Abstract The rapid and accurate detection of illegal adulteration of chemical drugs into dietary supplements is a big challenge in the food chemistry field. Detection of compounds without a standard reference is even more difficult; however, this is a common situation. Here in this study, a novel “standard‐free detection of adulteration” (SFDA) method was proposed and phosphodiesterase‐5 inhibitor derivatives were used as an example to figure out the possibility and reliability of this SFDA method. After analysis by quadrupole coupled time of flight–tandem mass spectrometry detection and multivariable statistics, six common fragment ions were chosen to indicate whether adulteration was present or not, while 20 characteristic fragment ions indicated whether adulteration was by nitrogen‐containing heterocycles or by anilines. Furthermore, the quantitative methods were conducted by high‐performance liquid chromatography–tandem mass spectrometry. In a word, this strategy allows for a quick determination of dietary supplement adulteration without any need for standard materials, improving the efficacy of food safety testing.

A novel standard‐free detection of adulteration method for sildenafil derivatives in dietary supplements