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Practical benefits of graphene-cellulose composites (GCC) are categorical. Diverse salient features like thermal and electrical conductivity, mechanical strength, and durability make GCC advantageous for widespread applications. Despite extensive studies the basic understanding of various fundamental aspects of this novel complex remains deficient. Based on this fact, a critical overview and bibliometric analysis involving the overall prospects of GCC was made wherein a total of 1245 research articles from the Scopus database published during the year 2002 to 2020 were used. For the bibliometric assessment, various criteria including the publication outputs, co-authorships, affiliated countries, and co-occurrences of the authors' keywords were explored. Environmental amiability, sustainability, economy, and energy efficiency of GCC were emphasized. In addition, the recent trends, upcoming challenges, and applied interests of GCC were highlighted. The findings revealed that the studies on GCC related to the energy storage, adsorption, sensing, and printing are ever-increasing, indicating the global research drifts on GCC. The bibliometric map analysis displayed that among the researchers from 61 countries/territories, China alone contributed about 50 % of the international publications. It is asserted that the current article may offer taxonomy to navigate into the field of GCC wherein stronger collaboration networks can be established worldwide through integrated research activities desirable for sustainable development.
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Sample clean-up and pre-concentration are critical components of pharmaceutical analysis. The dispersive liquid-liquid microextraction (DLLME) technique is widely recognized as the most effective approach for enhancing overall detection sensitivity. While various DLLME modes have been advanced in pharmaceutical analysis, there need to be more discussions on pre-concentration techniques specifically developed for this field. This review presents a comprehensive overview of the different DLLME modes used in pharmaceutical analysis from 2017 to May 2023. The review covers the principles of DLLME, the factors affecting microextraction, the selected applications of different DLLME modes, and their advantages and disadvantages. Additionally, it focuses on multi-extraction strategies employed for pharmaceutical analysis.
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Microplastic fibers from textiles have been known to significantly contribute to marine microplastic pollution. However, little is known about the microfiber formation and discharge during textile production. In this study, we have quantified microfiber emissions from one large and representative textile factory during different stages, spanning seven different materials, including cotton, polyester, and blended fabrics, to further guide control strategies. Wet-processing steps released up to 25 times more microfibers than home laundering, with dyeing contributing to 95.0% of the total emissions. Microfiber release could be reduced by using white coloring, a lower dyeing temperature, and a shorter dyeing duration. Thinner, denser yarns increased microfiber pollution, whereas using tightly twisted fibers mitigated release. Globally, wet textile processing potentially produced 6.4 kt of microfibers in 2020, with China, India, and the US as significant contributors. The study underlined the environmental impact of textile production and the need for mitigation strategies, particularly in dyeing processes and fiber choice. In addition, no significant difference was observed between the virgin polyesters and the used ones. Replacing virgin fibers with recycled fibers in polyester fabrics, due to their increasing consumption, might offer another potential solution. The findings highlighted the substantial impact of textile production on microfiber released into the environment, and optimization of material selection, knitting technologies, production processing, and recycled materials could be effective mitigation strategies.
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Microplásticos , Plásticos , Textiles , Poliésteres , Ambiente , Industria TextilRESUMEN
A polymer inclusion membrane (PIM) based sampling probe was developed for electrokinetic extraction of drugs from biological fluids. The probe was fabricated by dip-coating a nonconductive glass capillary tube in a homogeneous PIM solution for three cycles. The PIM solution comprised cellulose triacetate (CTA), 2-nitrophenyl octyl ether (NPOE), and 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [EMIM][NTf2] in a ratio of 5:4:2. The developed probe electrokinetically extracted doxorubicin from human plasma, human serum, and dried blood spot (DBS). The practicability and reliability of the electrokinetic extraction were evaluated by LC-MS/MS to quantify the desorption of extracted doxorubicin. Under the optimized conditions, a quantification limit of 0.2-2 ng/mL was achieved for the three biological samples. The probe was further integrated into a portable battery-powered device for safe low-voltage (36 V) electrokinetic extraction. The developed technique is envisioned to provide a more efficient analytical workflow in the laboratory.
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Polímeros , Espectrometría de Masas en Tándem , Humanos , Cromatografía Liquida , Reproducibilidad de los ResultadosRESUMEN
A new dispersive inclusion complex microextraction (DICM) approach coupled with ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) for the determination of n-nitrosamine impurities in different medicinal products is demonstrated for the first time. The proposed DICM procedures consist of a dispersive liquid phase microextraction steps employing cyclodextrin as an inclusion complex agent to extract n-nitrosamines namely N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine (NDEA), N-nitrosodiisopropylamine (NDIPA), N-ethyl-N-nitrosoisopropylamine (NEIPA) and N-nitroso-di-n-butylamine (NDBA) present in the medicinal products. The sample solutions were prepared by mixing 5% (m/v) NaCl solution with 1.5 mM ß-cyclodextrin and 20 mM sodium dodecyl sulphate to form a stable inclusion complex and subsequently extracted into dichloromethane as an extraction solvent. The enriched solution was reconstituted into aqueous solution prior to UPLC-MS/MS analysis. The method showed good linearity in the range of 0.036-1 ng/mL with a correlation coefficient of at least 0.995, acceptable reproducibility (RSD 0.5-5.8%, n=5), low limits of detection (0.011-0.018 ng/mL), and satisfactory relative recoveries (96-105%). The results obtained were found to be at least 10-fold more sensitive comparable to those obtained using validated direct sample dissolutions coupled with UPLC-MS/MS approach.
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Microextracción en Fase Líquida , Nitrosaminas , Nitrosaminas/análisis , Cromatografía Liquida , Espectrometría de Masas en Tándem/métodos , Reproducibilidad de los Resultados , Microextracción en Fase Líquida/métodos , Dimetilnitrosamina/análisisRESUMEN
Drug-drug cocrystalllization is a novel mechanism for effective pharmacological combination therapy. In this work, we have demonstrated the preparation of a drug-drug cocrystal of a hypertension drug (Telmisartan; TEL) with a hyperuricemia drug (Febuxostat; FEB) in 1:1 molar ratio using a solvent evaporation method for the first time. Generally, a multi-component system may yield either a eutectic, salt, and/or a cocrystal. This study adopted a methodical orthogonal framework to analyze the final solid form. A single crystal X-ray structural investigation revealed the formation of a heterosynthon with carboxylic and benzimidazole groups of FEB and TEL, respectively, in the triclinic P-1 space group. ΔpKa of the heterosynthon is â¼1.5, hence, based on the empirical rules, a salt-cocrystal continuum is hypothesized. Further, attenuated total reflectance Fourier transform infrared (ATR-FTIR), and Raman spectroscopy were employed to corroborate the hydrogen bond formation in the heterosynthon (-N---H-O-), which confirmed the propensity for cocrystal formation. An accelerated stability study and an in vitro biorelevant dissolution study of the cocrystal were performed, which demonstrated that it is physiochemically stable, but it resulted in a slower dissolution rate when compared with plain drugs.
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Gota , Hipertensión , Humanos , Febuxostat , Telmisartán , Gota/tratamiento farmacológico , Hipertensión/tratamiento farmacológico , Terapia Combinada , Cloruro de Sodio Dietético , Cloruro de SodioRESUMEN
One of the major drawbacks of electrophoresis in both capillary and microchip is the unsatisfactory sensitivity. Online sample preconcentration techniques can be regarded as the most common and powerful approaches commonly applied to enhance overall detection sensitivity. While the advances of various online preconcentration strategies in capillary and microchip employing aqueous background electrolytes are well-reviewed, there has been limited discussion of the feasible preconcentration techniques specifically developed for capillary and microchip using nonaqueous background electrolytes. This review provides the first consolidated overview of various online preconcentration techniques in nonaqueous capillary and microchip electrophoresis, covering the period of the last two decades. It covers developments in the field of sample stacking, isotachophoresis, and micellar-based stacking. Attention is also given to multi-stacking strategies that have been used for nonaqueous electrophoresis.
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Electroforesis Capilar/métodos , Electroforesis por Microchip/métodos , Electrólitos/química , Isotacoforesis , MicelasRESUMEN
Conventional sampling of biological fluids often involves a bulk quantity of samples that are tedious to collect, deliver and process. Miniaturized sampling approaches have emerged as promising tools for sample collection due to numerous advantages such as minute sample size, patient friendliness and ease of shipment. This article reviews the applications and advances of microsampling techniques in therapeutic drug monitoring (TDM), covering the period January 2015 - August 2020. As whole blood is the gold standard sampling matrix for TDM, this article comprehensively highlights the most historical microsampling technique, the dried blood spot (DBS), and its development. Advanced developments of DBS, ranging from various automation DBS, paper spray mass spectrometry (PS-MS), 3D dried blood spheroids and volumetric absorptive paper disc (VAPD) and mini-disc (VAPDmini) are discussed. The volumetric absorptive microsampling (VAMS) approach, which overcomes the hematocrit effect associated with the DBS sample, has been employed in recent TDM. The sample collection and sample preparation details in DBS and VAMS are outlined and summarized. This review also delineates the involvement of other biological fluids (plasma, urine, breast milk and saliva) and their miniaturized dried matrix forms in TDM. Specific features and challenges of each microsampling technique are identified and comparison studies are reviewed.
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Líquidos Corporales/química , Monitoreo de Drogas/métodos , Monitoreo de Drogas/tendencias , Manejo de Especímenes/métodos , Manejo de Especímenes/tendencias , HumanosRESUMEN
An electrokinetic platform was developed for extracting small-molecule pharmaceuticals from a dried blood spot. Through the exclusion of liquid reagents and use of low field strength (6â V cm-1 ), the electroextraction of a drug from a dried blood spot, deposited on a polymer inclusion membrane (PIM), could be realised while in transit in the mail. Inâ transit sample preparation provides a potential solution to inâ situ sample degradation and may accelerate the workflow upon arrival of a patient sample at the analytical facility. The electroextraction method was enabled through our discovery of the use of 15-20â µm thin PIMs as electrophoretic separation medium in absence of liquid reagents. Here, a PIM consisting of cellulose triacetate as polymer base, 2-nitrophenyl octyl ether as plasticizer and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide as carrier was used. The PIM, was packaged with two 12â V batteries to supply the separation voltage. A blood spot containing berberine chloride was deposited and dried before the applying the separation potential, allowing for the electroextraction while the packaged device was shipped in internal mail. Upon arrival in the analytical laboratory, the PIM was analysed using a fluorescence microscope with photon multiplier tube, quantifying the berberine extracted away from the sample matrix. This platform represents a new opportunity for processing clinical samples during transport to the laboratory, saving time and manual handling to accelerate the time to result.
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Berberina/sangre , Electroforesis/métodos , Berberina/aislamiento & purificación , Celulosa/análogos & derivados , Celulosa/química , Pruebas con Sangre Seca , Humanos , Sistemas de Atención de Punto , Polímeros/químicaRESUMEN
A new multi-stacking pre-concentration procedure based on field-enhanced sample injection (FESI), field-amplified sample stacking, and transient isotachophoresis was developed and implemented in a compact microchip electrophoresis (MCE) with a double T-junction glass chip, coupled with an on-chip capacitively coupled contactless conductivity detection (C4 D) system. A mixture of the cationic target analyte and the terminating electrolyte (TE) from the two sample reservoirs was injected under FESI conditions within the two sample-loading channels. At the double T-junction, the stacked analyte zones were further concentrated under field-amplified stacking conditions and then subsequently focused by transient-isotachophoresis and separated along the separation channels. The proposed multi-stacking strategy was verified under a Universal Serial Bus (USB) fluorescence microscope employing Rhodamine 6G as the model analyte. This developed approach was subsequently used to monitor the target quinine present in human plasma samples. The total analysis time for quinine was approximately 200 s with a sensitivity enhancement factor of approximately 61 when compared to the typical gated injection. The detection and quantification limits of the developed approach for quinine were 3.0 µg/mL and 10 µg/mL, respectively, with intraday and interday repeatability (%RSDs, n = 5) of 3.6 and 4.4%. Recoveries in spiked human plasma were 98.1-99.8%.
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Análisis Químico de la Sangre/instrumentación , Electroforesis por Microchip/instrumentación , Quinina/sangre , Análisis Químico de la Sangre/métodos , Electroforesis por Microchip/métodos , Diseño de Equipo , Humanos , Límite de Detección , Modelos Lineales , Reproducibilidad de los ResultadosRESUMEN
One of the most cited limitations of capillary and microchip electrophoresis is the poor sensitivity. This review continues to update this series of biannual reviews, first published in Electrophoresis in 2007, on developments in the field of online/in-line concentration methods in capillaries and microchips, covering the period July 2016-June 2018. It includes developments in the field of stacking, covering all methods from field-amplified sample stacking and large-volume sample stacking, through to isotachophoresis, dynamic pH junction, and sweeping. Attention is also given to online or in-line extraction methods that have been used for electrophoresis.
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Electroforesis Capilar , Animales , Biomarcadores/análisis , Línea Celular , Fraccionamiento Químico , Humanos , Concentración de Iones de Hidrógeno , Isotacoforesis , Ratones , Micelas , Sensibilidad y EspecificidadRESUMEN
A sample pre-treatment method based on a dynamic mixed matrix membrane tip extraction followed by capillary electrophoresis with contactless conductivity detection (CE-C4D) was evaluated for the determination of tobramycin in human plasma. The extraction tip device consisted of a cellulose triacetate membrane tip wall immobilised with 15% (w/w) of hydrophilic lipophilic balance (HLB) nanoparticles as adsorbent. The extraction was performed dynamically by withdrawing/dispensing the plasma sample through the tip device followed by desorption into 20⯵L of acidified aqueous solution at pH 3 prior to the CE-C4D analysis. Under the optimum conditions, the detection limit of the method for tobramycin was 10â¯ng/mL, with intraday and interday repeatability RSDs of 3.5% and 4.5%, respectively. Relative recoveries in spiked human plasma were 99.6%-99.9%. The developed approach was successfully demonstrated for the quantification of tobramycin in human plasma samples.
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Antibacterianos/sangre , Infecciones Bacterianas/tratamiento farmacológico , Fraccionamiento Químico/métodos , Monitoreo de Drogas/métodos , Tobramicina/sangre , Antibacterianos/uso terapéutico , Infecciones Bacterianas/sangre , Conductividad Eléctrica , Electroforesis Capilar/métodos , Humanos , Límite de Detección , Membranas Artificiales , Tobramicina/uso terapéuticoRESUMEN
A method for on-line matrix elimination to enable selective quantification of ultraviolet absorbing analytes by a flow-injection analysis procedure is described. Selectivity is achieved by electric field driven extraction across a polymer inclusion membrane. The method was demonstrated on the example of the determination of naproxen from spiked human urine. Membranes of 10 µm thickness were employed which consisted of 7.5 mg cellulose triacetate as base polymer, 5 mg of o-nitrophenyl octyl ether as plasticizer and 7.5 mg of Aliquat 336 as cationic carrier. Ten µL of sample was introduced into a continuous stream of background solution consisting of 100 µM aqueous NaClO4 with a flow rate of 2 µL/min while applying a voltage of 150 V to the extraction cell. The target ion was electrokinetically transported across the membrane and enriched in 1.5 µL of a stagnant acceptor solution. This was subsequently pumped past a flow-through UV detector for quantification. The method showed a linear range from 5 to 200 µM with a correlation coefficient of 0.9978 and a reproducibility of typically 7% (n = 8). The detection limit of the method for naproxen was 2 µM.
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Análisis de Inyección de Flujo , Modelos Teóricos , HumanosRESUMEN
Point-of-collection (POC) devices aim for a fast, on-site detection for medical and environmental purposes. In this area, microfluidic Paper-based Analytical Devices (µPADs) have recently gained popularity because these are potentially cheap and environmentally friendly to produce, and easy to use. From an analytical perspective, paper is well known for its use as a substrate for chromatography, but less known for its use in electrophoretic separations. With the recent interest in µPADs, most applications are based on rather simple assays with relatively few applications incorporating an analytical separation. The focus of this review is on paper-based electrophoresis, originating with the key developments in the 1940s and 1950s as well as the recent developments of electrophoretic µPADs, and concluding with a critical discussion of the opportunities and challenges for electrophoretic µPADS in the future.
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A new electric-field driven extraction approach based on the integration of a bubbleless electrode into the electromembrane extraction (EME) across hollow polymer inclusion membranes (HPIMs) was demonstrated for the first time. The bubbleless electrode was prepared based on an in-situ synthesised polyacrylamide within a fused silica capillary. The electrode functions as a salt bridge, which conducts the electrical current between the acceptor phase in the lumen of the HPIM and the acceptor solution in the reservoir connected to a high voltage supply through a platinum electrode. Two types of HPIMs were employed, which consisted of desired proportions of cellulose acetate as base polymer, tris(2-ethylhexyl)phosphate as plasticizer, and di-(2-ethylhexyl)phosphoric acid as anionic carrier or Aliquat 336 as cationic carrier, respectively. The EME strategy was evaluated for the simultaneous determination of cationic quaternary ammonium and anionic chlorophenoxy acetic acid herbicides present in the river water, respectively. The analysis was carried out using capillary electrophoresis coupled with UV and contactless conductivity detection. Under the optimised conditions, enrichment factors in the range of 152-185-fold were obtained from 4mL of river water sample with a 20min extraction time and an applied voltage of 3000V. The proposed method provided good linearity with correlation coefficients ranging from 0.9982 to 0.9997 over a concentration range of 1-1000µg/L. The detection limits of the method for the herbicides were in the range of 0.3-0.4µg/L, with relative standard deviations of between 4.8% and 8.5%. The relative recoveries obtained when analysing the spiked river water ranged from 99.1% to 100%. A comparison was also made between the newly developed approach with the conventional EME setup by placing the platinum electrode directly in the lumen of the HPIMs.
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Técnicas Electroquímicas/métodos , Herbicidas/aislamiento & purificación , Polímeros/química , Contaminantes Químicos del Agua/aislamiento & purificación , Técnicas Electroquímicas/instrumentación , Electrodos , Electroforesis Capilar , Agua Dulce/química , Herbicidas/química , Membranas Artificiales , Contaminantes Químicos del Agua/químicaRESUMEN
A portable microchip electrophoresis (MCE) coupled with on-chip contactless conductivity detection (C4D) system was evaluated for the determination of vancomycin in human plasma. In order to enhance the detection sensitivity, a new online multi-stacking preconcentration technique based on field-enhanced sample injection (FESI) and micelle-to-solvent stacking (MSS) was developed and implemented in MCE-C4D system equipped with a commercially available double T-junction glass chip. The cationic analytes from the two sample reservoirs were injected under FESI conditions and subsequently focused by MSS within the sample-loading channel. The proposed multi-stacking strategy was verified under a fluorescence microscope using Rhodamine 6G as the model analyte and a sensitivity enhancement factor (SEF) of up to 217 was achieved. The developed approach was subsequently implemented in the aqueous-based MCE, coupled to C4D in order to monitor the targeted antibiotic (in this case, vancomycin) present in human plasma samples. The multi-stacking and analysis time for vancomycin were 50s and 250s respectively, with SEF of approximately 83 when compared to typical gated injection. The detection limit of the method for vancomycin was 1.2µg/mL, with intraday and interday repeatability RSDs of 2.6% and 4.3%, respectively. Recoveries in spiked human plasma were 99.0%-99.2%.
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Antibacterianos/sangre , Vancomicina/sangre , Cationes , Electroforesis por Microchip/métodos , Humanos , Límite de Detección , Micelas , SolventesRESUMEN
One of the most cited limitations of capillary (and microchip) electrophoresis is the poor sensitivity. This review continues to update this series of biennial reviews, first published in Electrophoresis in 2007, on developments in the field of on-line/in-line concentration methods in capillaries and microchips, covering the period July 2014-June 2016. It includes developments in the field of stacking, covering all methods from field amplified sample stacking and large volume sample stacking, through to isotachophoresis, dynamic pH junction, and sweeping. Attention is also given to on-line or in-line extraction methods that have been used for electrophoresis.
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Electroforesis Capilar/métodos , Isotacoforesis/métodos , Procedimientos Analíticos en Microchip/métodos , Electrocromatografía Capilar , Línea Celular , Humanos , Compuestos Inorgánicos/análisis , Focalización Isoeléctrica , Nanoestructuras/análisis , Compuestos Orgánicos/análisis , Sensibilidad y EspecificidadRESUMEN
A new approach based on the integration of the free liquid membrane (FLM) into electrokinetic supercharging (EKS) was demonstrated to be a new powerful tool used in order to enhance online preconcentration efficiency in capillary electrophoresis (CE). A small plug of water immiscible organic solvent was used as a membrane interface during the electrokinetic sample injection step in EKS in order to significantly enhance the analyte stacking efficiency. The new online preconcentration strategy was evaluated for the determination of paraquat and diquat present in the environmental water samples. The optimised FLM-EKS conditions employed were as follows: hydrodynamic injection (HI) of 20mM potassium chloride as leading electrolyte at 50mbar for 75s (3% of the total capillary volume) followed by the HI of tris(2-ethylhexyl) phosphate (TEHP) as FLM at a 1mm length (0.1% of the capillary volume). The sample was injected at 10kV for 360s, followed by the HI of 20mM cetyl trimethylammonium bromide (CTAB) as terminating electrolyte at 50mbar for 50s (2% of the total capillary volume). The separation was performed in 12mM ammonium acetate and 30mM NaCl containing 20% MeOH at +25kV with UV detection at 205nm. Under optimised conditions, the sensitivity was enhanced between 1500- and 1866-fold when compared with the typical HI at 50mbar for 50s. The detection limit of the method for paraquat and diquat was 0.15-0.20ng/mL, with RSDs below 5.5%. Relative recoveries in spiked river water were in the range of 95.4-97.5%. A comparison was also made between the proposed approach with sole preconcentration of the field-enhanced sample injection (FASI) and EKS in the absence of the FLM.
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Electroforesis Capilar/métodos , Herbicidas/análisis , Membranas Artificiales , Contaminantes Químicos del Agua/análisis , Cationes , Diquat/análisis , Límite de Detección , Paraquat/análisis , Análisis de Regresión , Reproducibilidad de los Resultados , Ríos/químicaRESUMEN
The low conductivity of separation electrolytes employed in nonaqueous capillary electrophoresis (NACE) limits the use of on-line sample concentration or stacking by field enhancement. Herein, micelle-to-solvent stacking (MSS) was performed by the simple injection of a micellar solution plug prior to electrokinetic injection of sample prepared under field-enhanced stacking conditions (known as field-enhanced sample injection, FESI). The proposed approach allowed a 214-625-fold improvement in peak signals for targeted anticancer drugs (e.g., tamoxifen) and its major metabolites in NACE using 100% methanol-based separation electrolyte that comprised of 7.5mM deoxycholic acid sodium salt, 15mM acetic acid and 1mM 18-crown-6. These improvements yielded tamoxifen and its metabolites with 2-5 times better stacking efficiency as compared to those obtained without micellar solution injection or FESI only. This is comparable to the results typically achieved when FESI is combined with isotachophoresis (electrokinetic supercharging). The FESI-MSS-NACE was tested for the measuring levels of target drugs in plasma. The analytical figures of merit are also reported.