Greenness of magnetic nanomaterials in miniaturized extraction techniques: A review

Green analytical chemistry principles should be followed, as much as possible, and particularly during the development of analytical sample preparation methods. In the past few years, outstanding materials such as ionic liquids, metal-organic frameworks, carbonaceous materials, molecularly imprinted materials, and many others, have been introduced in a wide variety of miniaturized techniques in order to reduce the amount of solvents and sorbents required during the analytical sample preparation step while pursuing more efficient extraction methods. Among them, magnetic nanomaterials (MNMs) have gained special attention due to their versatile properties. Mainly, their ability to be separated from the sample matrix using an external magnetic field (thus enormously simplifying the entire process) and their easy combination with other materials, which implies the inclusion of a countless number of different functionalities, highly specific in some cases. Therefore, MNMs can be used as sorbents or as magnetic support for other materials which do not have magnetic properties, the latter permiting their combination with novel materials. The greenness of these magnetic sorbents in miniaturized extractions techniques is generally demonstrated in terms of their ease of separation and amount of sorbent required, while the nature of the material itself is left unnoticed. However, the synthesis of MNMs is not always as green as their applications, and the resulting MNMs are not always as safe as desired. Is the analytical sample preparation field ready for using green magnetic nanomaterials? This review offers an overview, from a green analytical chemistry perspective, of the current state of the use of MNMs as sorbents in microextraction strategies, their preparation, and the analytical performance offered, together with a critical discussion on where efforts should go.