Comparison of GC–MS and MEKC methods for caffeine determination in preworkout supplements

In this study, GC–MS‐ and MEKC‐based methods for determination of caffeine (CAF) in preworkout supplements were developed and validated. The proposed protocols utilized minimal sample preparation (simple dilution and syringe filtration). The developed methods achieved satisfactory validation parameters, i.e. good linearity (R² > 0.9988 and R² > 0.9985 for GC–MS‐ and MEKC‐based method, respectively), satisfactory intra‐ and interaccuracy (within 92.6–100.7% for method utilizing GC–MS and 92.1–110.3% for protocol based on MEKC) and precision (CV < 15.9% and CV < 6.3% for GC–MS‐ and MEKC‐based method, respectively) and recovery (within 100.1–100.8% for method utilizing GC–MS and 101.5–106.2% for protocol based on MEKC). The LOD was 0.03 and 3 μg/mL for method utilizing GC–MS and MEKC, respectively. The CAF concentrations determined by GC–MS‐ and MEKC‐based methods were found to be in the range of 8.53–11.23 and 8.20–11.61 μg/mL, respectively. Taking into consideration information on the labels, the investigated supplements were found to contain from 110.0 to 167.3% of the declared CAF content, which confirmed the literature reports on incompatibility of the declared product compositions with real ones. Nevertheless, the consumption of examined supplements as recommended by producers did not lead to exceeding the CAF safe limit of 400 mg per day. Additionally, the MEKC‐based method allowed for detection and identification of vitamin B3 and B6 in all of the investigated supplement samples, which demonstrated that MEKC‐based protocols may be an appropriate assays for simultaneous determination of CAF and vitamins.