Advancements in effervescent-assisted dispersive micro-solid phase extraction for the analysis of emerging pollutants.

Emerging pollutants pose an increasing threat to the environment and human well-being, requiring substantial progress in analytical methodologies. Dispersive micro-solid phase extraction (µ-dSPE) has proven successful in detecting and measuring these contaminants, particularly in trace quantities. However, challenges persist in achieving a uniform sorbent distribution and efficient separation from the sample matrix. To address these issues, effervescent-assisted dispersive micro-solid phase extraction (EA-µ-dSPE) was developed. This method uses on-site produced carbon dioxide as a dispersing agent, eliminating the need for vortexing or ultrasonication. Due to the sorbent dispersion in the sample solution, the contact surface between the analyte and the sorbent increases, resulting in increased extraction efficiency, reduced extraction time, and promotes of sustainability. Several parameters are critical to the successful execution of this procedure to extract the analytes, including the type and structure of sorbent, composition of dispersing agents, sorbent separation procedure, and type and properties of desorption solvents. The sorbent plays a critical role in successful extraction of emerging pollutants. It is clear that for the extraction of the analyte on the sorbent, proper interaction must be established between the analyte and the sorbent via physical and chemical interactions. This review thoroughly evaluates the underlying principles of the approach, its potential, and the significant advancements that have been documented. It explores the method's capacity to analyse and identify emerging pollutants, emphasising its potential across various sample matrices for enhanced pollutant identification and quantification.

Novel ultrasensitive automated kinetic exclusion assay for measurement of plasma levels of soluble PD-L1, the predictive and prognostic biomarker in cancer patients treated with immune checkpoint inhibitors.

Recently, the blood plasma or serum levels of soluble programmed death protein 1 (PD-L1), but not tissue PD-L1 expression level, have been proposed as an effective predictive and prognostic biomarker in patients treated with immune checkpoint inhibitors for different types of cancers. The quantification of soluble PD-L1 in blood will provide a quick evaluation of patients' immune status; however, the available assays have limitations in their sensitivity, reproducibility, and accuracy for use in clinical settings. To overcome these problems, this study was dedicated to developing an ultrasensitive automated flow-based kinetic exclusion assay (KinExA) for the accurate and precise measurement of soluble PD-L1 in plasma. The assay was developed with the assistance of KinExA™ 3200 biosensor. In this assay, PD-L1 in its calibrator or plasma sample solution was pre-equilibrated with anti-PD-L1 monoclonal antibody. The equilibrated mixture solution was then passed rapidly over PD-L1 protein that has been coated onto polymethylmethacrylate beads consolidated as a microcolumn in the observation cell of the KinExA™ biosensor. The free anti- PD-L1 antibody was bound to the immobilized PD-L1, however, the unbound molecules were removed from the beads microcolumn by flushing the system with phosphate-buffered saline. Fluorescein-labeled secondary antibody was passed rapidly over the beads, and the fluorescence signals were monitored during the flow of the labeled antibody through the beads. The calibration curve was generated by plotting the binding percentages as a function of PD-L1 concentrations in its sample solution. The working range of the assay with very a good correlation coefficient on a 4-parameter equation (r = 0.9992) was 0.5 - 100 pg mL─1. The assay limit of detection and quantitation were 0.15 and 0.5 pg mL─1, respectively. The recovery values of plasma-spiked PD-L1 were in the range of 96.4-104.3 % (±3.7-6.2 %). The precision of the assay was satisfactory; the values of the coefficient of variations did not exceed 6.2 % for both intra- and inter-day precision. The automated analysis by the proposed KinExA facilitates the processing of many specimens in clinical settings. The overall performance of the proposed KinExA is superior to the available assays for plasma levels of soluble PD-L1. The proposed assay is anticipated to have a great value in the measurement of PD-L1 where a more confident result is needed.

Innovative Graphene-Based Nanocomposites for Improvement of Electrochemical Sensors: Synthesis, Characterization, and Applications.

Graphene, renowned for its exceptional physicochemical attributes, has emerged as a favored substrate for integrating a wide array of inorganic and organic materials in scientific endeavors and innovations. Electrochemical graphene-based nanocomposite sensors have been developed by incorporating diverse nanoparticles into graphene, effectively immobilized onto electrodes through various techniques. These graphene-based nanocomposite sensors have effectively detected and quantified various electroactive species in samples. This review delves into using graphene nanocomposites to fabricate electrochemical sensors, leveraging the exceptional electrical, mechanical, and thermal properties inherent to graphene derivatives. These nanocomposites showcase electrocatalytic activity, substantial surface area, superior electrical conductivity, adsorption capabilities, and notable porosity, which are highly advantageous for sensing applications. A myriad of characterization techniques, including Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), BET surface area analysis, and X-ray diffraction (XRD), have proven effective in exploring the properties of graphene nanocomposites and validating the adjustable formation of these nanomaterials with graphene. The applicability of these sensors across various matrices, encompassing environmental, food, and biological domains, has been evaluated through electrochemical measurements, such as cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and differential pulse voltammetry (DPV). This review provides a comprehensive overview of synthesis methods, characterization techniques, and sensor applications pertinent to graphene-based nanocomposites. Furthermore, it deliberates on the challenges and future prospects within this burgeoning field.

Designing an electrochemical sensor based on ZnO nanoparticle-supported molecularly imprinted polymer for ultra-sensitive and selective detection of sorafenib.

BACKGROUND: Sorafenib (SOR) is a multikinase inhibitor anticancer drug that is used in treating non-small cell lung cancer. In this work, we focused on developing nanomaterial-supported smart porous interfaces by following the molecular imprinting approach for the selective determination of SOR. Determination-based studies in the literature for SOR are limited, and they are chromatographic techniques-based; hence, there is a need in the literature to elaborate the selective and sensitive analysis/monitoring of SOR in both biological and pharmaceutical samples with more studies. RESULTS: The results showed that adding ZnO NPs enhanced the signal five times compared to the solo molecularly imprinted polymer (MIP). Under the optimized conditions, ZnO/AMPS@MIP-GCE showed a linear response in the concentration range between 1.0 × 10-12 and 1.0 × 10-11 M with LOD and LOQ values of 2.25 × 10-13 M and 7.51 × 10-13 M, respectively, in the serum sample. The selectivity study was conducted against common cations, anions, and compounds such as dopamine, paracetamol, ascorbic acid, and uric acid. Also, the imprinting factor (IF) analysis was performed on selected drug substances having structural similarities to SOR and the relative IF values of regorafenib, leflunomide, teriflunomide, nilotinib, axitinib, and dasatinib indicated the selectivity of the developed sensor for SOR. Finally, ZnO/AMPS@MIP-GCE was implemented to determine SOR in the spiked commercial human serum samples and tablet dosage form with bias% between -0.43 and + 0.66. SIGNIFICANCE AND NOVELTY: This study is the first electrochemical study for the determination of SOR, and thanks to the ZnO NPs supported MIP sensor, it stands out in terms of both high sensitivity and superior selectivity. Also, this designed sensor provides controlled orientation of the template and complete removal of templates in a one-step process, allowing extremely low detection and quantification limits.

Application of oxygen scavengers in gel electromembrane extraction: A green methodology for simultaneous determination of nitrate and nitrite in sausage samples.

The generation of oxygen from electrolysis in gel electromembrane extraction (G-EME) causes a negative error when applied to the analysis of easily oxidized species such as nitrite. Nitrite in G-EME is oxidized by oxygen to nitrate, leading to the negative error and the impossibility of simultaneous analysis. In this work, the application of oxygen scavengers to the acceptor phase of the G-EME system was attempted to minimize the oxidation effect. Several oxygen scavengers were selected and examined according to their compatibility with ion chromatography. The mixture of sulfite and bisulfite (14 mg L-1) showed the highest efficiency in preventing the oxidation of nitrite to nitrate. Under the optimized conditions, a good linear range was obtained (10-200 µg L-1; R2 > 0.998) with a detection limit of 8 µg L-1 for both nitrite and nitrate. This method was applied to the simultaneous determination of nitrite and nitrate in sausage samples.

Recent Developments and Applications of Microfluidic Paper-Based Analytical Devices for the Detection of Biological and Chemical Hazards in Foods: A Critical Review.

Nowadays, food safety has become a major concern for the sustainability of global public health. Through the production and distribution steps, food can be contaminated by either chemical hazards or pathogens, and the determination of these plays a critical role in the processes of ensuring food safety. Therefore, the development of analytical tools that can provide rapid screening of these hazards is highly necessary. Microfluidic paper-based analytical devices (µPADs) have advanced significantly in recent years as they are rapid and low-cost analytical screening tools for testing contaminated food products. This review focuses on recent developments of µPADs for various applications in the food safety field. A description of the fabrication of selected papers is briefly discussed, and evaluation of the µPADs' performance with regard to their precision and accuracy as well as their limits of detection is critically assessed. The advantages and disadvantages of these devices are highlighted.

Application of electrocolorimetric extraction for the determination of Ni(II) ions in chocolate samples: A green methodology for food analysis.

This study developed an electrocolorimetric extraction technique as a simple, rapid, and green method for the simultaneous preconcentration and determination of Ni(II) in chocolate samples. The system was designed using an agarose gel (3% w/v) solution containing 10% v/v 80 mM dimethylglyoxime (DMG) and 10% v/v 0.03 M ammonia as colorimetric reagents to determine Ni(II) ions. When voltage was applied to the system, Ni(II) ions were extracted from the donor solution into the gel and formed Ni-DMG complexes with a pink color. Under the optimal conditions, a good linear range was obtained from 30 to 750 µg L-1 (R2 > 0.998) with a detection limit of 1 µg L-1. Inter- and intra-assay results showing relative standard deviations were less than 2.6% and 1.9%, respectively. Our developed method was applied to determine Ni(II) in chocolate samples. The results were in agreement with those obtained using ICP-OES.

Evaluation of complexing agents in the gel electro-membrane extraction: An efficient approach for the quantification of zinc (II) ions in water samples.

In this work, gel electro-membrane extraction (G-EME) combined with flame atomic absorption spectrometry (FAAS) was used for the determination of zinc ions (Zn2+) in water samples. For the first time, the effect of the presence of three types of complexing agents such as phenanthroline (Phen), crown ethers (12C4, 15C5, 18C6), and ethylene-diamine-tetra-acetic acid (EDTA) on the extraction efficiency of zinc ions was studied. In addition, the electroendosmosis (EEO) flow as an unwanted actuator was monitored in the presence and absence of complexing agents. By applying 50 V electrical potential across the membrane, the positive charged Zn2+ ions were migrated from a donor phase (pH 5.0) through the agarose gel membrane (pH 5.0, containing a complexing agent) into the acceptor phase (pH 3.0). The obtained results showed that the highest extraction recoveries were obtained when crown ethers, especially 1% (w/v) 18C6 was added to the gel membrane. In addition, EEO flow was decreased in the presence of all complexing agents (except EDTA), probably due to the increase in electrical resistance. Using the optimum conditions, the limit of detection (LOD), the limit of quantification (LOQ), and extraction recovery% (ER%) were 5.0 µg L-1, 15.0 µg L-1, and 92.5%, respectively. In the end, the applicability of the developed approach was successfully evaluated to determine Zn2+ in tap, mineral, and river water samples.

Online and offline preconcentration techniques on paper-based analytical devices for ultrasensitive chemical and biochemical analysis: A review.

Microfluidic paper-based analytical devices (µPADs) have attracted much attention over the past decade. They embody many advantages, such as abundance, portability, cost-effectiveness, and ease of fabrication, making them superior for clinical diagnostics, environmental monitoring, and food safety assurance. Despite these advantages, µPADs lack the high sensitivity to detect many analytes at trace levels than other commercial analytical instruments such as mass spectrometry. Therefore, a preconcentration step is required to enhance their sensitivity. This review focuses on the techniques used to separate and preconcentrate the analytes onto the µPADs, such as ion concentration polarization, isotachophoresis, and field amplification sample stacking. Other separations and preconcentration techniques, including liquid-solid and liquid-liquid extractions coupled with µPADs, are also reviewed and discussed. In addition, the fabrication methods, advantages, disadvantages, and the performance evaluation of the µPADs concerning their precision and accuracy were highlighted and critically assessed. Finally, the challenges and future perspectives have been discussed.

Electrocolorimetric gel-based sensing approach for simultaneous extraction, preconcentration, and detection of iodide and chromium (VI) ions.

A total integrated electrocolorimetric sensing approach consisting of gel-based electromembrane extraction and colorimetric detection in a one-step process was developed. This system was designed using colorimetric reagents preadded to the agarose gel for the determination of the following two model analytes: iodide and hexavalent chromium [Cr(VI)]. In this system, when a voltage was applied, the analytes were extracted and transferred from the sample solution (donor phase) to the gel (acceptor phase). The analytes then simultaneously reacted with the colorimetric reagents inside the gel, yielding blue and violet colors for iodide and Cr(VI), respectively. These colors were then analyzed using a portable spectrometer and could also be distinguished with the naked eye. Parameters affecting the extraction efficiency were studied and optimized for both analytes. The gel composition for iodide detection was 4% (w/v) agarose, 5% (v/v) H2O2, and 1% (w/v) starch in 2 mM HCl. The gel composition for Cr(VI) detection was 2% (w/v) agarose and 1% (w/v) DPC in 0.5 mM HNO3. Both analytes were extracted at an applied potential of 50 V, an extraction time of 15 min and a stirring rate of 600 rpm. Under the optimized conditions, the developed systems provided linear responses within 15 min for iodide concentrations ranging from 50 to 250 µg L-1 with a detection limit of 18 µg L-1 and for Cr(VI) concentrations ranging from 30 to 125 µg L-1 with a detection limit of 5 µg L-1. Finally, these systems were successfully applied to the determination of iodide in iodide food supplement samples and Cr(VI) in drinking water samples, showing a negligible matrix effect. This integration could also be extended to other analytes and detection systems to develop sensitive, on-site, and environmentally friendly sensing approaches.

Gel electromembrane microextraction followed by ion chromatography for direct determination of iodine in supplements and fortified food samples: Green chemistry for food analysis.

In this study, a sensitive, selective, and environmentally friendly analytical method for direct extraction and preconcentration of iodine was developed. Iodine, as an iodate ion or iodide ion, was simultaneously extracted and preconcentrated by gel electromembrane microextraction (G-EME) and analyzed for total iodine by ion chromatography. The total iodine was determined by combining the peak areas of both iodate and iodide ions. Under the optimized conditions, linear calibration for iodine using a mixture of iodate and iodide ions was obtained from 10 to 100 µg L-1 (r2 > 0.996). The detection limit was 7.0 µg L-1. Recoveries of spiked iodine (as iodate) in the samples were greater than 90%. The method was applied for the determination of iodine in dietary supplements and fortified food samples, i.e., iodine-enriched eggs. Our developed method could be directly applied for the determination of iodine in different matrix samples including eggs without a pretreatment step.

Simultaneous determination of benzoic acid, sorbic acid, and propionic acid in fermented food by headspace solid-phase microextraction followed by GC-FID.

A simple and environmentally friendly method was developed for simultaneous determination of benzoic acid, sorbic acid, and propionic acid in fermented food samples. The analytes were extracted and pre-concentrated by headspace solid-phase microextraction (HS-SPME) and analysed by GC-FID. Central composite design (CCD) was conducted for the optimization of HS-SPME conditions. Under optimal conditions, a good linear range was obtained in the range of 5-150 mg L-1. The limit of detection (LOD) values were 1.1-1.7 mg L-1. The developed method was successfully applied to determine the concentration of three organic acid preservatives in various fermented food samples, including thai shrimp paste, pickled vegetables, soy sauce and fish sauce, with high accuracy (recoveries were between 83% and 109%) and good precision (%RSD was less than 6.0% and 4.5% for intra-day and inter-day, respectively).

Combining graphite with hollow-fiber liquid-phase microextraction for improving the extraction efficiency of relatively polar organic compounds.

In this study, we have developed a simple and effective hybrid extraction method based on the incorporation of raw carbon nanosorbents and octanol in the pores of a hollow-fiber membrane for improving the extraction efficiency of relatively polar organic compounds. Trihalomethanes (THMs) were used as model analytes. Three types of carbon nanosorbents (graphite, graphene, and multi-walled carbon nanotubes) were studied. The carbon sorbent incorporating membrane was used in a two-phase mode liquid-phase microextraction, with 1-octanol as the acceptor solution. Using a graphite-reinforced hollow-fiber membrane and an extraction time of 10 min, enrichment factors of 40-71 were obtained for trichloromethane, bromodichloromethane, bromoform, and chlorodibromomethane. Linear working ranges of 0.2-100 µg L-1 and limits of detection ranging from 0.01 µg L-1 (for CHCl2Br and CHClBr2) to 0.1 µg L-1 (for CHCl3) were achieved. The minimum detectable concentrations were far below the maximum concentration levels (60-200 µg L-1) set by the WHO for drinking water. The carbon-sorbent-reinforced hollow-fiber liquid-phase microextraction afforded higher extraction efficiency and shorter extraction time compared with conventional hollow-fiber liquid-phase microextraction. Finally, the method was applied to the analysis of real water samples, such as drinking water, tap water, and swimming pool water samples.

Development of a Sample Treatment Method for a Flow Injection Determination of Iodine in Eggs: A Comparison Study.

A simple treatment method was proposed for the determination of iodine in eggs, followed by a flow-injection spectrophotometry based on the catalytic effect of iodine in the reduction reaction of Ce(IV) with As(III). The egg matrix was removed based on protein precipitation principles. Several protein precipitation methods were investigated. The treatment using trichloroacetic acid satisfactorily removed most of the egg matrix components. A colorless solution and a good signal were achieved. The method provided more reliable results compared to the conventional alkali dry ashing.

Chromium speciation using paper-based analytical devices by direct determination and with electromembrane microextraction.

In this study, we developed and compared three different methods for chromium speciation in water samples using microfluidic paper-based analytical devices (µPADs). In all methods, detection was based on the complexation reaction of Cr(VI) with diphenylcarbazide on the µPADs. Cr(III) ions were oxidized to Cr(VI) by Ce(IV) prior to colorimetric detection on the µPADs. In the first method, oxidization of Cr(III) to Cr(VI) in the solution containing both trivalent and hexavalent chromium was performed using a batch procedure to obtain total chromium. A dual electromembrane extraction (DEME) technique for simultaneous preconcentration and extraction of chromium species and a single electromembrane extraction (SEME) for preconcentration and extraction of Cr(VI)/total chromium [quantified as Cr(VI) content after oxidation of Cr(III) ions to Cr(VI)] were used in the second and third methods, respectively. The electromembrane extraction was based on the electrokinetic migration of cationic Cr(III) and anionic Cr(VI) toward the cathode and anode, respectively, into the two different hollow fibres. Octanol-1 and bis(2-ethylhexyl) phosphate (DEHP) in octanol-1 (0.7% v/v) were the most suitable supported liquid membranes for extraction of Cr(VI) and Cr(III), respectively. Among these methods, SEME showed the lowest limits of detection for both analytes. Under optimized conditions, linear calibrations were obtained for Cr(III) from 3 to 30 µg L-1 and for Cr(VI) from 3 to 70 µg L-1. The detection limits were 1.0 µg L-1 and 0.7 µg L-1 for Cr(III) and Cr(VI), respectively. Our developed method was applied to analyse water samples spiked with different concentrations of Cr(III) and Cr(VI) at the parts-per-billion (ppb) level. The statistical evaluation showed that the proposed method agreed well with the validation method, i.e., inductively coupled plasma atomic emission spectroscopy (ICP-AES).

A colorimetric paper-based analytical device coupled with hollow fiber membrane liquid phase microextraction (HF-LPME) for highly sensitive detection of hexavalent chromium in water samples.

A simple and highly sensitive procedure based on the combination of hollow fiber membrane liquid phase microextraction and a microfluidic paper-based analytical device (µPAD) was developed for pre-concentration and determination of hexavalent chromium in water samples. The hexavalent chromium was pre-concentrated using the HF-LPME technique via ion exchange or a coupled transport process through a supported ionic liquid (Aliquat 336) prior to colorimetric detection with diphenylcarbazide on the µPAD. The violet colour could be seen by the naked eye. Images from the µPADs were scanned using a commercial desktop scanner at 600 dpi resolution. ImageJ software was used for quantitative analysis by measuring the intensity values at green colour channel since it gave the best sensitivity among the RGB colour. Under optimal conditions, the calibration curve was linear in the range 10-90 µg L-1, with a limit of detection of 3 µg L-1. The developed method was successfully applied to determine the level of hexavalent chromium spiked into natural water samples at the parts-per-billion (ppb) level, and the results were in good agreement with those obtained using inductively coupled plasma atomic emission spectroscopy (ICP-AES). The developed method was able to improve the detection limit of the conventional µPAD, and was expected to be used for the effective analysis of hexavalent chromium in natural water.

Development of flow systems incorporating membraneless vaporization units and flow-through contactless conductivity detector for determination of dissolved ammonium and sulfide in canal water.

Use of membraneless vaporization (MBL-VP) unit with two cone-shaped reservoirs is presented for on-line separation and detection of non-volatile species. A flow system comprising two sets of MBL-VP units with a single in-house capacitively coupled contactless conductivity detector (C4D) was developed for dual determination of ammonium and sulfide ions. Using the continuous-flow section, two zones (280µL) of a sample, either mixed with sodium hydroxide (for ammonium) or hydrochloric acid (for sulfide), are separately delivered into the donor reservoir of the MBL-VP units. The acceptor reservoir contains either 150µL of 15µM HCl solution (for ammonia) or pure water (for hydrogen sulfide), respectively. Vaporization and trapping of the ammonia or hydrogen sulfide gas from the donor reservoir into the liquid acceptor cone occur concurrently in the two separate MBL-VP units. After trapping the gas for 3min, the two 150-µL liquid acceptors are sequentially aspirated through the C4D flow cell for recording the changes in the conductivity. Linear calibrations were obtained for ammonium from 5 to 80µM (Volt = (0.0134 ± 0.0003) [NH4+] - (0.01 ± 0.01), r2 = 0.998) and for sulfide from 5 to 200µM (Volt = (0.0335 ± 0.0009) [S2-] - (0.13 ± 0.09), r2 = 0.996). Analysis time for both analytes is only 320s. Our method was applied to analyze canal water samples. The results agree well with membrane gas-diffusion flow injection techniques, using bromothymol blue for ammonium and methylene blue for sulfide. Recoveries ranged from 95% to 104%.