Graduation Year

2011

Document Type

Thesis

Degree

M.S.

Degree Granting Department

Chemistry

Major Professor

Abdul Malik, Ph.D.

Committee Member

Kirpal Bisht, Ph.D.

Committee Member

Xiao Li, Ph.D.

Keywords

Capillary Microextraction, Non-exhaustive, Preconcentration, Sol-gel coating, Solvent-free, Trace analysis

Abstract

For the first time, octahydroxyl methylresorcinarene with four hexyl groups on the lower rim was utilized in the in-situ preparation of a silica-based sol-gel organicinorganic hybrid coating for sample preconcentration by capillary microextraction (CME). Tetraethoxysilane (TEOS) was chosen as a sol-gel precursor to create a crosslinked sol-gel network via acid-catalyzed hydrolytic polycondensation reactions. Sol-gel chemistry helped in the in situ preparation of resorcinarene-containing extraction phase in the form of a surface coating. It also provided an effective means to chemically bind the coating to the inner surface of fused silica capillary via condensation of the hydroxyl groups in the sol-gel network with the silanol groups on the fused silica capillary inner surface. These chemically bonded sol-gel coatings demonstrated excellent thermal stability (up to 350 oC). The sol-gel resorcinarene coatings successfully extracted traces of polycyclic aromatic hydrocarbons (PAHs), ketones, phenols, amines, and alcohols from aqueous samples providing parts per trillion level detection limits (0.828 – 46.01 ng/L) in GC using a Flame Ionization Detector (FID). CME was performed by passing the aqueous samples through the resorcinarene coated microextraction capillary (10 cm). The extracted analytes where then thermally desorbed into the GC column connected to the exit end of the sol-gel microextraction capillary via a press-fit quartz connector. Peak x area relative standard deviation (RSD %), a measure of the extraction performance reproducibility for the coated capillary, was found in the range of (1.1 % - 8.3 %). The sol-gel resorcinarene sorbent was characterized by FTIR spectrum which indicated the presence of hydroxyl groups in the coating even after the sol-gel reactions were completed which explains the affinity of the resorcinarene sol-gel coating toward polar analytes. Scanning Electron Microscopy (SEM) images of the coating revealed the porous morphology and thickness of 3.5 – 4.0 µm for the coating. The sol-gel resorcinarene coated capillary provided excellent extraction performance for wide range of analytes.

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