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Supramolecular solvents (SUPRASs) have been long recognized as outstanding extractants in analytical processes. In addition to their remarkable properties for solubilization of a number of polar and apolar compounds using minute volumes of solvent, they can be tailored at will and produced spontaneously at reduced cost. Although not enough effort has been devoted to the synthesis of new solvents and elucidation of their structure, important progress has been performed in the past decade to the development of new formats and the coupling to different detection systems. This article gives an overview of the state of art of how solvents are produced, their capability for extraction and concentration, the formats used, the strategies developed to make SUPRASs compatible with a number of detection systems, and major applications reported on the extraction of metals and organic compounds in the biological, environmental, and agrifood areas.

Supramolecular analytical chemistry is an emergent science covering the study and application of supramolecular systems (host molecules and molecular aggregates) in analytical processes. This article covers the progress on both theoretical and practical aspects related to the use of supramolecular systems in separation techniques reported over the last decade. Principles of supramolecular chemistry that allow a better understanding of the mechanisms of formation of the supramolecular entities and solubilization of solutes are outlined. Developments related to the use of supramolecular solvents and hemimicellar or admicellar sorbents in analytical extractions are critically discussed. Advances in the use of micelles in liquid chromatography (LC) and electrophoresis as well as developments in chiral chromatography and electrophoresis based on the use of cyclodextrins (CDs) and their derivatives are presented. Emphasis is placed on the strategies developed to make these techniques compatible with mass spectrometry (MS). The capability of supramolecular systems to effectively solubilize solutes in a wide polarity range is highlighted. Keywords: supramolecular analytical chemistry; liquid chromatography; gas chromatography; capillary electrophoresis; cyclodextrins; supramolecular solvents; hemimicelles/admicelles