there is much room for further improvement. The key challenges, in particular the binding site homogeneity and water compatibility of MIPs, and the possibility of synthesizing MIPs specific for proteins, are actively addressed by research groups over the World. Other important points are the conception of composite materials based on MIPs, in order to include additional interesting properties into the material, and the synthesis of very small and quasi-soluble MIPs, close in size to proteins.

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Determination of a flame retardant hydrolysis product in human urine by SPE and LC?MS. Comparison of molecularly imprinted solid-phase extraction with a mixed-mode anion exchanger

Cited by 67 publications

References 26 publications

Review of OPFRs in animals and humans: Absorption, bioaccumulation, metabolism, and internal exposure research

Review of OPFRs in animals and humans: Absorption, bioaccumulation, metabolism, and internal exposure research

Analysis of the flame retardant metabolites bis(1,3-dichloro-2-propyl) phosphate (BDCPP) and diphenyl phosphate (DPP) in urine using liquid chromatography–tandem mass spectrometry

Molecularly Imprinted Polymers

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