Online Sol-gel Capillary Microextraction-Mass Spectrometry (CME-MS) Analysis of Illicit Drugs

Providing rapid and sensitive sample cleanup, sol-gel capillary microextraction (CME) is a form of solid phase microextraction (SPME). The capillary format of CME couples easily with mass spectrometry (MS) by employing sol-gel sorbent coatings in inexpensive fused silica capillaries. By leveraging the syringe pump and six-port valve readily available on the commercial MS, we can obviate the need for chromatography for samples as complex as urine in quantitative assays. Two different sol-gel materials were studied as microextraction sorbents: one with a single ligand of octadecyl (C₁₈) and the other with a dual-ligand combination of C₁₈ and phenyl (Phe) groups. The CME-MS method was optimized for flow rate and solvent desorption and studied for overall microextraction performance between the two sorbents studied. We extract illicit drugs including cocaine, heroin, amphetamine, methamphetamine, 3,4-methylenedioxymethamphetamine, and oxycodone, proving good run-to-run reproducibility (RSD% < 10%) and low detection limits (< 10 ng mL^-1). The dual-ligand sorbent demonstrated superior performance due to typical hydrophobic properties of C₁₈ as well as potential π-π interactions of the Phe functionality and the aromatic moiety common to many drugs. This study demonstrates the advantage of fine-tuning sol-gel sorbents for application-specific CME-MS. We apply our method to the analysis of various drugs in synthetic and human urine samples and show low carryover effect (~ 5%) and low matrix effect in the presence of the urine matrix. Thus, the sol-gel CME-MS technique described herein stands to be an attractive alternative to other SPME-MS techniques.