We have demonstrated the use of surface-enhanced Raman scattering (SERS) spectroscopy for the detection of the phenylalkylamines amphetamine and methamphetamine. This work can be viewed as the first phase of development toward a one-step drug detection method with a selective reactive coating on a SERS substrate. This work involves a fairly complicated coupling reaction prior to surface derivatization. Future efforts will be directed at creating a reactive coating directly on the surface. The amines were derivatized by a coupling reaction with 2-mercaptonicotinic acid (2-MNA) with the use of dicyclohexylcarbodiimide (DCC) as the coupling reagent to form the amide compounds AMNA [N-(1-methyl-2-phenylethyl)-2-mercaptopyridine-3-carboxamide] and MMNA [N-methyl-N-(1-methyl-2-phenylethyl)-2-mercaptopyridine-3-carboxamide]. The amides were qualitatively identified from SERS spectra. Quantification of the amides was accomplished by adding the internal standard pentachlorothiophenol (PCTP) and measuring the intensity of Raman bands of the analyte relative to a Raman band of the internal standard. Calibration curves were plotted of the relative peak intensity ratios as a function of analyte concentration. Detection limits of 19 ppm and 17 ppm were found for amphetamine/2-MNA (AMNA) amide and methamphetamine/2-MNA (MMNA) amide, respectively.
Results of a study to detect bilirubin and salicylate using SERS and a reactive coating are presented. The motivation for this work was to develop an assay that would simplify an analysis by detecting the analyte in a whole blood sample. This would remove the risks and time associated with preparing a serum sample. Quantitative analysis was performed using partial least-squares. The results are that one can detect bilirubin and salicylate in whole blood at levels below the normal or therapeutic levels using a coating based on an argentiphilic diazonium molecule. The sharp Raman bands associated with the analyte-coating adduct are sufficiently resolved to allow the analyte to be detected in the presence of a complex matrix such as whole blood.
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