Novel Applications of Microextraction Techniques Focused on Biological and Forensic Analyses

In recent years, major attention has been focused on microextraction procedures that allow high recovery of target analytes, regardless of the complexity of the sample matrices. The most used techniques included liquid-liquid extraction (LLE), solid-phase extraction (SPE), solid-phase microextraction (SPME), dispersive liquid-liquid microextraction (DLLME), microextraction by packed sorbent (MEPS), and fabric-phase sorptive extraction (FPSE). These techniques manifest a rapid development of sample preparation techniques in different fields, such as biological, environmental, food sciences, natural products, forensic medicine, and toxicology. In the biological and forensic fields, where a wide variety of drugs with different chemical properties are analyzed, the sample preparation is required to make the sample suitable for the instrumental analysis, which often includes gas chromatography (GC) and liquid chromatography (LC) coupled with mass detectors or tandem mass detectors (MS/MS). In this review, we have focused our attention on the biological and forensic application of these innovative procedures, highlighting the major advantages and results that have been accomplished in laboratory and clinical practice.

Solventless Microextration Techniques for Pharmaceutical Analysis: The Greener Solution

Extensive efforts have been made in the last decades to simplify the holistic sample preparation process. The idea of maximizing the extraction efficiency along with the reduction of extraction time, minimization/elimination of hazardous solvents, and miniaturization of the extraction device, eliminating sample pre- and posttreatment steps and reducing the sample volume requirement is always the goal for an analyst as it ensures the method’s congruency with the green analytical chemistry (GAC) principles and steps toward sustainability. In this context, the microextraction techniques such as solid-phase microextraction (SPME), stir bar sorptive extraction (SBSE), microextraction by packed sorbent (MEPS), fabric phase sorptive extraction (FPSE), in-tube extraction dynamic headspace (ITEX-DHS), and PAL SPME Arrow are being very active areas of research. To help transition into wider applications, the new solventless microextraction techniques have to be commercialized, automated, and validated, and their operating principles to be anchored to theory. In this work, the benefits and drawbacks of the advanced microextraction techniques will be discussed and compared, together with their applicability to the analysis of pharmaceuticals in different matrices.

Determination of Benzophenones in Water and Cosmetics Samples: A Comparison of Solid-Phase Extraction and Microextraction by Packed Sorbent Methods

Benzophenones (BPs) are extensively used in a wide variety of cosmetic products and other materials (e.g., textiles or plastics) to avoid damaging effects of UV radiation. In the present work, we compared two extraction methods for the determination of BPs, namely, 2,4-dihydroxybenzophenone (BP-1), 2-hydroxy-4-methoxybenzophenone (BP-3) and 2,2-dihydroxy-4-methoxybenzophenone (BP-8), in water and cosmetics samples. The following extraction methods were used for the research: solid-phase extraction (SPE) and microextraction by packed sorbent (MEPS), whereas analysis was performed by gas chromatography with mass spectrometric detection. A comparison between the methods indicates that the MEPS technique(s) can be reliably used for analysis of BPs (sunscreen residue) in water samples and cosmetic samples with satisfactory results. This microextraction technique is cheap, easy, quick to implement, and consumes small amounts of solvents. On the other hand, the main advantage of the SPE method are low detection limits for the determination of BPs in water samples, i.e., from 0.034 to 0.067 µg L−1, while, for the MEPS method, LODs were at the level of 1.8–3.2 µg L−1. For both methods, the recoveries of BPs were 96–107% and 44–70% for water and cosmetics samples, respectively. The presented methods are suitable for use in cosmetics quality control and environmental pollution assessment.

Simultaneous Quantification of 25 Fentanyl Derivatives and Metabolites in Oral Fluid by Means of Microextraction on Packed Sorbent and LC–HRMS/MS Analysis

Fentanyl and fentalogs’ intake as drugs of abuse is experiencing a great increase in recent years. For this reason, there are more and more cases in which it is important to recognize and quantify these molecules and related metabolites in biological matrices. Oral fluid (OF) is often used to find out if a subject has recently used a psychoactive substance and if, therefore, the person is still under the effect of psychotropics. Given its difficulty in handling, good sample preparation and the development of instrumental methods for analysis are essential. In this work, an analytical method is proposed for the simultaneous determination of 25 analytes, including fentanyl, several derivatives and metabolites. OF was collected by means of passive drool; sample pretreatment was developed in order to be fast, simple and possibly semi-automated by exploiting microextraction on packed sorbent (MEPS). The analysis was performed by means of LC–HRMS/MS obtaining good identification and quantification of all the analytes in less than 10 min. The proposed method was fully validated according to the Scientific Working Group for Forensic Toxicology (SWGTOX) international guidelines. Good results were obtained in terms of recoveries, matrix effect and sensitivity, showing that this method could represent a useful tool in forensic toxicology. The presented method was successfully applied to the analysis of proficiency test samples.

Metabolic Profiling and Quantitative Analysis of Cerebrospinal Fluid Using Gas Chromatography–Mass Spectrometry: Current Methods and Future Perspectives

Cerebrospinal fluid is a key biological fluid for the investigation of new potential biomarkers of central nervous system diseases. Gas chromatography coupled to mass-selective detectors can be used for this investigation at the stages of metabolic profiling and method development. Different sample preparation conditions, including extraction and derivatization, can be applied for the analysis of the most of low-molecular-weight compounds of the cerebrospinal fluid, including metabolites of tryptophan, arachidonic acid, glucose; amino, polyunsaturated fatty and other organic acids; neuroactive steroids; drugs; and toxic metabolites. The literature data analysis revealed the absence of fully validated methods for cerebrospinal fluid analysis, and it presents opportunities for scientists to develop and validate analytical protocols using modern sample preparation techniques, such as microextraction by packed sorbent, dispersive liquid–liquid microextraction, and other potentially applicable techniques.