Preparation and characterization of molecularly imprinted polymer for di(2-ethylhexyl) phthalate: application to sample clean-up prior to gas chromatographic determination.
The molecularly imprinted polymer (MIP) selective for di(2-ethylhexyl) phthalate (DEHP) an environmental endocrine disruptor was prepared by suspension polymerization using methacrylamide as functional monomer and N,N'-methylene-bis-acrylamide as cross-linker. The imprinted polymer was employed for solid-phase extraction of DEHP from water samples of environmental importance and characterized by FT-IR and SEM. The adsorption properties of the imprinted polymer were demonstrated by equilibrium rebinding experiments, Pseudo-second-order kinetic model, Sips isotherm and Scatchard analysis. The reusability of MIP was checked for at least six repeated batch adsorption cycles and the results showed almost no deterioration in the adsorption capacity. The competitive recognition studies were performed with DEHP and structurally similar compounds; dimethyl phthalate (DMP), diethyl phthalate (DEP), and dibutyl phthalate (DBP). The imprinting factor (IF) of DEHP was found to be 12.86 which was much higher than the imprinting factors (IF) of other phthalates. A method constituted by molecularly imprinted solid-phase extraction (MISPE) with GC-FID was developed for DEHP analysis in water samples under very simple conditions. Sample loading and desorption conditions were also optimized. The MISPE method's linearity ranged from 0.035 to 3.0 μg ml⁻¹ with r² = 0.9998. Intra-assay, interassay precision and accuracy ranged from 0.0168% to 1.017%, 1.130% to 4.799% and 94.98% to 99.35%, respectively. The LOD and LOQ were found to be 0.011 and 0.035 μg ml⁻¹, respectively. Synthesized MIP was employed in MISPE for cleaning up the spiked river water samples prior to gas chromatographic analysis. The river samples were found to contain DEHP in the range of 1.4 × 10⁻³ to 0.349 μg ml⁻¹.
National Center of Excellence in Analytical Chemistry, University of Sindh, Jamshoro 76080, Pakistan.
Huma
H
Shaikh
Najma
N
Memon
Hamayun
H
Khan
M I
MI
Bhanger
S M
SM
Nizamani
D000178:Acrylamides / Q000737:chemistry; D000327:Adsorption; D002849:Chromatography, Gas / Q000379:methods*; D004051:Diethylhexyl Phthalate / Q000032:analysis / Q000737:chemistry* / Q000302:isolation & purification; D017743:Equipment Reuse; D007700:Kinetics; D016014:Linear Models; D054802:Molecular Imprinting / Q000379:methods*; D011108:Polymers / Q000138:chemical synthesis / Q000737:chemistry*; D045483:Rivers / Q000737:chemistry; D052616:Solid Phase Extraction / Q000295:instrumentation* / Q000379:methods; D014874:Water Pollutants, Chemical / Q000032:analysis / Q000737:chemistry / Q000302:isolation & purification
D000178:Acrylamides; D011108:Polymers; D014874:Water Pollutants, Chemical; D004051:Diethylhexyl Phthalate; C021221:N,N'-methylenebisacrylamide; C045985:methacrylamide