In this review, the ever-increasing use of deep eutectic solvents (DES) in microextraction techniques will be discussed, focusing on the reasons needed to replace conventional extraction techniques with greener approaches that follow the principles of green analytical chemistry. The properties of DES will be discussed, pinpointing their exceptional performance and analytical parameters, justifying their current extensive scientific interest. Finally, a variety of applications for commonly used microextraction techniques will be reported.

Nowadays, the interest in preparing new, cheap and simple adsorbents that are used in sample preparation is on the rise. Graphene oxide (GO) nanomaterials and nanocomposites have become increasingly popular due to the novel methods of syntheses that have been published. Owing to their vast specific surface area and their π-delocalized electron system they possess, they are appropriate for the adsorption of a variety of aromatic organic compounds, being utilized either as adsorbents in analytical methods or as filter materials for the removal of pollutants in water. Pharmaceutical compounds, such as benzodiazepines, end up in surface waters caused by consumption or their disposal through sewage, thus becoming pollutants. In the present study, an analytical method has been developed and validated for the determination of two model-analytes of benzodiazepines by HPLC-DAD and their sample preparation protocol which consists of the Stir bar magnetic solid phase extraction (SB-MSPE) method, evaluating therefore the nanocomposite material as a decent adsorbent. The separation took place with the usage of an analytical column C18 RP-HPLC in 10 min. For the alprazolam (ALP) and the flunitrazepam (FLT), the LODs and LOQs were 3 ng/mL and 10 ng/mL, respectively, while the relative recoveries ranged between 93.6–112.9% and the RSDs were 1.11–9.50%. Finally, the material was examined for its reusability and was found that it can be used for over eight cycles of extraction/elution.

The quantitative determination of xenobiotic compounds, as well as biotics in biological matrices, is generally described with the term bioanalysis. Due to the complexity of biofluids, in combination with the low concentration of the small molecules, their determination in biological matrices is a challenging procedure. Apart from the conventional solid-phase extraction, liquid-liquid extraction, protein precipitation, and direct injection approaches, nowadays, a plethora of microextraction and miniaturized extraction techniques have been reported. Furthermore, the development and evaluation of novel extraction adsorbents for sample preparation has become a popular research field. Metal-organic frameworks (MOFs) are novel materials composed of metal ions or clusters in coordination with organic linkers. Unequivocally, MOFs are gaining more and more attention in analytical chemistry due to their superior properties, including high surface area and tunability of pore size and functionality. This review discusses the utilization of MOFs in the sample preparation of biological samples for the green extraction of small organic molecules. Their common preparation and characterization strategies are discussed, while emphasis is given to their applications for green sample preparation.

The use of deep eutectic solvents (DES) is on the rise worldwide because of the astounding properties they offer, such as simplicity of synthesis and utilization, low-cost, and environmental friendliness, which can, without a doubt, replace conventional solvents used in heaps. In this review, the focus will be on the usage of DES in extracting a substantial variety of organic compounds from different sample matrices, which not only exhibit great results but surpass the analytical performance of conventional solvents. Moreover, the properties of the most commonly used DES will be summarized.