► Thin-film microextraction offers a new geometry for solid-phase microextraction. ► Experimental results show thin-film microextraction has good agreement with theory. ► To develop thin-film ...microextraction calibration is important for real applications. ► A desorption method is a challenge for thin film microextraction to be widely used. ► Review of application of thin-film microextraction to gas, liquid, solid sampling.
As a new geometry for solid-phase microextraction, thin-film microextraction (TFME) has become an attractive sample-preparation technique. The high surface area-to-volume ratio together with the increase of extraction-phase volume enhanced the sensitivity of this technique without sacrificing the sampling time compared to other microextraction approaches. Comprehensive research has demonstrated the good agreement of the experimental data with the fundamental principle of this technique.
In this review, we summarize the theory of the sampling process, the reported calibration methods and diverse TFME formats, different structures of the extraction phase and related preparation methods. Furthermore, we discuss approaches to TFME desorption, coupling with different analytical instruments and the main applications of this technique.
The development of new support and geometries of solid phase microextraction (SPME), including metal fiber assemblies, coated-tip, and thin film microextraction (TFME) (i.e. self-supported, fabric ...and blade supported), as well as their effects on diffusion and extraction rate of analytes were discussed in the current review. Application of main techniques widely used for preparation of a variety of coating materials of SPME, including sol-gel technique, electrochemical and electrospinning methods as well as the available commercial coatings, were presented. Advantages and limitations of each technique from several aspects, such as range of application, biocompatibility, availability in different geometrical configurations, method of preparation, incorporation of various materials to tune the coating properties, and thermal and physical stability, were also investigated. Future perspectives of each technique to improve the efficiency and stability of the coatings were also summarized. Some interesting materials including ionic liquids (ILs), metal organic frameworks (MOFs) and particle loaded coatings were briefly presented.
Display omitted
•Solid phase microextraction (SPME) for analysis of water samples.•Inter-laboratory validation of SPME and comparison with official methods.•Presentation of official methods of SPME including US EPA, ...ISO and ASTM.•On-site sampling and high-throughput 96-blade format as the new perspective of SPME.•Time weighted average sampling by retracted devices and open bed configurations.
The review summarizes applications of solid phase microextraction (SPME) for water sample analysis. Official methods and standards of SPME in water research and inter-laboratory validation are discussed. A comparison of SPME with current EPA-approved methods from several analytical aspects is presented. The review also provides some perspectives of the recent development of SPME on sampling water using artificial river systems, in the passive sampling and on-site sampling. Recently developed configuration of SPME such as thin film microextraction and high-throughput applications (e.g. when used in a 96-blade configuration) are shown.
•Critical strategies of solid-phase microextraction (SPME) in complex food matrices.•Special emphasis on the development of new matrix-compatible extraction phases.•Evolution of SPME from headspace ...monitoring of complex systems.•Evolution of SPME to in-vivo investigation of vegetal systems.•Quantification in food matrices utilizing different SPME calibration strategies.
The present review – Part II of a comprehensive review on solid-phase microextraction (SPME) applied to complex matrices – aims to describe recent developments in SPME technology applied in the fields of food analysis. We briefly introduce a perspective on the most commonly performed types of analysis within food studies, and place particular attention on the more recent SPME developments of new extraction phases, as this is recognized as the driving force behind most of the advances in the technique in this area. We address quantitation in this review with a concise, yet assertive, discussion on calibration strategies of SPME methods in complex matrices.
In this study, we propose for the first time the use of solid-phase microextraction (SPME) in combination with liquid chromatography−mass spectrometry for untargeted metabolomic profiling of ...biological fluids. To achieve this goal, we first systematically evaluated 42 different SPME coatings for the extraction of 36 metabolites from different chemical classes and of widely varying polarities (log P range of −7.9 to 7.4) in order to identify SPME coatings which are the most suitable for metabolomic studies and to improve the extraction of polar metabolites over the existing commercial SPME devices. Three types of SPME coatings (mixed-mode coatings, polar-enhanced polystyrene−divinylbenzene, and phenylboronic acid) performed the best for simultaneous extraction of both hydrophilic and hydrophobic metabolites at physiological conditions, thus making them suitable for untargeted metabolomic profiling applications. A rapid and simple SPME method was then developed with single-use biocompatible mixed-mode coating for the metabolomic profiling of human plasma in combination with liquid chromatography−high-resolution mass spectrometry on a benchtop Orbitrap system. This optimized SPME method was evaluated versus ultrafiltration and solvent precipitation in terms of metabolite coverage and method precision. SPME detected 1592−3320 features versus 2082−3245 features detected by solvent precipitation methods and 2093−2686 detected for ultrafiltration using the same pooled human plasma sample. Method precision of SPME ranged between 11% and 18% (expressed as median relative standard deviation (RSD) of n = 7 replicates) versus 8−19% for solvent precipitation and 20−22% for ultrafiltration. The results demonstrate that the proposed SPME methodology reduces ionization suppression, provides free concentration information for hydrophobic analytes which are not detected by ultrafiltration methods, and can improve metabolite coverage over existing methodologies.
Solid-phase microextraction (SPME) was developed to address the need for rapid sampling and sample preparation, both in the laboratory and on-site. Unlike traditional sample preparation methods, SPME ...is a non-exhaustive extraction technique in which only a small portion of the target analyte is removed from the sample matrix. Therefore, calibration of SPME for quantitative analysis is very important. In this review, we summarized the proposed SPME calibration methods and the characteristics of these methods were discussed.
Coated blade spray (CBS) is a technology based on solid‐phase microextraction (SPME) that has been designed for the quick extraction/cleanup of analytes from complex matrices and direct ...desorption/ionization under ambient mass spectrometry conditions. The entire analytical process can be completed in less than 3 min and enables limits of quantitation in the low picogram‐per‐milliliter region to be reached.
There's no hiding now: Coated blade spray is a technique based on solid‐phase microextraction that has been designed for the quick extraction/cleanup of analytes from complex matrices and direct desorption/ionization under ambient MS conditions. The entire analytical process can be completed within 3 min (see picture; HV=high voltage, SRM=selected reaction monitoring) with limits of quantitation in the low picogram‐per‐millimeter region.
In this work, a durable and easy to handle thin film microextraction (TFME) device is reported. The membrane is comprised of poly(divinylbenzene) (DVB) resin particles suspended in a high-density ...polydimethylsiloxane (PDMS) glue, which is spread onto a carbon fiber mesh. The currently presented membrane was shown to exhibit a substantially lesser amount of siloxane bleed during thermal desorption, while providing a statistically similar extraction efficiency toward a broad spectrum of analytes varying in polarity when compared to an unsupported DVB/PDMS membrane of similar shape and size which was prepared with previously published methods. With the use of hand-portable GC-TMS instrumentation, membranes cut with dimensions 40 mm long by 4.85 mm wide and 40 ± 5 μm thick (per side) were shown to extract 21.2, 19.8, 18.5, 18,4, 26.8, and 23.7 times the amount of 2,4 dichlorophenol, 2,4,6 trichlorophenol, phorate D10, fonofos, chloropyrifos, and parathion, respectively, within 15 min from a 10 ppb aqueous solution as compared to a 65 μm DVB/PDMS solid phase microextraction (SPME) fiber. A portable high volume desorption module prototype was also evaluated and shown to be appropriate for the desorption of analytes with a volatility equal to or lesser than benzene when employed in conjunction with TFME membranes. Indeed, the coupling of these TFME devices to hand-portable gas chromatography toroidial ion trap mass spectrometry (GC-TMS) instrumentation was shown to push detection limits for these pesticides down to the hundreds of ppt levels, nearing that which can be achieved with benchtop instrumentation. Where these membranes can also be coupled to benchtop instrumentation it is reasonable to assume that detection limits could be pushed down even further. As a final proof of the concept, the first ever, entirely on-site TFME-GC-TMS analysis was performed at a construction impacted lake. Results had indicated the presence of contaminants such as toluene, ethylbenzene, xylene, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, and tris(1-chloro-2-propyl)phosphate, which stood out from other naturally occurring compounds detected.
•A fast and robust reagent-free method for determination of neurotransmitters was developed.•SPME conditions were optimized.•Very good sensitivity achieved within short extraction time.•Accurate ...quantitative results could be easily achieved.
A simple solid phase microextraction method coupled to liquid chromatography mass spectrometry is introduced for the analysis of neurotransmitter compounds with a wide range of polarities in biological matrices. A novel “reversed” reverse-phase chromatographic method was developed without pre-column derivatization for the analysis of dopamine, serotonin, gamma aminobutyric acid and glutamate. New solid phase microextraction “in house” coatings using mixed-mode solid phase extraction particles were prepared, and used for the extraction of polar neurotransmitters. The polymer-support base reverse phase mixed-mode sorbents with strong ion exchange properties generally had higher extraction efficiencies compared to similar sorbents with weak ion exchange properties. The linear range was determined to be between 0.01 and 150ng/mL for all the analytes, except for GABA, which was from 0.1 to 100ng/mL. The limit of detection range was from 6 to 10pg/mL for all the neurotransmitters, and the limits of quantitation were in the range of 20–35pg/mL. The results demonstrate the potential of the SPME-LC–MS/MS technique for bioanalysis of small polar endogenous compounds, such as neurotransmitters, from various biological matrices using the mixed-mode sorbents as the extraction phase.
A new SPME device was developed and applied for quick solventless extraction/enrichment of small molecules from complex matrices. Subsequently, the device was coupled as a transmission mode substrate ...to DART resulting in limits of detection in the low pg mL(-1) level in less than 3 minutes with reproducibility below 5% RSD.
PDF
