Microextraction By Packed Sorbent Research Articles

Determination of amphetamines in hair samples using microextraction by packed sorbent and gas chromatography-mass spectrometry.

Several protocols for the analysis of amphetamine-type stimulants (ATS) in hair have been developed over the years, with microextraction by packed sorbent (MEPS) being used for drugs like opiates, cocaine and ketamine. However, concerning ATS determination in hair samples, this approach has only been applied so far to amphetamine (AMP) and methamphetamine (MAMP). This study aimed at developing and validating a MEPS-based procedure for the determination in hair of not only AMP and MAMP but also of 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxymethamphetamine (MDMA), 1-(1,3-benzodioxol-5-yl)propan-2-yl (ethyl)amine (MDE) and N-methyl-1-(1,3-benzodioxol-5-yl)-2-aminobutane (MBDB) as well. Hair, 50 mg, was incubated with 1M sodium hydroxide (NaOH) at 45°C overnight, neutralization with 10M hydrochloric acid (HCl) and centrifugation followed. The design of experiments approach was used for MEPS optimization, with the final optimized conditions including conditioning (250 μL methanol and deionized water), loading (18 × 100 μL) and elution (7× 100 μL 2% NH4OH in acetonitrile). The eluted extract was evaporated to dryness and underwent microwave-assisted derivatization with N-methyl-bis(trifluoroacetamide) (MBTFA), and it was afterwards injected onto the gas chromatography-mass spectrometer (GC-MS). The obtained recoveries ranged between 8% and 14% for AMP, 14% and 20% for MAMP, 10% and 15% for MDA, 18% and 28% for MDMA, 25% and 43% for MDE and 34% and 52% for MBDB, and the method was linear from 0.2 to 5.0ng/mg. Precision and accuracy were in accordance with international method validation guidelines. This novel method involving MEPS coupled to GC-MS offers a swift, eco-friendly and cost-effective alternative to traditional procedures for detecting these AMPs in hair samples.

Integration of miniaturized sample preparation and molecularly imprinted polymers in food analysis

The use of innumerable chemical compounds in food production to enhance agricultural quality and yield has raised significant global concerns regarding food safety. To address these concerns, miniaturized solid sample preparation techniques have emerged as an appealing strategy for analyzing chemical residues in complex samples, notably those found in food matrices. The efficacy of these miniaturized solid extraction procedures hinges largely on the choice of the sorbent phase. Molecularly imprinted polymers (MIPs) have been introduced as highly selective and versatile sorbent phases for a wide range of miniaturized solid techniques. Their remarkable selectivity is attributed to the creation of distinct cavities during the synthesis process, which subsequently accommodate the target analyte when the sample is applied. This unique characteristic empowers MIP polymers to exhibit exceptional specificity toward the desired analyte. The use of MIPs as sorbent phases in miniaturized sample preparation methods has shown great potential to increase the analytical performance of residue evaluation in food matrices. Therefore, here we present a comprehensive overview of the current landscape of miniaturized solid sample techniques employing MIPs as sorbent phases for the assessment of residues in food samples. Moreover, this review is primarily on recent reports concerning the application of MIPs in solid-phase microextraction (SPME), in-tube SPME, microextraction by packed sorbent (MEPS), disposable pipette extraction (DPX), solid-phase extraction in pipette tip (SPE-PT) and stir bar sorptive extraction (SBSE). Lastly, we will bring some future topics concerning the use of MIPs in miniaturized sample preparation methods for food analysis in order to bring some new avenues for enhancing food products' safety and quality assessment.

Quantification of antidepressants in oral fluid and plasma samples using microextraction by packed sorbent and analysis by gas chromatography-tandem mass spectrometry

The consumption of antidepressants is extremely significant as they are a class of medications widely used in the treatment of numerous disorders and are therefore considered a public health problem throughout the world. The aim of this work was to develop and optimize two methodologies for the determination of selected antidepressants and metabolites (fluoxetine, venlafaxine, O-desmethylvenlafaxine, citalopram, sertraline, paroxetine), in 250 µL of sample (oral fluid and plasma) using microextraction by packed sorbent (MEPS) as the extraction technique and gas chromatography coupled to tandem mass spectrometry (GC–MS/MS) for analysis. The two methods were fully validated considering the internationally accepted criteria for bioanalytical procedures, presenting linearity within the studied range, with limits of quantification between 10 and 100 ng/mL, coefficients of determination (R2) of at least 0.99 and precision and accuracy with acceptable values of coefficients of variation and relative errors for all antidepressants in study and for both specimens. Recoveries ranged between approximately 12 and 93 % for oral fluid samples and between approximately 28 and 101 % for plasma samples. To our best knowledge, the described methods are the first to be reported using MEPS and GC–MS/MS for the identification of antidepressants in oral fluid and plasma samples, proving to be sensitive, simple, fast and capable of being applied in routine clinical and forensic toxicology scenarios.

A molecularly imprinted polymer for microextraction by packed sorbent of sulfonylureas herbicides from corn samples

A molecularly imprinted polymer (MIP) was synthesized and assessed as a selective extraction phase in the microextraction by packed sorbent (MEPS) of sulfonylureas herbicides (SUHs) — Thifensulfuron, Chlorosulfuron, Tribenuron, and Bensulfuron — from grounded corn samples. Bensulfuron was employed as the template for the MIP preparation. MIP particles were chemically and structurally characterized. Distribution (Kd), selectivity (k), and relative selectivity (k') coefficients were estimated using binary mixtures of bensulfuron/betazon and bensulfuron/prometon. The most significant parameters affecting the MEPS performance were systematically studied in univariate and multivariate experiments. Analyses were performed by liquid chromatography coupled to time-of-flight mass spectrometry (LC-ToF). Under selected conditions, the developed MIP-MEPS-LC-ToF method demonstrated suitable analytical confidence and reliability. Determination coefficients (r2) higher than 0.9940, and limits of detection (LODs) of 2.5 µg kg-1 were obtained. Intra- and interday precision was lower than 14.2%, and accuracy ranged between 89.6% and 113.6%. The synthesized MIP demonstrated enhanced selectivity and higher SUHs uptake capability compared to the non-imprinted polymer (NIP) and tested commercial sorbents. Besides, the method is a cheap, feasible, and environmentally friendly analytical tool. A single MEPS device packed with 1.0 mg of MIP was reused more than 180 times without loss in its extraction capabilities.

Green analytical toxicology method for determination of synthetic cathinones in oral fluid samples by microextraction by packed sorbent and liquid chromatography-tandem mass spectrometry.

We developed and validated a method for quantitative analysis of ten synthetic cathinones in oral fluid (OF) samples, using microextraction by packed sorbent (MEPS) for sample preparation followed by liquid chromatography‒tandem mass spectrometry (LC‒MS/MS). OF samples were collected with a Quantisal™ device and 200 µL was extracted using a C18 MEPS cartridge installed on a semi-automated pipette and then analyzed using LC‒M/SMS. Linearity was achieved between 0.1 and 25ng/mL, with a limit of detection (LOD) of 0.05ng/mL and a limit of quantification (LOQ) of 0.1ng/mL. Imprecision (% relative standard deviation) and bias (%) were better than 11.6% and 7.5%, respectively. The method had good specificity and selectivity against 9 different blank OF samples (from different donors) and 68 pharmaceutical and drugs of abuse with concentrations varying between 400 and 10,000ng/mL. No evidence of carryover was observed. The analytes were stable after three freeze/thaw cycles and when kept in the autosampler (10°C) for up to 24h. The method was successfully applied to quantify 41 authentic positive samples. Methylone (mean 0.6ng/mL, median 0.2ng/mL), N-ethylpentylone (mean 16.7ng/mL, median 0.35ng/mL), eutylone (mean 39.1ng/mL, median 3.6ng/mL), mephedrone (mean 0.5ng/mL, median 0.5ng/mL), and 4-chloroethcathinone (8.1ng/mL) were quantified in these samples. MEPS was an efficient technique for Green Analytical Toxicology purposes, which required only 650 µL organic solvent and 200 µL sodium hydroxide, and the BIN cartridge had a lifespan of 100 sample extractions.

Microextraction by packed sorbent of some β-blocker drugs with chitosan@mof-199 bio-composite in human saliva, plasma, and urine samples

The current study introduces microextraction by packed sorbent (MEPS) to extract three beta-blocker drugs (propranolol, atenolol, and betaxolol) from biological samples. The separation and detection of the drugs were performed by high performance liquid chromatography followed by UV detection. A green approach was applied for synthesizing chitosan@MOF-199 bio-composite, which was packed into the initial part of a metal spinal (22 gage). The effective parameters on the adsorption and desorption efficiencies, including sample solution pH, eluent flow rate, cycle numbers, type and volume of eluent solvent were evaluated and optimized. Under optimal conditions linear ranges (LRs = 5–600 µg L−1), limits of detection (LODs = 1.5–4.5 µg L−1), and relative standard deviations (RSDs% = 4.7 −5.3% with three replicates and concentration of 100 µg L−1) were obtained. Relative recoveries (RR%) for plasma (77–99%), saliva (81–108%), and urine (80–112%) samples were obtained. In this study, the drug release profile of propranolol in urine was evaluated. The results showed that the highest amount of propranolol is released 4 h after taking the drug. Based on the obtained results, this is an effective, fast, sensitive, reproducible, green, and user-friendly method for beta-blocker drug extraction in biological samples.

Assessment of benzothiazoles, benzotriazoles and benzenesulfonamides in environmental waters using an optimized combination of microextraction by packed sorbent with programmed temperature vaporization-gas chromatography tandem-mass spectrometry

This work proposes a new method for the quantification of benzothiazoles (BTs), benzotriazoles (BTRs), and benzenesulfonamides (BSAs) in tap water, river water, and wastewater. The protocol involved the use of microextraction by packed sorbent (MEPS), applied for the first time for the extraction of the target analytes, combined with programmed temperature vaporization-gas chromatography-triple quadrupole mass spectrometry (PTV-GC-QqQ-MS). Considering the synergism between MEPS extraction and PTV injection, the experimental variables affecting their performance were simultaneously optimized by "experimental design", while principal component analysis (PCA) was used to find the overall optimal working conditions. Response surface methodology was used to gain a comprehensive understanding of the effects of working variables on method performance. The developed method achieved very good linearities and satisfactory intra- and inter-day accuracies and precisions. The protocol permitted the detection of the target molecules with limit of detection (LODs) values between 0.005 and 0.85μg/L. The green character of the procedure was evaluated using three metrics: "Analytical Eco-Scale", "Green Analytical Procedure Index" (GAPI), and "Analytical Greenness metric for sample preparation (AGREEprep). The satisfactory results obtained with real water samples demonstrate the applicability of the method for monitoring campaigns and exposome studies.

Determination of synthetic hallucinogens in oral fluids by microextraction by packed sorbent and liquid chromatography–tandem mass spectrometry

A fast and simple procedure based on microextraction by packed sorbent (MEPS) and liquid chromatography–tandem mass spectrometry (LC–MS/MS) has been developed for the simultaneous quantification of 28 synthetic hallucinogens in oral fluids, including lysergic acid diethylamide and substances from NBOMe, NBOH, NBF, 2C, and substituted amphetamine categories. Extraction conditions such as type of sorbent, sample pH, number of charge/discharge cycles, and elution volume were studied. Hallucinogenic compounds were extracted from oral fluid samples using C18 MEPS, loading with 100 μL sample (adjusted to pH 7) in 3 cycles, washing with 100 μL deionized water, and eluting with 50 μL methanol in 1 cycle, giving quantitative recoveries and no significant matrix effects. Limits of detection from 0.09 to 1.22 μg L−1; recoveries from 80 to 129% performed in spiked oral fluid samples at 20, 50, and 100 μg L−1; and high precision with relative standard deviations lower than 9% were obtained. The proposed methodology was demonstrated to be appropriate for the simple and sensitive determination of NBOMe derivates and other synthetic hallucinogenic substances in oral fluid samples.Graphical

A brief review of the application of microextraction by packed sorbent for antibiotics analysis from biological, food, and environmental samples

Abstract Currently, sample preparation is the most laborious part of the analytical process, requiring the most time and being susceptible to the most errors. In this context, numerous investigations have focused on the miniaturization of these techniques to reduce work time, costs, and errors. In this regard, microextraction by packed sorbent (MEPS) is a simple, fast, and robust sample preparation technique suitable for easy automation in several analytical systems and is applied to a wide variety of samples. Antibiotics are among the most commonly used drugs; however, their extensive and inappropriate use has garnered significant attention in the environment, human health, and food safety. This brief review is intended to provide an overview of recently reported antibiotic extraction methods based on MEPS, with a special interest in those applied to the analysis of biological, environmental, and food samples. In addition, the sample pretreatment step before extraction by the MEPS device was highlighted, as was the description of the sample-related steps within the MEPS procedure, such as extraction, washing, and elution.

Determination of Ethylene Glycol Dinitrate in Environmental and Forensic Water Samples Using Microextraction by Packed Sorbent Followed by Gas Chromatography

Ethylene glycol dinitrate (EGDN) is a liquid nitrate ester, a secondary explosive. In the past, it was used as an explosive ingredient in dynamite along with nitroglycerine. Due to its various applications, the reliable detection of EGDN in the environment is a key issue for both forensic and environmental applications. In these areas, sensitive and reliable methods for determining the concentration of nitro compounds are needed. Microextraction by packed sorbent (MEPS) is an innovative approach to green technology in the sample preparation field. Compared to conventional solid-phase extraction (SPE), MEPS uses a smaller sample volume and can be easily combined with various chromatographic techniques. An important benefit is the reduction of sorbent amount and up to 100-times repeatable use compared to disposable SPE columns, thus reducing the costs of analysis as well as waste production. Optimal extraction parameters for isolating EGDN from water, e.g., 30 µL of toluene as extraction agent, working in one cycle and in draw/discard mode, were selected. Method validation was performed, obtaining a limit of detection and a limit of quantification of 0.45 pg/μL and 1.34 pg/μL, respectively. Accuracy in terms of recovery rates was evaluated over a wide concentration range, obtaining values from 83.7 to 90.0%. The satisfactory linearity expressed by the coefficient of determination was 0.9914. A matrix factor of −9.3% indicates a weak matrix effect. The application to real environmental water samples and a forensic post-blast wash water sample was realized. EGDN detection in the post-blast samples provides valuable information for forensic technicians.

Microextraction by packed sorbent and high-performance liquid chromatography for determination of benznidazole in human plasma

Benznidazole is the main drug used in Chagas disease and its determination in plasma samples is useful in several situations. Hence, robust and accurate bioanalytical methods are needed. In this context, sample preparation deserves special attention, as it is the most error-prone, labor-intensive and time-consuming step. Microextraction by packed sorbent (MEPS) is a miniaturized technique, developed to minimize the use of hazardous solvents and sample amount. In this context, this study aimed to develop and validate a MEPS coupled to high performance liquid chromatography method for the analysis of benznidazole in human plasma. MEPS optimization was performed by a 24 full factorial experimental design, which resulted in about 25 % of recovery. The best condition was achieved when 500 µL of plasma,10 draw-eject cycles, sample volume drawn of 100 µL, and desorption with three times of 50 µL of acetonitrile were used. The chromatographic separation was performed with a C18 (150 × 4.5 mm, 5 µm) column. The mobile phase was composed of water:acetonitrile (60:40) at a flow rate of 1.0 mL min−1. The developed method was validated and proved to be selective, precise, accurate, robust and linear in the range from 0.5 to 6.0 µg mL−1. The method was applied to three healthy volunteers that made use of benznidazole tablets and showed to be adequate to assess this drug in plasma samples.

New Challenges in (Bio)Analytical Sample Treatment Procedures for Clinical Applications

The primary cause of poor and ambiguous results obtained from the bioanalytical process is the sample pre-treatment, especially in clinical analysis because it involves dealing with complex sample matrices, such as whole blood, urine, saliva, serum, and plasma. So, the aim of this review is to focus attention on the classical and new techniques of pre-treatment for biological samples used in the bioanalytical process. We discussed the methods generally used for these types of complex samples. Undoubtedly, it is a daunting task to deal with biological samples because the analyst may encounter a substantial loss of the analytes of interest, or the overall analysis may be too time-consuming. Nowadays, we are inclined to use green solvents for the environment, but without sacrificing analytical performance and selectivity. All the characteristics mentioned above should be added to the difficulty of the withdrawal of samples like blood because it can be an invasive practice. For these reasons, now we can also find in the literature the use of saliva as alternative biological samples and new techniques that do not require substantial sample pre-treatment, such as fabric phase sorptive extraction (FPSE). The text has been divided into the following two distinct parts: firstly, we described clinical applications under different subsections, such as anticancer drugs, antibiotics, vitamins, antivirals, non-steroidal anti-inflammatory drugs, statin, imidazoles, and triazoles. The second part is dedicated to sample preparation techniques for diagnostic purposes and is divided into the following different sample preparation techniques: solid-phase microextraction (SPME), microextraction by packed sorbent (MEPS), dispersive liquid–liquid microextraction (DDLME), and fabric phase sorptive extraction (FPSE).

Novel eco-friendly methodology to determine polycyclic aromatic hydrocarbons in polyurethane foam for air monitoring: Application to spatial and temporal distribution survey

This study aimed at developing a new method for the extraction of polycyclic aromatic hydrocarbons (PAHs) in polyurethane foam (PUF). In the field of PAH monitoring, passive samplers using PUF disks are widely used. However, current extraction methods are time and solvent consuming. This new method employs 3 times a sixteenth of the PUF disk, with method detection limits (MDL) values below 5 and 13 ng/sampler for 3- and 4-rings PAHs, respectively. The use of only parts of the disk allows extraction by ultrasounds using exclusively 120 mL of ethanol, making it environmentally friendly. Ethanolic extracts are then purified and concentrated using microextraction by packed sorbent (MEPS) before GC-MS analyses. This method was applied for an environmental survey in a French urban area with an oceanic climate. Variations in PAH concentrations were observed depending on the site studied (urban, traffic, periurban and rural), as well as temporal variations.

Lyophilization with Subsequent Derivatization vs Microextraction by Packed Sorbent (MEPS) in the Analysis of Exhaled Breath Condensate by Gas Chromatography–Mass Spectrometry

Lyophilization with Subsequent Derivatization vs Microextraction by Packed Sorbent (MEPS) in the Analysis of Exhaled Breath Condensate by Gas Chromatography–Mass Spectrometry

The Determination of Cannabinoids in Urine Samples Using Microextraction by Packed Sorbent and Gas Chromatography-Mass Spectrometry.

Cannabis is the most consumed illicit drug worldwide, and its legal status is a source of concern. This study proposes a rapid procedure for the simultaneous quantification of Δ9-tetrahydrocannabinol (THC), 11-hydroxy-Δ9-tetrahydrocannabinol (11-OH-THC), 11-nor-9-carboxy-Δ9-tetrahydrocannabinol (THC-COOH), cannabidiol (CBD), and cannabinol (CBN) in urine samples. Microextraction by packed sorbent (MEPS) was used to pre-concentrate the analytes, which were detected by gas chromatography–mass spectrometry. The procedure was previously optimized, and the final conditions were: conditioning with 50 µL methanol and 50 µL of water, sample load with two draw–eject cycles, and washing with 310 µL of 0.1% formic acid in water with 5% isopropanol; the elution was made with 35 µL of 0.1% ammonium hydroxide in methanol. This fast extraction procedure allowed quantification in the ranges of 1–400 ng/mL for THC and CBD, 5–400 ng/mL for CBN and 11-OH-THC, and 10–400 ng/mL for THC-COOH with coefficients of determination higher than 0.99. The limits of quantification and detection were between 1 and 10 ng/mL using 0.25 mL of sample. The extraction efficiencies varied between 26 and 85%. This analytical method is the first allowing the for determination of cannabinoids in urine samples using MEPS, a fast, simple, and low-cost alternative to conventional techniques.

Microextraction by packed sorbent of polycyclic aromatic hydrocarbons in brewed coffee samples with a new zwitterionic ionic liquid-modified silica sorbent

A simple, sensible, and high-throughput method was developed for determining selected polycyclic aromatic hydrocarbons (PAHs) from brewed coffee samples. Three sorbents based on ionic liquids supported on silica particles were synthesized, characterized, and assessed as extraction phases in microextraction by packed sorbent (MEPS). A synthesized zwitterionic ionic liquid-based sorbet (zIL@SiO2) exhibited superior extraction capabilities. The most relevant influencing parameters on the zIL@SiO2-based MEPS performance were systematically investigated. Under selected conditions, the MEPS method took less than 5 min and showed excellent linearity, precision, and trueness, from 5 to 100 µg L-1 (R2 from 0.998 to 0.999). The method's accuracy was between ca. 73.34% and 118.66%; the precision, evaluated as the coefficient of variance (% RSD) for intraday and interday analysis, varied from 0.21% to 11.50%. The recovery percentage was 81.06–118.81%, and the detection limits (S/N = 3) ranged between 1.0 and 1.5 μg L-1. The developed zIL@SiO2 -MEPS-GC-MS method was applied to investigate 13 different Colombian and Brazilian coffee samples, allowing the detection and quantification of dangerous PAHs in the studied samples. The method is demonstrated to be a straightforward, fast, confident, and environment-friendly approach for surveillance pollutants in complex beverage samples.

Hollow polymer nanospheres (HPSs) as the adsorbent in microextraction by packed sorbent (MEPS) for determining BTEXs chief metabolites in urine samples

Hollow polymer nanospheres (HPSs) as the adsorbent in microextraction by packed sorbent (MEPS) for determining BTEXs chief metabolites in urine samples

Application of Fe3O4@TbBd nanobeads in microextraction by packed sorbent (MEPS) for determination of BTEXs biomarkers by HPLC–UV in urine samples

A relatively new adsorbent based on covalent organic frameworks (COFs) was employed for the first time to extract and determine Trans, trans-muconic acid (tt-MA), Mandelic acid (MA), Hippuric acid (HA), and 3-Methylhippuric acid (m-MHA) in urine. For this purpose, microextraction was performed using the packed sorbent (MEPS) method. Following the extraction process, the prepared samples were specified via the high-performance liquid chromatography-ultraviolet detector system. The precipitation polymerization was applied to synthesize the Fe3O4@TbBd nanobeads, and the morphological and dimensional structures of the products were specified with FE-SEM images. Some key variables affecting the extraction efficiency (i.e., sample volume, elution volume, condition and washing solvents, type and volume of elution solvent, extraction cycles, temperature, and pH of the sample solution) were investigated. In ideal conditions, the limit of detection (LOD) was obtained from 0.02 µg/ml for tt-MA to 0.5 µg/ml for MA. Calibration curves (at five-point) were plotted in the range 0.05–5 µg/ml for tt-MA to 1–300 µg/ml for MA (R2 > 0.98). Moreover, intra- and inter-day precision values were 3.1–5.5 and 4.6–9.8%, respectively. The developed method was successfully employed to determine four analytes in three concentrations (low, medium, and high QCs). The results showed a satisfactory recovery (70–87%). COF-MEPS technique is a rapid, easy, user-friendly, and environment-friendly method for separating the minimum values of all BTEXs chief biomarkers from urine samples without using complicated processes and only with one adsorbent. Also, it can be a good alternative for biomonitoring the workers exposed to BTEX compounds in occupational and environmental access.

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.