Selective molecularly imprinted polymer combined with restricted access material for in-tube SPME/UHPLC-MS/MS of parabens in breast milk samples

Author(s)

Souza, Israel D. ^[1] ; Melo, Lidervan P. ^[1] ; Jardim, Isabel C. S. F. ^[2] ; Monteiro, Juliana C. S. ^[3] ; Nakano, Ana Marcia S. ^[3] ; Queiroz, Maria Eugenia C. ^[1]

Affiliation

^[1] Univ Sao Paulo, Dept Quim, Fac Filosofia Ciencias & Letras Ribeirao Preto, BR-14049 Ribeirao Preto, SP - Brazil

^[2] Univ Estadual Campinas, Inst Quim, Campinas, SP - Brazil

^[3] Univ Sao Paulo, Escola Enfermagem Ribeirao Preto, BR-14049 Ribeirao Preto, SP - Brazil

• Document type: Journal article
• Source: Analytica Chimica Acta; v. 932, p. 49-59, AUG 17 2016.
• Web of Science Citations: 31

Abstract

A new molecularly imprinted polymer modified with restricted access material (a hydrophilic external layer), (MIP-RAM) was synthesized via polymerization in situ in an open fused silica capillary. This stationary phase was used as sorbent for in-tube solid phase microextraction (in-tube SPME) to determine parabens in breast milk samples by ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). Scanning electron micrographs (SEM) illustrate MIP surface modification after glycerol dimethacrylate (hydrophilic monomer) incorporation. The interaction between parabens and MIP-RAM was investigated by Fourier-transform infrared (FTIR) spectroscopy. The Scatchard plot for MIP-RAM presented two linear parts with different slopes, illustrating binding sites with high-and low-affinity. Endogenous compounds exclusion from the MIP-RAM capillary was demonstrated by in-tube SPME/LC-UV assays carried out with blank milk samples. The in-tube SPME/UHPLC-MS/MS method presented linear range from 10 ng mL(-1) (LLOQ) to 400 ng mL(-1) with coefficients of determination higher than 0.99, inter-assay precision with coefficient of variation (CV) values ranging from 2 to 15%, and interassay accuracy with relative standard deviation (RSD) values ranging from -1% to 19%. Analytical validation parameters attested that in-tube SPME/UHPLC-MS/MS is an appropriate method to determine parabens in human milk samples to assess human exposure to these compounds. Analysis of breast milk samples from lactating women demonstrated that the proposed method is effective. (C) 2016 Elsevier B.V. All rights reserved. (AU)

• FAPESP's process: 12/07949-3 - Development of molecularly imprinted extraction phase with hydrophilic coating (MIP-RAM) for analysis in-tube SPME/LC-MS/MS of parabens in human milk samples
• Grantee: Lidervan de Paula Melo
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 12/10705-9 - Development of selective phases for in-tube SPME/LC-MS/MS analysis of parabens and drugs in biological samples
• Grantee: Maria Eugênia Queiroz Nassur
• Support Opportunities: Regular Research Grants