Critical development by design of a rugged HPLC-MS/MS method for direct determination of ibuprofen enantiomers in human plasma

J Chromatogr B Analyt Technol Biomed Life Sci. 2015 Jun 15:992:67-75. doi: 10.1016/j.jchromb.2015.04.029. Epub 2015 Apr 25.

Abstract

Development and validation of a HPLC-MS/MS method for direct determination of R- and S-ibuprofen (Ibu) in human plasma without a need of derivatization or other complexities such as postcolumn infusion of solvents or reagents was performed. Critical steps were investigated during method development using experimental design to achieve a reliable and rugged assay. The LC-MS/MS separation of R-Ibu and S-Ibu was obtained on Lux Cellulose chiral column utilizing 0.1% (v/v) acetic acid in mixture of methanol and water (90:10%, v/v) as a mobile phase. Two types of extraction procedure for Ibu and Ketoprofen (internal standard, IS) were optimized using Full factorial 3(2) design (LLE) and D-Optimal Experimental Design (SPE). Excellent recovery values, 80% (mean) and 95% (mean) for LLE and SPE respectively, were obtained using 50μL plasma. The matrix effect was assessed for both of the extraction procedures, including hyperlipidaemic and haemolyzed plasma. The extensive investigation of matrix effect showed that LLE yields cleaner extracts than the SPE. The result of the investigation of in vitro interconversion of R-Ibu and S-Ibu showed that it does not occur under the influence of pH, temperature, and in the overall analytical procedure. The validation data, adhered to EMA guideline for validation of bioanalytical methods, showed that the proposed method provides accurate and reproducible results in range of 0.1-50mg/L with a lower limit of detection of 0.02mg/L. The applicability of the method was demonstrated through determination of R-Ibu and S-Ibu in human plasma after oral administration of 400mg rac-Ibu.

Keywords: Experimental design; Ibuprofen enantiomers; LC-MS/MS; Matrix effect; Sample preparation; in vitro Chiral interconversion.

MeSH terms

  • Adult
  • Chromatography, High Pressure Liquid / methods*
  • Humans
  • Ibuprofen / blood*
  • Ibuprofen / chemistry*
  • Ibuprofen / pharmacokinetics
  • Limit of Detection
  • Linear Models
  • Liquid-Liquid Extraction
  • Reproducibility of Results
  • Solid Phase Extraction
  • Stereoisomerism
  • Tandem Mass Spectrometry / methods*

Substances

  • Ibuprofen