Solid‐Phase Microextraction (SPME) followed by On‐Fiber Derivatization of Solasodine and Solanidine Aglycones of Steroidal Glycoalkaloids

Abstract

Solid‐phase microextraction (SPME), followed by on‐fiber derivatization was investigated for the analysis of the steroidal glycoalkaloid aglycones, solasodine and solanidine. The aglycones were first extracted by direct immersion of the SPME fiber in the sample medium and then derivatized on the fiber in a separate step using 1‐(trimethylsilyl)imidazole (TMSI). The derivatized compounds were then desorbed from the SPME fiber and detected by GC‐MS. Polydimethylsiloxane/Divinylbenzene (PDMS‐DVB), Carboxen/Polydimethylsiloxane (CAR‐PDMS), and Carbowax/Divinylbenzene (CW‐DVB) fibers were employed with the CW‐DVB fibers being the most successful, as expected. Closed‐end capillary tubes were used to hold the extraction media. Both aglycones were successfully extracted, derivatized, and detected by GC‐MS. Solasodine always required derivatization, but solanidine did not. The same method was successfully applied to cholesterol so that it could be used as an internal standard. Also, using the closed‐end capillary tubes, a two‐phase extraction system was also investigated, whereby the fiber was only exposed to the phase in which it was presumed to be less damaged. However, in all cases, fiber degradation was significant, preventing the use of extended extraction times and limiting reuse of the fibers. However, the results represent a first look into the feasibility of the method. With the development of more suitable SPME phases, this method could potentially provide a complementary route for routine determinations of glycoalkaloids for both research and food quality control.