title: Determination of 1-(2-methoxyphenyl)piperazine derivatives of isocyanates at low concentrations by temperature-programmed miniaturized liquid chromatography.
abstract: A temperature-programmed packed capillary LC method with large-volume injection on-column focusing has been developed for screening and determination of 1-(2-methoxyphenyl)piperazine derivatives of airborne toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, hexamethylenediisocyanate and methylenebisphenyl-4,4-diisocyanate, based on sampling methods described in MDHS 25/3. Injection volumes up to 100 microl were successfully loaded onto the 250x0.32 mm I.D. capillary column packed with 3 microm Hypersil ODS particles. The isocyanate derivatives were loaded at 10 degrees C and eluted by a three-step temperature program starting at 10 degrees C for 10 min, followed by a temperature ramp of 2.5 degrees C min(-1) to 45 degrees C and then 9.9 degrees C min(-1) to 90 degrees C. The mobile phase consisted of acetonitrile-acetate buffer (3% triethylamine, pH 4.5) (45:55, v/v). The isocyanate derivatives were dissolved in acetonitrile-acetate buffer (3% triethylamine, pH 4.5) (30:70, v/v) to achieve sufficient focusing. The concentration limit of detection of the individual derivatives utilizing an "U" shaped flow cell with a 8.0 mm light path and an injection volume of 100 microl was 44, 87, 43 and 210 pg ml(-1) for toluene-2,6-diisocyanate, hexamethylenediisocyanate, toluene-2,4-diisocyanate and methylenebisphenyl-4,4-diisocyanate, respectively. Within the investigated concentration range, 10-500 ng ml(-1), the linear calibration curves gave correlation coefficients ranging from 0.994 to 0.998. The repeatability of the method with regard to retention time and peak height ranged from 0.3 to 1.1% and 1.1 to 2.3% (n=9) relative standard deviation, respectively. The average recovery of the method, with regard to toluene-2,4-diisocyanate, was 97.7+/-1.6% (n=9).
authors.affiliation: Department of Chemistry, University of Oslo, Norway. pal.molander@kjemi.uio.no
authors.forename: P
authors.initials: P
authors.lastname: Molander
authors.forename: K
authors.initials: K
authors.lastname: Haugland
authors.forename: G
authors.initials: G
authors.lastname: Fladseth
authors.forename: E
authors.initials: E
authors.lastname: Lundanes
authors.forename: S
authors.initials: S
authors.lastname: Thorud
authors.forename: Y
authors.initials: Y
authors.lastname: Thomassen
authors.forename: T
authors.initials: T
authors.lastname: Greibrokk
mesh_terms: D002853:Chromatography, Liquid / Q000379:methods*; D017953:Isocyanates / Q000737:chemistry*; D010879:Piperazines / Q000032:analysis*; D015203:Reproducibility of Results; D012680:Sensitivity and Specificity; D013696:Temperature
chemical_list: D017953:Isocyanates; D010879:Piperazines; C040083:1-(2-methoxyphenyl)piperazine