Minimize Matrix Effects Research Articles

Quantification of bile acids: a mass spectrometry platform for studying gut microbe connection to metabolic diseases

Bile acids (BAs) serve multiple biological functions, ranging from the absorption of lipids and fat-soluble vitamins to serving as signaling molecules through the direct activation of dedicated cellular receptors. Synthesized by both host and microbial pathways, BAs are increasingly understood as participating in the regulation of numerous pathways relevant to metabolic diseases, including lipid and glucose metabolism, energy expenditure, and inflammation. Quantitative analyses of BAs in biological matrices can be problematic due to their unusual and diverse physicochemical properties, making optimization of a method that shows good accuracy, precision, efficiency of extraction, and minimized matrix effects across structurally distinct human and murine BAs challenging. Herein we develop and clinically validate a stable-isotope-dilution LC/MS/MS method for the quantitative analysis of numerous primary and secondary BAs in both human and mouse biological matrices. We also utilize this tool to investigate gut microbiota participation in the generation of structurally specific BAs in both humans and mice. We examine circulating levels of specific BAs and in a clinical case-control study of age- and gender-matched type 2 diabetes mellitus (T2DM) versus nondiabetics. BAs whose circulating levels are associated with T2DM include numerous 12α-hydroxyl BAs (taurocholic acid, taurodeoxycholic acid, glycodeoxycholic acid, deoxycholic acid, and 3-ketodeoxycholic acid), while taurohyodeoxycholic acid was negatively associated with diabetes. The LC/MS/MS-based platform described should serve as a robust, high-throughput investigative tool for studying the potential involvement of structurally specific BAs and the gut microbiome on both physiological and disease processes.

Quadruplex stable isotope derivatization strategy for the determination of panaxadiol and panaxatriol in foodstuffs and medicinal materials using ultra high performance liquid chromatography tandem mass spectrometry

This work proposed a novel strategy based on quadruplex stable isotope derivatization for sensitive, accurate, speedy and green determination of panaxadiol (PD) and panaxatriol (PT). This strategy integrated with ultrasound-assisted dispersive liquid-liquid microextraction, microwave-assisted derivatization, and magnetic graphene oxide dispersive solid phase extraction as efficient sample pretreatment techniques, coupling with ultra-high performance liquid chromatography tandem mass spectrometry detection in multiple reaction monitoring mode for the analytical purpose of high-throughput, sensitivity, selectivity, green and accuracy. Quadruplex mass spectrometry sensitizing derivatization reagents, 3-N-(D0-/D3-methyl-, and D0-/D5-ethyl-)-2′-carboxyl chloride rhodamine 6 G, were designed, synthesized and applied for the high-throughput derivatization of hydroxyl‑containing PD and PT for the first time. The analogue derivatives of PD and PT standards using 3-N-propyl-2′-carboxyl chloride rhodamine 6 G as derivatization reagent were employed as the internal standards for the mass spectrometry quantitation to minimize matrix effect. All rhodamine 6 G derivatives of PD and PT were easily and selectively adsorbed by magnetic graphene oxide for efficient magnetic dispersive solid phase extraction before injection. Parameters of (micro-) extractions, derivatization and liquid chromatography-mass spectrometry conditions were all optimized in details. Method validation results consisting of linearity, accuracy, precision, repeatability, matrix effect, stability and limits of detection (LODs, 0.02 ng/mL for PD and 0.03 ng/mL for PT) were determined. The analytical performance of this method benefited from efficient integration of suitable sample pretreatment techniques and characteristic structure of rhodamine 6 G with four mass tags in derivatization reagents. The developed and validated method has been applied to the quantitation of PD and PT for the quality assessment of related foodstuffs and traditional Chinese medicinal materials.

Determination of Sudan dyes in chili products by micellar electrokinetic chromatography-MS/MS using a volatile surfactant

A new MEKC-MS/MS method was developed for the determination of four Sudan dyes in chili products. The separation and MS detection conditions were optimized to achieve fast, efficient, selective, and sensitive determination of Sudan I, Sudan II, Sudan III, and Sudan IV dyes. The target compounds were extracted from chili samples with acetonitrile and cleaned by freeze-out. This two-step sample preparation led to excellent extraction efficiency and minimal matrix effect. The analytical performance of the method was very good, with r2 ≥ 0.9914 and limits of quantification lower than 22 μg kg−1. The precision was below 15.7%. The recovery for spiked samples ranged from 84.4 to 99.6%, with relative standard deviations less than 8.0%. For all evaluated samples, the matrix effects did not exceed ± 10%. The applicability of the proposed method was demonstrated with 20 chili products, two of which were found to contain Sudan I and IV residues.

Solid-phase extraction and high performance liquid chromatography with diode array detection method for the determination of antibiotic residues in poultry tissues

Abstract This article presents information on high performance liquid chromatography with diode array detection (HPLC-DAD) method for the simultaneous determination of six antibiotic residues (enrofloxacin, sulfadimethoxine, sulfamerazine, sulfamethoxazole, sulfamoxole, and tylosin) in three poultry tissues. The target antibiotic residues were extracted from raw poultry samples following concentration, clean-up through solid phase extraction. The data describe the extraction, determination and screening procedures of these common antibiotic residues in 111 samples of fresh and frozen poultry meats. The limit of detection (LOD) ranged from 5.37–55.4 ng/g, while the quantification limit (LOQ) was in the range of 17.9–184 ng/g, respectively, with minimal matrix effect. The calibration curves obtained exhibited a good linear response with the coefficient of determination, R2 > 0.996. Some concentrations exceeded their maximum residue limits in most samples. These findings indicated elevated levels of antibiotic residues in tissues of locally produced and illegally imported poultry meat samples.

Quantification of organic contaminants in urban stormwater by isotope dilution and liquid chromatography-tandem mass spectrometry

Pollutants transported in urban stormwater runoff induce pervasive water quality degradation in receiving waters. To accurately characterize stormwater quality and treatment system performance across the range of possible contaminant characteristics, comprehensive multi-residue analytical methods are necessary. Here, we developed a solid-phase extraction (SPE) and high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method to quantify representative stormwater-derived organic contaminants across multiple chemical classes, including vehicle-related chemicals, corrosion inhibitors, industrial chemicals, pesticides, pharmaceuticals and personal care products, and antioxidants. Extraction conditions, isotope-labeled internal standards, and LC-MS/MS parameters were optimized to enhance recovery, minimize matrix effects, and maximize selectivity and sensitivity. The developed method was sensitive (method quantification limits < 10 ng/L for > 80% of selected analytes) and accurate (mean relative recoveries in the range of 70-130%, with relative standard deviations < 25% for 77% of the analytes) for most of the analytes. The method was used to analyze samples collected from nine urban watersheds during a storm event; 62% of the 39 analytes were detected at least once at concentrations up to 540 ng/L (1,3-diphenylguanidine). Spatial trends in detection and concentration were observed for vehicle-related and industrial chemicals that correlated with vehicle traffic. Total concentrations of pesticides suggested that residential uses could be more important sources than agriculture. This study illustrates the pervasive occurrence of a wide variety of stormwater-derived chemicals in urban receiving waters and highlights the need to better understand their environmental fate and ecological implications. Graphical abstract.

22 CANONICAL CORRELATION ANALYSIS OF ADHD POLYGENIC RISK AND FUNCTIONAL BRAIN CONNECTIVITY

A novel assay for the simultaneous determination of ibuprofen (IBU) and its four probable metabolites, 1-hydroxyibuprofen (1-OH IBU), 2-hydroxyibuprofen (2-OH IBU), 3-hydroxyibuprofen (3-OH IBU) and carboxyibuprofen (CBX IBU) in equine urine samples with the application of Gas Chromatography-Electron Ionization-Mass Spectrometry (GC-EI-MS) has been developed and elaborated. The new approach for sample preparation including minimizing matrix effects by the application of weak cation exchange solid-phase extraction together with strong cation exchange solid-phase extraction has been applied. The GC-EI-MS method was validated to demonstrate specificity, matrix effect, linearity, limit of detection (LOD) and quantification (LOQ), precision, trueness, carry-over and stability by using the matrix-matched quality control samples. Additionally, extraction yield was evaluated. The assay achieved the LOQ of 1.75 μg mL−1, 0.62 μg mL−1, 4.15 μg mL−1, 0.58 μg mL−1 and 4.04 μg mL−1 for IBU, 1-OH IBU, 2-OH IBU, 3-OH IBU and CBX IBU, respectively. The developed method has been successfully applied to the excretion study in horses, in which a single oral IBU dose was administered to twelve horses (mares and geldings) and equine urine samples were collected for 5 or 6 days after the drug administration. Data on the detection and determination of three IBU metabolites, 2-OH IBU, 3-OH IBU and CBX IBU in equine urine samples has been presented for the first time. The obtained results indicated the rapid excretion of IBU and its metabolites that were detectable only in the first day after the drug administration. IBU was mainly the most abundant compound detected in equine urine samples (with two exceptions in the case of samples collected from two horses, for which the highest instrumental responses were obtained for CBX IBU). The received results have indicated that two major IBU metabolites, CBX IBU and 2-OH IBU can be important markers for the IBU abuse in view of doping control in equestrian sports.

Investigation of midazolam electro-oxidation on boron doped diamond electrode by voltammetric techniques and density functional theory calculations: Application in beverage samples

Midazolam (MID) is a sedative drug which can be added in beverage samples as drug-facilitated-sexual assault (date rape drug). This type of drug has short half-life in biological fluids (not detectable) which often prevents the correlation between drug abuse and crime. In this work, we described a simple and low-cost method for fast screening and selective determination of MID in beverage samples (vodka, whiskey and red wine). For the first time, the electrochemical oxidation of MID was used for this purpose. The oxidation mechanism was studied using electrochemical techniques (cyclic and square-wave voltammetry) and computational simulations (density functional theory calculations). Differential-pulse voltammetry, boron-doped diamond electrode (BDDE), and Britton-Robinson (BR) buffer (pH = 2) were selected as electrochemical analysis technique, working electrode and supporting electrolyte, respectively. Different linear response ranges (4–25 μmol L−1 with r = 0.9972; 1–10 μmol L−1 with r = 0.9951; 1–15 μmol L−1 with r = 0.9982) and limits of detection (0.46, 0.43 and 0.33 μmol L−1) were obtained for the analysis of vodka, whisky, and red wine solutions, respectively. The precision and accuracy were satisfactory considering the low relative standard deviation values (RSD < 6.3%, n = 15) and minimal sample matrix effects (recovery values between 87 and 103%).

Paper spray mass spectrometry: A new drug checking tool for harm reduction in the opioid overdose crisis.

Fentanyl and related psychoactive substances are at the forefront of the opioid overdose crisis, for which a complete solution is not immediately obvious. Drug testing for harm reduction may be an effective approach to both reduce overdoses and importantly, engage people who use drugs (PWUD) with the medical system. Paper spray mass spectrometry (PS-MS) is an ambient ionization strategy that is uniquely suited to address this complicated analytical task. This perspectives article presents the merits of PS-MS, with a focus upon the current state of its use as a candidate drug checking strategy for harm reduction. PS-MS is inherently sensitive and selective, with detection limits in the picogram range. It requires small drug samples (~1 mg) for quantitative drug testing, critical to encourage pre-consumption measurements by PWUD in the context of a harm reduction strategy. Calibrations obtained in surrogate drug matrices containing highly concentrated primary drugs demonstrate comparable sensitivities, a wide calibration range, and minimal matrix effects. PS-MS can be interfaced with high-resolution MS for non-targeted analysis, allowing the identification of novel psychoactive substances as they appear in street drugs. Individual quantitative PS-MS measurements for drug testing can be done in 1 minute or less, resulting in high sample throughput. Significant advancement in mass spectrometer miniaturization and mobilization has concomitant benefits for direct, on-site drug checking, such as reduced cost, simplified maintenance and ease of use by less skilled operators. While PS-MS technology continues to rapidly advance, it is our opinion that PS-MS can be utilized as an effective tool for harm reduction in the opioid overdose crisis.

Rapid one-step cleanup method to minimize matrix effects for residue analysis of alkaline pesticides in tea using liquid chromatography–high resolution mass spectrometry

Matrix effects in complex tea matrices remains a great challenge to rapid quantitative analysis of multi-residue pesticides by analysis of mass spectrometry. Herein, a mixed-mode polymer cationic exchange based dispersive solid-phase extraction (DSPE) procedure was established to eliminate matrix effects of tea for a rapid target alkaline multi-residue pesticides analysis. One-step DSPE procedure can eliminate matrix interferences from the tea extract without additional dilution or tedious cleanup operations. Liquid chromatography–high resolution mass spectrometry using pre-column dilution injection mode was used as the detection technique, while eliminating solvent effects of target analytes and improving the detection sensitivity. Based on this effective analytical method, the results of absolute matrix effects were within 0.77–1.08 for quantitation of the 68 alkaline pesticides, and superior relative matrix effects were also achieved with RSD values below 9.8%. Finally, this method was validated and applied to the alkaline pesticides analysis of the 123 tea samples.

Simultaneous Quantification of 13 Cannabinoids and Metabolites in Human Plasma by Liquid Chromatography Tandem Mass Spectrometry in Adult Epilepsy Patients.

A sensitive, robust method was developed and validated to quantitate 13 major natural cannabinoid parent and metabolite compounds in human plasma at or below 0.5 ng/mL. A liquid chromatography tandem mass spectrometry method was developed and validated to measure 13 cannabinoid compounds: cannabidiol (CBD), cannabidiolic acid, cannabidivarin, cannabinol, cannabigerol, cannabigerolic acid, cannabichromene, Δ-tetrahydocannabinol (THC), Δ-tetrahydrocannabinolic acid A (THCA), Δ-tetrahydrocannabivarin (THCV), 11-hydroxy-Δ-tetrahydrocannbinol (11-OH-THC), 11-nor-9-carboxy-Δ-tetrahydrocannbinol (THC-COOH), and 11-nor-9-carboxy-Δ-tetrahydrocannabinol glucuronide (THC-COOH-glu). Samples (200 µL) were extracted through protein precipitation and separated with a Kinetex EVO C18 column and a 65%-95% gradient of methanol and 0.2% ammonium hydroxide/H2O at a flow rate of 0.4 mL/min. Samples were obtained from patients with epilepsy receiving cannabis for the treatment of seizures. The extracted lower limit of quantification was 0.05 ng/mL for CBD, cannabidivarin, cannabinol, and 11-OH-THC; 0.10 ng/mL for cannabidiolic acid, cannabigerol, cannabichromene, cannabigerolic acid, THC, THCA, and THCV; and 0.50 ng/mL for THC-COOH and THC-COOH-glu. Mean quality control intraday accuracy and precision for all analytes ranged 96.5%-104% and 2.7%-4.9%, respectively, whereas interday accuracy and precision ranged 98%-103.3% and 0.2%-3.6%, respectively. An absolute matrix effect was observed for some analytes, however, with minimal relative matrix effect. Lack of nonspecific drug binding to extraction glass and plasticware was verified. Patient CBD levels ranged from 0.135 to 11.13 ng/mL. The validated method met FDA guidelines for bioanalytical assays precision and accuracy criteria. The assay reliably confirmed the use of particular medical cannabis formulations in patient samples as well as reliably measured low CBD concentrations from single-dose CBD exposure.

Analytical methods for the routinely evaluation of pesticide residues in lemon fruits and by products

Citrus fruits and their by-products such as concentrated juices and essential oils are important intermediate by-products in the food industry that can selectively accumulate plant protection agrochemicals employed in their production. They are very difficult matrices for pesticide residue analysis due their high number and concentration of phytochemicals that could hamper the determinations. The fruit processing leads to the concentration/dilution or elimination of some of these natural products that change totally the nature of the matrix where the pesticides partition unevenly. Looking at the industrial process of the fruit, a unified vision for the pesticide residues analysis throughout the lemon fruit chain production, useful for the routine analysis of the above mentioned three matrices is presented. The driven concept is the minimization of matrix effects through sample dilution of the concentrated by-products, either after sample treatment or not. This approach will contribute to the maintenance of the whole instrumental system. QuEChERS AOAC 2007.01 was selected as the most suitable protocol for routine determination of, residues of 16 the pesticides most commonly used in the fruits during the citrus production through liquid chromatography coupled to tandem mass spectrometry (LC–MS/MS). The same protocol was applied for pesticide residue analysis in concentrated juice after diluting 4 times the sample to minimize the matrix effects. For the analysis of lemon essential oils, the dilution and shoot procedure proved to be useful for LC–MS/MS and gas chromatography–mass spectrometry determination. The three methodologies were validated following SANTE guidelines, with quantitation limits below the established European Union and Codex Alimentarius maximum residue limits. The developed methodologies are useful tools for the routine control analysis of pesticide residues in lemon matrices, allowing high sample throughput and enhancing labs productivity.

Magnetic nanoparticles for smart electrochemical immunoassays: a review on recent developments.

This review (with 129 refs) summarizes the progress in electrochemical immunoassays combined with magnetic particles that was made in the past 5years. The specifity of antibodies linked to electrochemical transduction (by amperometry, voltammetry, impedimetry or electrochemiluminescence) gains further attractive features by introducing magnetic nanoparticles (MNPs). This enables fairly easy preconcentration of analytes, minimizes matrix effects, and introduces an appropriate label. Following an introduction into the fundamentals of electrochemical immunoassays and on nanomaterials for respective uses, a large chapter addresses method for magnetic capture and preconcentration of analytes. A next chapter discusses commonly used labels such as dots, enzymes, metal and metal oxide nanoparticles and combined clusters. The large field of hybrid nanomaterials for use in such immunoassays is discussed next, with a focus on MNPs composites with various kinds of graphene variants, polydopamine, noble metal nanoparticles or nanotubes. Typical applications address clinical markers (mainly blood and urine parameters), diagnosis of cancer (markers and cells), detection of pathogens (with subsections on viruses and bacteria), and environmental and food contaminants as toxic agents and pesticides. A concluding section summarizes the present status, current challenges, and highlights future trends. Graphical abstract Magnetic nanoparticles (MNP) with antibodies (Ab) capture and preconcentrate analyte from sample (a) and afterwards become magnetically (b) or immunospecifically (c) bound at anelectrode. Signal either increases due to the presence of alabel (b) or decreases as theredox probe is blocked(c).

A smartphone-assisted pressure-measuring-based diagnosis system for acute myocardial infarction diagnosis.

BackgroundAcute myocardial infarction (AMI), usually caused by atherosclerosis of coronary artery, is the most severe manifestation of coronary artery disease which results in a large amount of death annually. A new diagnosis approach with high accuracy, reliability and low measuring-time-consuming is essential for AMI quick diagnosis.PurposeThe objective of this study was to develop a new point-of-care testing system with high accuracy and reliability for AMI quick diagnosis.Patients and methods50 plasma samples of acute myocardial infarction patients were analyzed by developed Smartphone-Assisted Pressure-Measuring-Based Diagnosis System (SPDS). The concentration of substrate was firstly optimized. The effect of antibody labeling and matrix solution on measuring result were then evaluated. And standard curves for cTnI, CK-MB and Myo were built for clinical sample analysis. The measuring results of 50 clinical samples were finally evaluated by comparing with the measuring result obtained by CLIA.ResultsThe concentration of substrate H2O2 was firstly optimized as 30% to increase measuring signal. A commercial serum matrix was chosen as the matrix solution to dilute biomarkers for standard curve building to minimize matrix effect on the accuracy of clinical plasma sample measuring. The standard curves for cTnI, CK-MB and Myo were built, with measuring dynamic range of 0–25 ng/mL, 0–33 ng/mL and 0–250 ng/mL, and limit of detection of 0.014 ng/mL, 0.16 ng/mL and 0.85 ng/mL respectively. The measuring results obtained by the developed system of 50 clinical plasma samples for three biomarkers matched well with the results obtained by chemiluminescent immunoassay.ConclusionDue to its small device size, high sensitivity and accuracy, SPDS showed a bright potential for point-of-care testing (POCT) applications.

Room temperature and sensitive determination of haloanisoles in wine using vacuum-assisted headspace solid-phase microextraction

Headspace solid-phase microextraction (HSSPME) is a widespread technique used to extract trace amounts of haloanisoles from wine samples. A major challenge to overcome is the high ethanol content in wines that affects the solubilities of haloanisoles and reduces their headspace abundance. To overcome this obstacle and meet sensitivity requirements, reported HSSPME procedures typically suggest heating the wine samples and/or sampling for extended times. The present work proposes the use of vacuum-assisted HSSPME (Vac-HSSPME) to accelerate the extraction kinetics whilst sampling at room temperature. Although ethanol affected the physico-chemical properties of the target analytes, these changes were not sufficient to prevent the positive effect of vacuum on HSSPME sampling. To demonstrate the benefits of adopting the vacuum approach, Vac-HSSPME and regular HSSPME methods were independently optimized and the results were compared at all times. The effect of ethanol under each pressure condition was also discussed. Under the optimum conditions found, Vac-HSSPME sampling for 30 min at room temperature at 25 °C yielded lower detection limits (0.13 to 0.19 ng L−1) than those obtained with regular HSSPME sampling for 30 min at 55 °C (0.26 to 0.76 ng L−1). The proposed Vac-HSSPME method was successfully applied to quantify haloanisoles in bottled red wines and a discussion on the effect of wine volatiles was included. The standard addition method was used to minimize matrix effects. The increase in total pressure due to the presence of ethanol and other volatile wine components did not reduce the positive effect of vacuum on HSSPME. Nonetheless, in accordance to past HSSPME methods, the limits of detection and quantification were affected due to the noise level increase and analyte interaction with matrix. The proposed Vac-HSSPME procedure was applied to twelve bottled red wines and one sample was found positive on 2,4,6-trichloronanisole.

Analysis of 44 pharmaceuticals consumed by elderly using liquid chromatography coupled to tandem mass spectrometry

Elderly people represent about the 15% of the total world population and often include a polymedicated age group with an average consumption of 5–10 pills per day. The main pharmaceuticals consumed are antianalgesics, antidiabetics, anti-parkinson compounds, anti-convulsants, drugs to treat constipation and drugs to treat cancer. In this study, we have developed a multiresidue method for the analysis of 44 selected pharmaceuticals prioritized according to the foremost consumption by the elderly in effluents from senior residences. Given the complexity of these waters, method optimization included the selection of the extraction cartridge, pH and volume, and the optimization of the liquid chromatography-tandem mass spectrometry conditions to minimize matrix effects and obtain high yields. Good method performance was obtained, with recoveries between 27 and 116% and high sensitivity. The method was tested in a preliminar study to determine pharmaceuticals released in situ from the untreated effluents of the senior residences. High concentrations were detected, with levels between 0.20 and 2891 μg L−1 attributed to the high consumption of drugs in the studied residences, which gather around 100 residents. The most detected pharmaceuticals were aspirin, macrogol, levofloxacin, cyclophosphamide, diclofenac, ibuprofen, paracetamol, carbamazepine, levetiracetam, pregabalin, quetiapine, chlormetiazole, trazodone, caffeine, 2,4-dichlorobenzyl alcohol and amylmetacresol. This study describes the analytical conditions to determine the outmost consumed pharmaceuticals in wastewaters released from senior residences.

Selective enrichment and quantification of okadaic acid in shellfish using an immunomagnetic-bead-based liquid chromatography with tandem mass spectrometry assay.

Okadaic acid is a marine biotoxin that primarily occurs in shellfish and can cause diarrheic shellfish poisoning in humans. When analyzing biological samples using liquid chromatography with tandem mass spectrometry, the presence of complex matrices is a major issue. Thus, it is crucial to selectively and simply extract the target analyte from samples and minimize matrix effects simultaneously. To meet this need, an immunomagnetic-bead-based liquid chromatography with tandem mass spectrometry method was developed to detect okadaic acid in shellfish. Magnetic beads bound to monoclonal antibody against okadaic acid were used as affinity probes to specifically enrich okadaic acid in samples, which effectively eliminated matrix effects. A magnetic separator was used to aggregate and separate magnetic particles from sample matrices, and methanol was used to elute okadaic acid from the magnetic beads. Standard solution prepared with methanol was employed directly for quantitative analysis. Several experimental conditions were optimized to improve performance. The method is of interest as a rapid (10min) sample clean-up and selective enrichment tool, and it showed good linearity and sensitivity, with reported limits of detection and quantitation of 3 and 10 μg/kg, respectively. Fifty-three shellfish samples from an aquatic products market were tested using this method, and four samples positive for okadaic acid were found.

High throughput residue analysis of paraquat and diquat involving hydrophilic interaction liquid chromatographic separation and mass spectrometric determination

ABSTRACTA selective, sensitive and robust LC-MS/MS method is reported for the determination of the residues of paraquat and diquat in various fruit matrices, including grape, apple and pomegranate. The extraction with acidified water (0.1 M HCl) at 80°C (15 min) offered superior recoveries for both analytes with a significantly lower matrix effects as compared to the extraction with acidified methanol by the methods reported in the existing literature. The optimised HPLC conditions on hydrophilic interaction liquid chromatography (HILIC) columns, when coupled with electrospray ionisation-tandem mass spectrometry, offered their limit of quantification at 0.01 mg kg−1. The analysis on an XBridge HILIC column required a thorough optimisation of the gradient programme to induce chromatographic separation and minimise matrix effects. This was not necessary when a CORTECS HILIC column was used, which provided selective and sensitive analysis within 5 min runtime using isocratic flow. Isotopically labelled internal standards corrected the recoveries of both analytes within 70–120% (RSD < 20%). For the first time, the applications of high resolution accurate mass analysis in the ‘time of flight – multiple reaction monitoring’ mode have been demonstrated as a complementary means of targeted screening of these compounds at 0.01 mg kg−1 level. The method has a strong potential for applications in both official control and by those involved in food production for checking compliance with the EU MRLs.

Electrochemical Determination of Sunitinib in Biological Samples Using Polyacrylonitrile Nanofibers/Nickel-Zinc-Ferrite Nanocomposite/Carbon Paste Electrode

This article presents the novel modifier; polyacrylonitrile nanofibers/Ni0.5Zn0.5Fe2O4 nanoparticles nanoparticles as a novel modifier, which has been synthesized using an electrospinning method. This nanocomposite has been used to construct an electrochemical sensor for highly sensitive determination of sunitinib (STB) drug in biological samples. The synthesized nanocomposite was fully characterized using methods such as Fourier transform infrared spectroscopy, scanning electron microscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. For the electrochemical determination of STB, the differential pulse voltammetry signal of the drug electrooxidation on carbon paste electrode modified with the newly developed nanocomposite was investigated. Preliminary experiments showed that the nanocomposite had an electrocatalytic effect on the electrooxidation of STB and a significant improvement in the anodic current of the drug was obtained at +0.66 V. Under the optimum conditions, the analytical figures of merit were extracted and the method was fully validated. A relatively wide dynamic linear range of 0.018–18.77 μ mol L−1 with the detection limit of 0.9 n mol L−1 was obtained. Furthermore, the method was applied for the determination of STB in biological fluid samples such as human serum samples with acceptable recoveries (97–102), satisfactory precision (2–4%RSD) and minimal matrix effects.

Multi-Energy Calibration: A Practical Method for Determination of Macro and Micro Nutrients in Meat by ICP OES

The multi-energy calibration (MEC) was evaluated for the determination of Ca, Cu, Fe, K, Mg, Na, P, S, and Zn in meat samples by inductively coupled plasma optical spectrometry (ICP OES). This calibration method consists of using only two calibration standards and several atomic and ionic emission wavelengths with different sensitivities to determine the analyte concentration in the sample. Both calibration mixtures are prepared using the same amount of sample, which contributes to minimize matrix effects. The accuracy was evaluated using two certified reference materials, bovine liver (SRM 1577c) and bovine muscle (SRM 8414), with recoveries within 87-107% range. The method was applied for the determination of the analytes in meats of chicken, sheep loin, sheep carcass and bovine, and prove to be usable in samples with different characteristics.

Three approaches to minimize matrix effects in residue analysis of multiclass pesticides in dried complex matrices using gas chromatography tandem mass spectrometry

This paper discusses one of the major concerns in pesticide residue analysis: the matrix effect related to gas chromatography (GC), which can adversely affect quantification. In this study, a comparison of approaches for dealing with the matrix effect was investigated for 236 pesticides in complex matrices, including dried herbs (Centaurea cyanus L., Matricaria chamomilla L., Thymus vulgaris L.) and dried fruit (currants, chokeberry), using a modified QuEChERS method and GC–MS/MS analysis. Three approaches were evaluated: (i) using matrix-matched calibration, (ii) adding a mixture of analyte protectants (APs) to every extract or (iii) injection prior to GC–MS/MS analysis. Finally, minimization of the matrix effect to the acceptable levels of −20 to 20% for over 80% of investigated pesticides was found when APs mixture was injected at the beginning of the sequence. In this approach, the matrix effects were significantly weaker for some pesticides than when matrix-matched calibration was used.