Free and Esterified Tocopherols, Tocotrienols and Other Extractable and Non-Extractable Tocochromanol-Related Molecules: Compendium of Knowledge, Future Perspectives and Recommendations for Chromatographic Techniques, Tools, and Approaches Used for Tocochromanol Determination.

Free and esterified (bound) tocopherols, tocotrienols and other tocochromanol-related compounds, often referred to "tocols", are lipophilic antioxidants of great importance for health. For instance, α-tocopherol is the only tocochromanol with vitamin E activity, while tocotrienols have a positive impact on health and are proposed in the prevention and therapy of so-called modern diseases. Tocopherols, tocotrienols and plastochromanol-8 are the most well-known tocochromanols; in turn, knowledge about tocodienols, tocomonoenols, and other rare tocochromanol-related compounds is limited due to several challenges in analytical chemistry and/or low concentration in plant material. The presence of free, esterified, and non-extractable tocochromanols in plant material as well as their biological function, which may be of great scientific, agricultural and medicinal importance, is also poorly studied. Due to the lack of modern protocols as well as equipment and tools, for instance, techniques suitable for the efficient and simultaneous chromatographical separation of major and minor tocochromanols, the topic requires attention and new solutions, and/or standardization, and proper terminology. This review discusses the advantages and disadvantages of different chromatographic techniques, tools and approaches used for the separation and detection of different tocochromanols in plant material and foodstuffs. Sources of tocochromanols and procedures for obtaining different tocochromanol analytical standards are also described. Finally, future challenges are discussed and perspective green techniques for tocochromanol determination are proposed along with best practice recommendations. The present manuscript aims to present key aspects and protocols related to tocochromanol determination, correct identification, and the interpretation of obtained results.