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Determination of amines as pentafluoropropionic acid anhydride derivatives in biological samples using liquid chromatography and tandem mass spectrometry
Stockholm University, Faculty of Science, Department of Analytical Chemistry.
Stockholm University, Faculty of Science, Department of Analytical Chemistry.
Stockholm University, Faculty of Science, Department of Analytical Chemistry.
2004 (English)In: The Analyst, ISSN 0003-2654, Vol. 129, no 6, 522-528 p.Article in journal (Refereed) Published
Abstract [en]

Determination of amines in biological samples as markers of exposure to the amines or the corresponding isocyanates is an important tool for industrial exposure assessment. In this study, a liquid chromatography and tandem mass spectrometry (LC- MS/ MS) method for determination of amines in biological samples as perfluorofatty amides derivatives is presented. The method enables determination of diamines such as methylene diamine (MDA), toluene diamine (TDA), naphthalene diamine (NDA), hexamethylene diamine (HDA), isophorone diamine (IPDA), methylenedi( cyclohexylamine) (HMDA) and 4,4'-methylene-(2-chloroaniline) (MOCA) in human urine and plasma. The work-up procedure included hydrolysis of the biological samples with 3 M H2SO4 at 100degreesC for 16 h and extraction of the amines into toluene, where derivatisation of the amines with perfluorofatty acid anhydride was performed. Following removal of excess reagent and the acid formed and an exchange of solvent, the derivatives were analysed using gradient elution with an acetonitrile/water mobile phase composition and electrospray ionisation (ESI) with multiple reaction monitoring (MRM) of [M - H](-) --> [M - H - 120](-) or [119](-). Several perfluorofatty acid anhydrides were evaluated as derivatisation reagents, but the LC chromatographic properties of the pentafluoropropionic acid anhydride (PFPA) derivatives were favourable. Quantification of amine - PFPA derivatives was performed using deuterium labelled amine - PFPA derivatives as internals standards with good precision and linearity in the investigated range of 0 - 20 ng ml(-1) urine. The instrumental detection limits for the amine - PFPA derivatives were 0.2 - 3 fmol for MRM of [M - H](-) --> [119](-) and 0.3 - 8 fmol for [M - H](-) --> [M - H - 120](-). In 10 urine and 6 plasma samples from workers exposed to isocyanates, determination of TDA and MDA as PFPA derivatives was performed using LC- MS/ MS and a reference GC-MS method. No significant difference between the two methods was observed.

Place, publisher, year, edition, pages
Royal Society of Chemistry , 2004. Vol. 129, no 6, 522-528 p.
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
URN: urn:nbn:se:su:diva-23251DOI: 10.1039/b403439bOAI: oai:DiVA.org:su-23251DiVA: diva2:190908
Note
Part of urn:nbn:se:su:diva-204Available from: 2004-08-20 Created: 2004-08-20 Last updated: 2010-01-05Bibliographically approved
In thesis
1. Isocyanates and Amines – Sampling and Analytical Procedures
Open this publication in new window or tab >>Isocyanates and Amines – Sampling and Analytical Procedures
2004 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis covers sampling and analytical procedures for isocyanates (R-NCO) and amines (R-NH2), two kinds of chemicals frequently used in association with the polymeric material polyurethane (PUR). Exposure to isocyanates may result in respiratory disorders and dermal sensitisation, and they are one of the main causes of occupational asthma. Several of the aromatic diamines associated with PUR production are classified as suspected carcinogens. Hence, the presence of these chemicals in different exposure situations must be monitored.

In the context of determining isocyanates in air, the methodologies included derivatisation with the reagent di-n-butylamine (DBA) upon collection and subsequent determination using liquid chromatography (LC) and mass spectrometric detection (MS). A user-friendly solvent-free sampler for collection of airborne isocyanates was developed as an alternative to a more cumbersome impinger-filter sampling technique. The combination of the DBA reagent together with MS detection techniques revealed several new exposure situations for isocyanates, such as isocyanic acid during thermal degradation of PUR and urea-based resins. Further, a method for characterising isocyanates in technical products used in the production of PUR was developed. This enabled determination of isocyanates in air for which pure analytical standards are missing. Tandem MS (MS/MS) determination of isocyanates in air below 10-6 of the threshold limit values was achieved.

As for the determination of amines, the analytical methods included derivatisation into pentafluoropropionic amide or ethyl carbamate ester derivatives and subsequent MS analysis. Several amines in biological fluids, as markers of exposure for either the amines themselves or the corresponding isocyanates, were determined by LC-MS/MS at amol level. In aqueous extraction solutions of flexible PUR foam products, toluene diamine and related compounds were found.

In conclusion, this thesis demonstrates the usefulness of well characterised analytical procedures and techniques for determination of hazardous compounds. Without reliable and robust methodologies there is a risk that exposure levels will be underestimated or, even worse, that relevant compounds will be completely missed.

Place, publisher, year, edition, pages
Stockholm: Institutionen för analytisk kemi, 2004. 65 p.
Keyword
Isocyanates, Amines, Polyurethane, Air sampling, Industrial hygiene, Mass spectrometry, Liquid chromatography, Chemiluminescence
National Category
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-204 (URN)91-7265-917-3 (ISBN)
Public defence
2004-09-10, Vita salongen, Hässleholms kulturhus, Järnvägsgatan 23, Hässleholm, 10:00
Opponent
Supervisors
Available from: 2004-08-20 Created: 2004-08-20Bibliographically approved

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