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Current trends in Analytical Chemistry are focused on the development and application of safer and more environmentally friendly procedures that meet the Green Analytical Chemistry principles. In this sense, since their introduction by Abbott et al. in 2003, deep eutectic solvents (DESs) have gained importance as solvents of great utility in extraction processes, due to their low toxicity, easy preparation, and good physicochemical properties, as well as their low cost and their biodegradability. In recent years, DESs synthesized from natural compounds such as sugars, alcohols, and amino acids, named natural DESs (NADESs), have aroused the interest of the scientific community since the toxicity of these eutectic mixtures is non-existent or negligible and at the same time they are highly biodegradable. In fact, one of the most attractive properties of NADESs is that they can be both biosynthesized and metabolized by most organisms, which explains why they are highly biocompatible, making them excellent solvents to be considered in analytical applications. The aim of this book chapter is to provide an overview of the different DESs that have been used up to now in the Analytical Chemistry field in the development of green sample preparation approaches.

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