Low Matrix Effects Research Articles

Hierarchical Biclustering of Mouse Pancreas Mass Spectrometry Imaging Data Using Recursive Rank-2 Non-negative Matrix Factorization.

One of the main challenges in mass spectrometry imaging data analysis remains the analysis of m/z-spectra displaying a low signal-to-noise ratio caused by their low abundance, sample preparation, matrix effects, fragmentation, and other artifacts. Additionally, we observe that molecules with a high abundance suppress those with lower intensities and misdirect classical tools for MSI data analysis, such as principal component analysis. As a result, the observed significance of a molecule may not always be directly related to its abundance. In this work, we present a recursive rank-2 non-negative matrix factorization (rr2-NMF) algorithm that automatically returns spectral and spatial visualization of colocalized molecules, both highly and lowly abundant. Using this hierarchical decomposition, our method finds spatial and spectral correlations on different levels of abundances. The quality of the analysis is evaluated on MALDI-TOF data of healthy mouse pancreatic tissue for the annotation of molecules of interest in the lower abundances. The results show interesting findings regarding the functioning and colocalization of certain molecules.

Determination of Flunixin and 5-Hydroxy Flunixin Residues in Livestock and Fishery Products Using Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS).

Flunixin is a veterinary nonsteroidal anti-inflammatory agent whose residues have been investigated in their original form within tissues such as muscle and liver. However, flunixin remains in milk as a metabolite, and 5-hydroxy flunixin has been used as the primary marker for its surveillance. This study aimed to develop a quantitative method for detecting flunixin and 5-hydroxy flunixin in milk and to strengthen the monitoring system by applying to other livestock and fishery products. Two different methods were compared, and the target compounds were extracted from milk using an organic solvent, purified with C18, concentrated, and reconstituted using a methanol-based solvent. Following filtering, the final sample was analyzed using liquid chromatography- tandem mass spectrometry. Method 1 is environmentally friendly due to the low use of reagents and is based on a multi-residue, multi-class analysis method approved by the Ministry of Food and Drug Safety. The accuracy and precision of both methods were 84.6%-115% and 0.7%-9.3%, respectively. Owing to the low matrix effect in milk and its convenience, Method 1 was evaluated for other matrices (beef, chicken, egg, flatfish, and shrimp) and its recovery and coefficient of variation are sufficient according to the Codex criteria (CAC/GL 71-2009). The limits of detection and quantification were 2-8 and 5-27 μg/kg for flunixin and 2-10 and 6-33 μg/kg for 5-hydroxy flunixin, respectively. This study can be used as a monitoring method for a positive list system that regulates veterinary drug residues for all livestock and fisheries products.

Strategic design of magnetic ionic covalent organic frameworks incorporating amino acid ionic liquids for enhanced selectivity adsorption of benzimidazoles

Advancing the frontier of material design, our innovative magnetic ionic covalent organic framework (MiCOF) masterfully overcomes traditional barriers in selective adsorption, pioneering new functionalities and surface engineering techniques to effectively target and mitigate the impacts of benzimidazoles (BZDs). In previous studies, the idea of designing magnetic nanomaterials through theoretical screening of ionic liquids has been successfully proposed. This work proposed a theoretical and practical design for MiCOFs, aimed at providing a sensitive, selective, rapid, and straightforward method for analyzing trace substances in complex biological matrices. In a gentle one-pot process, the surface of Fe3O4 was coated with covalent organic frameworks (COFs) layer, followed by the modification with amino acid ionic liquid (AAIL) through covalent radical polymerization, facilitated by the abundant unsaturated vinyl groups present. This resulted in MiCOFs (Fe3O4@COF-AAIL) with a stable structure. Compared to unmodified Fe3O4@COF, Fe3O4@COF-AAIL exhibited excellent adsorption selectivity for BZDs. This enhanced selectivity is primarily due to the strong hydrogen bonds and π-π interactions between AAIL and BZDs, aligning well with COSMO-RS theoretical screening predictions. The development of magnetic dispersive solid-phase extraction (MDSPE) enabled rapid processing of BZDs in plasma with low matrix effects (0.9–1.3). This study not only validates a robust framework for the selective separation of trace contaminants in complex biological matrices but also advances the design and application of MiCOFs, setting a new paradigm in material science that could transform the design of novel materials for specific tasks.

Superparamagnetic nanofluid based on target-specific deep eutectic solvent for determination of multiple perfluoroalkyl substances in edible oils

Deep eutectic solvents (DESs) are recognized as sustainable mediums, and DES-related materials have been used for the detection of perfluoroalkyl substances (PFASs). However, such studies were usually limited to only one category of PFASs among the massive target PFASs compounds. Additionally, the selectivity of the related detection method still needs improvement. In this study, a convenient and effective method for the direct selective microextraction of multiple PFASs was developed based on a target-specific DES-based superparamagnetic nanofluid. Parameters such as DES compositions, amount of DES-based nanofluid, and microextraction time were systematically investigated to establish a straightforward, rapid, sensitive, and efficient green pretreatment method. Under optimal conditions, the method demonstrated high sensitivity, good precision, a detection limit of 0.04–8.71 ng kg−1, a spike recovery of 80.49–119.95%, and low matrix effects (<20%). The potential mechanism was elucidated by ab initio molecular dynamics (AIMD) simulations. The solvent system exhibited diverse interaction modes with analytes of varying types, including hydrogen bond acceptors (HBA)···PFASs, HBA···FAAs···hydrogen bond donors (HBD), and hetero-halogen interactions. Finally, this method was applied to the monitoring of 13 PFASs compounds in 17 edible oil samples, and targets were detected in the range of 0.05–10.04 ng kg−1.

Deep eutectic solvent-functionalized amorphous UiO-66 for efficient extraction and ultrasensitive analysis of perfluoroalkyl substances in infant milk powder

In this study, a convenient and effective method for determination of perfluoroalkyl substances (PFASs) in infant formula was developed based on a novel dispersive solid-phase extraction using deep eutectic solvent-functionalized amorphous UiO-66 (DES/aUiO-66) as sorbent. The synthesis of materials could be achieved without the use of complex and environmentally unfriendly procedures. Parameters were systematically investigated to establish a simple, fast, and efficient green pretreatment method. The method demonstrated high sensitivity, good precision, a detection limit of 0.330–0.529 ng·kg−1, and low matrix effects (< 12.8%). The mechanism for this material was elucidated by ab initio molecular dynamics (AIMD) simulations and quantum chemistry calculations. The presence of massive pore structures and collectively synergistic binding sites facilitated affinity adsorption toward PFASs. Finally, this method was applied to the monitoring of PFASs in 10 actual milk powder samples. This groundbreaking approach opens new possibilities for the advancement of analytical techniques and food safety monitoring.

One-Pot Preparation of Mixed-Mode Reversed-Phase Anion-Exchange Silica Sorbent and its Application in the Detection of Cyclopiazonic Acid in Feeds and Agricultural Products.

A novel co-bonded octyl and pyridine silica (OPS) sorbent was prepared and applied for the solid phase extraction (SPE) of cyclopiazonic acid (CPA, a type of mycotoxin) in feed and agricultural products for the first time. A simple mixed-ligand one-pot reaction strategy was employed for OPS sorbent preparation. Nitrogen adsorption-desorption measurements, elemental analysis (EI), thermal gravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FT-IR) analysis demonstrated the successful immobilization of octyl and quaternary ammonium groups onto the surface of silica gel. The large specific surface area, high-density functional groups, and mixed-mode anion-exchange characteristics of these silica particles made them the ideal material for the efficient extraction of CPA. Additionally, the OPS sorbents displayed excellent batch-to-batch reproducibility, satisfactory reusability, and low cost. The SPE parameters were optimized to explore the ionic and hydrophobic interactions between CPA and the functional groups, and the ultra-high performance liquid chromatography coupled with triple-quadrupole tandem mass spectrometry (UPLC-MS/MS) parameters were optimized to obtain a desirable extraction efficiency and high sensitivity to CPA. Meanwhile, the OPS sorbent presented a satisfactory extraction selectivity and low matrix effect. Under the optimized conditions, our developed CPA detection method was used to determine CPA level in rice, wheat flour, corn flour, peanut, and feed samples, exhibiting a lower detection limit, better linearity, higher sensitivity, and satisfactory extraction recovery rate than previously reported methods. Therefore, our method can be preferentially used as a method for the detection of CPA in agricultural products and feeds.

Low Mo mobility during the laterization of ultramafic bedrock: Evidence from the East Sulawesi Ophiolite, Indonesia

Mo (isotope) cycling during the chemical weathering of ultramafic bedrock remains poorly quantified, mainly as a result of the analytical challenges caused by low Mo concentration and complex matrix effects in these rock types. Here, we utilize an improved chemical separation protocol that enables the extraction of Mo while reducing Ru and Fe matrix effects. We apply this method to lateritic weathering profiles developed over ultramafic bedrock in a high-intensity tropical weathering regime. The Mo concentrations in the laterite samples are higher (0.022 to 0.58 μg·g−1) than those of the peridotite bedrock (0.006 to 0.021 μg·g−1). The concentration-weighted average δ98Mo of the laterite profiles is −0.05‰ (n = 17), which is slightly higher but very close to the average δ98Mo of the peridotite bedrock (0.17 ± 0.21‰; 2SD; n = 5). Weakly-laterized samples show somewhat low δ98Mo with a minimum of −1.03‰ and Δ98Molaterite-bedrock up to −0.86‰, possibly as a result of preferential adsorption of liberated light Mo onto Fe (oxyhydr)oxides. In contrast, strongly-laterized samples show an overall Mo concentration gain and a slight isotopic shift towards higher bulk δ98Mo, with a maximum δ98Mo of +0.12‰ and Δ98Molaterite-bedrock up to +0.42‰. This likely reflects the re-scavenging of Mo released from weakly-laterized horizons to the ubiquitous Fe (oxyhydr)oxides, with potential superimposition of additional heavy Mo from atmospheric and/or groundwater input. Overall, this suggests a small contribution of dissolved Mo derived from ultramafic bedrock weathering in tropical settings to the aquatic environment.

Rapid determination of 15 N-nitrosamines in air-dried yak meat using one-step QuEChERS-gas chromatography-triple quadrupole mass spectrometry

A method based on gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS) coupled with one-step QuEChERS technique was developed for the simultaneous determination of 15 N-nitrosamines in air-dried yak meat. The hydration volume, extraction solvent, extracting salt, and cleaning material were optimized according to the characteristics of the N-nitrosamines and sample matrix. The optimized conditions were as follows: 10 mL of purified water for sample hydration, acetonitrile as the extraction solvent for the sample after hydration, 4.0 g of anhydrous MgSO4 and 1.0 g of NaCl as extracting salts, 500 mg of MgSO4+25 mg of C18+50 mg of PSA as cleaning materials. Favorable recoveries of the 15 N-nitrosamines were obtained when the extraction solution was incompletely dried. Thus, the final extract was dried to below 0.5 mL under a mild nitrogen stream and then redissolved to 0.5 mL with acetonitrile. After filtration, 200 μL of the sample was transferred to an autosampler vial for GC-MS/MS analysis. The 15 N-nitrosamines were determined using GC-MS/MS on a DB-HeavyWAX column (30 m×0.25 mm×0.25 μm) with an electron impact ion source in multiple-reaction monitoring (MRM) mode, and quantified using an external standard method. Under the optimized experimental conditions, the results showed that the calibration curves exhibited good linearities for the 15 N-nitrosamines, with correlation coefficients (r2) greater than 0.9990. The limits of detection (LODs) and the limits of quantification (LOQs) ranged from 0.05 to 0.20 μg/kg and from 0.10 to 0.50 μg/kg, respectively. At spiked levels of 1LOQ, 2LOQ, and 10LOQ, the average recoveries were 79.4%-102.1%, 80.6%-109.5%, and 83.0%-110.6%, respectively, and the relative standard deviations were in the range of 0.8%-16.0%. The low matrix effects of the 15 N-nitrosamines indicated the high sensitivity of the proposed method. The method was applied to detect representative commercial air-dried yak meat samples obtained using different processing techniques. Seven N-nitrosamines, including N-nitrosodimethylamine, N-nitrosodiisobutylamine, N-nitrosodibutylamine, N-methyl-N-phenylnitrous amide, N-ethyl-N-nitrosoaniline, N-nitrosopyrrolidine, and N-nitrosodiphenylamine were detected in all samples. The average contents of the seven N-nitrosamines was 0.08-20.18 μg/kg. The detection rates and average contents of the N-nitrosamines in cooked air-dried yak meat samples were higher than those in traditional raw air-dried yak meat samples. Compared with the manual QuEChERS method, the one-step QuEChERS method developed integrated the extraction and clean-up procedures into one single run, and the detection efficiency was considerably improved. The developed method is simple, rapid, highly sensitive, and insusceptible to human errors. Thus, it is useful for the determination of N-nitrosamines in air-dried yak meat and can be extended to the qualitative and quantitative analysis of N-nitrosamines in other meat products. It also provides method support and a data reference for the general determination of N-nitrosamines, which is of great significance for food safety.

Development of a rapid LC-MS/MS method for simultaneous quantification of ten commonly used antibiotic drugs in human serum

The use of TDM in clinical practice to monitor the plasma levels of antibiotics administered to critically ill patients is a well-established approach that allows for optimization of the patient's response to drug therapy, considering the characteristics of the drug, the clinical and physiological status of the patient and any peculiar of the pathogen that caused the clinical picture. In our laboratory, we have developed a single LC-MS/MS analysis for dosing the serum concentration of an antibacterial panel composed of eight antibacterial and two selective inhibitors. The method presented used a certified material furnished by a commercial company and was internally validated using the EMA guidelines. The results have shown high sensitivity, precision, and accuracy, a lower matrix effect combined with simple sample preparation and a time-saving procedure. We have evaluated the recovery rate and matrix effect by testing serum samples without pathological index and serum pools obtained from haemolysed, icteric, or lipemic samples. The assay has shown a recovery range between 94% and 101%.

Low-background interference detection of glyphosate, glufosinate, and AMPA in foods using UPLC-MS/MS without derivatization.

The abuse of herbicides has emerged as a great threat to food security. Herein, a low-background interference detection method based on UPLC-MS was developed for the simultaneous determination of glufosinate, glyphosate, and its metabolite aminomethylphosphonic acid (AMPA) in foods. Initially, this study proposed a simple and rapid pretreatment method, utilizing water extraction and PRiME HLB purification to isolate glyphosate, glufosinate, and AMPA from food samples. After the optimization of pretreatment conditions, the processed samples are then analyzed directly by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS) without pre-column derivatization. The method can effectively reduce interference from by-products of pre-column derivatization and background substrates of food sample, showing low matrix effects (ME) ranging from - 24.83 to 32.10%. Subsequently, the method has been validated by 13 kinds of food samples. The recoveries of the three herbicides in the food samples range from 84.2 to 115.6%. The limit of detection (LOD) is lower to 0.073mg/kg, 0.017mg/kg, and 0.037mg/kg, respectively. Moreover, the method shows an excellent reproducibility with relative standard deviations (RSD) within 16.9%. Thus, the method can provide high trueness, reproducibility, sensitivity, and interference-free detection to ensure human health safety.

Facile construction of magnetic solid-phase extraction of polyaniline blend poly(amidoamine) dendrimers modified graphene oxide quantum dots for efficient adsorption of polycyclic aromatic hydrocarbons in environmental water

An efficient magneto–adsorbent composed of polyaniline blend poly(amidoamine) dendrimers modified graphene oxide quantum dots and magnetic Fe3O4 particles (Fe3O4@PANI–PSS/PAMAM–QGO) for magnetic solid–phase extraction (MSPE) of polycyclic aromatic hydrocarbons (PAHs) in environmental water was synthesized. Fe3O4@PANI–PSS/PAMAM–QGO exhibited exceptional adsorption property for most PAHs analytes. The nanocomposite sorbent demonstrated a ferromagnetic behavior of 17.457 emu g−1, which is adequate for subsequent use in MSPE. Key parameters affecting the processes of adsorption and desorption, including the sorbent amount, vortex adsorption time, vortex extraction time, sample volume, a solvent for desorption and the solvent volume were all examined and optimized. The performance of MSPE using Fe3O4@PANI–PSS/PAMAM–QGO as adsorbent for four PAHs, including fluoranthene, acenaphthene, phenanthrene and pyrene were studied through high performance liquid chromatography equipped with spectrofluorometer. Under the optimal conditions, Fe3O4@PANI–PSS/PAMAM–QGO showed a wide linearity of 10–1,000 ng mL−1, low detection limit (LOD) ranging from 1.92 to 4.25 ng mL -1 and high accuracy (recoveries of 93.6–96.5 %). Enrichment factors up to 185 were achieved. Furthermore, Fe3O4@PANI–PSS/PAMAM–QGO exhibited good recyclability (10 times, RSDs ≤ 5.35%), while maintaining its high efficiency in the extraction of PAHs. The proposed method was successfully applied for environmental samples. Recoveries ranging from 81.2 to 106.2 % were obtained, indicating a low matrix effect and the robustness of the optimized MSPE method. Based on these features and under the optimal extraction conditions, Fe3O4@PANI–PSS/PAMAM–QGO was demonstrated to be a successful tool for the rapid and sensitive extraction of PAHs in the samples.

Perspective on SPME-MS: Green and high-performance methods for rapid screening

The direct coupling of solid-phase microextraction (SPME) with mass spectrometry (MS) offers rapid analysis with high sensitivity and low matrix effects by benefiting from the integration of sampling, high enrichment, and clean-up functions of SPME. Eliminating chromatographic separation reduces the amount of gas/solvent needed for analysis, while direct desorption in SPME-MS consumes none or few microliters of organic solvents per sample, further enhancing the greenness of the SPME technology. Over the past two decades, the rapid evolution of SPME-MS has given rise to numerous novel technologies that employ diverse ionization techniques and interfaces, several of which have already been commercialized. Drawing from an extensive review published earlier this year and our research experience, we provide perspectives on three aspects of these technologies: interface design and automation, integration with state-of-art MS instrumentation, and anticipated future developments.

Determination of teicoplanin and ramoplanin residues in aquaculture products by a modified QuEChERS method combined with UPLC-MS/MS

A QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) method was developed to provide good analytical results for teicoplanin (TEC) and ramoplanin (RAM) residues in aquaticproducts. The analytes was extraction from aquatic product samples using chitosan in the QuEChERS procedure. Compared to conventional adsorbents, chitosan has a relatively good purification ability for the targets.The matrix effects of aquatic products, such as crucian carp, carp, silver carp, tilapia, mandarin fish, turbot, shrimp, sea cucumber and so on, were evaluated by high performance liquid chromatography coupled to triple-quadrupole tandem mass spectrometry. Throughout the validation experiments, the limits of detections and quantifications ranged from 0.4 ∼ 0.8 μg kg−1 and 1.0 ∼ 3.0 μg kg−1, respectively. Calibration curves showed correlation coefficient values higher than 0.998 in range between 1 and 100 μg kg−1. The recoveries ranged from 89.8 % to 110.0 % with relative standard deviation less than 7.2 % in nine typical aquaticproducts. The method shows low matrix effect (-18.5 %∼-2.6 %) for all targets in different aquaticproducts. The proposed methods proved to be reliable, effective and enables rapid determination of large batch samples, indicating its good applicability for detection and monitoring of TEC and RAM residues in aquaticproducts.

Beyond helium: hydrogen as a carrier gas in multiresidue pesticide analysis in fruits and vegetables by GC-MS/MS.

In this comprehensive study, we evaluated the feasibility of using hydrogen instead of helium as a carrier gas in a GC-MS/MS system for pesticide residue analysis, spanning three matrices: pepper, tomato, and zucchini. Initial assessments focused on the ion source's chemical inertness, employing nitrobenzene as a benchmark to monitor the hydrogenation process. A method with a duration of less than 12 minutes was developed, achieving good chromatographic peak resolution attributable to the enhanced chromatographic performance of hydrogen as a carrier gas. The study emphasized the optimization of system parameters, testing various ion source temperatures, detector voltages, and injection volumes. Sensitivity assessments, based on the DG-SANTE criteria, indicated that the majority of compounds were identifiable at a concentration of 5 μg kg-1 (81% in tomato, 84% in pepper and 73% in zucchini). Detailed validation for reproducibility, matrix effects, and linearity across 150 pesticides unveiled generally favorable outcomes, with a notable majority of compounds displaying low matrix effects, satisfactory linearity ranges and good reproducibility with most compounds returning a relative standard deviation (RSD) below 10%. When applied to 15 real samples, the hydrogen-based system's performance was juxtaposed against a helium-based counterpart, revealing that results are very comparable between both systems. This comparative approach highlights hydrogen's potential as a reliable and efficient carrier gas in pesticide residue analysis for routine food control laboratories, overcoming difficulties resulting from the lack of helium supplies.

Single-run gas chromatography-mass spectrometry method for the analysis of phthalates, polycyclic aromatic hydrocarbons, and pesticide residues in infant formula based on dispersive microextraction techniques

For the first time, three important contaminant groups (phthalates, polycyclic aromatic hydrocarbons, and pesticides), traditionally monitored by separated methods, were simultaneously analyzed in complex infant formula matrices. An accurate and sensitive analytical method based on gas chromatography-mass spectrometry (GC–MS) was developed for 45 food contaminants. Dispersive solid-phase extraction and low-density solvent-based dispersive liquid–liquid microextraction techniques were combined for clean-up and analyte enrichment purposes. Distinct GC–MS injection conditions were studied with the highest analytical responses obtained at high temperatures in pulsed splitless mode at high pulse pressures. Low matrix effects were observed for the majority of analytes under study, indicating a possible relation of these effects with the physicochemical parameters of the analytes. Adequate method performance characteristics were achieved, covering limits of detection and quantification sufficiently low to monitor the regulated compounds at the maximum limits fixed for infant formula. Furthermore, the greenness and practicality of the proposed method were evaluated through the AGREE and BAGI metric tools, respectively. In summary, the application of the proposed method to commercial infant formulas, with the identification and quantification of benzo[a]pyrene, benz[a]anthracene, dibutyl phthalate, di(2-ethylhexyl) phthalate, dimethyl phthalate, and diisobutyl phthalate at levels between 1.4 and 47.1 µg kg−1 in a total of 30.0 % samples, demonstrates their suitability for routine analysis as well as contributes to the first data on the co-occurrence of PAHs and phthalates in infant formula.

Simultaneous determination of typical toxic aldehydes formed during food frying and digestion using isotope dilution UHPLC-QqQ-MS/MS

An isotope dilution ultra-performance liquid chromatography–triple quadrupole mass spectrometry method was developed to simultaneously detect two typical kinds of α,β-unsaturated aldehydes, namely 4-hydroxy-2-hexenal (4-HHE) and 4-hydroxy-2-nonenal (4-HNE), in foods. The proposed method exhibited a linear range of 10–1000 ng/mL with a limit of detection of 0.1–2.0 ng/g and a limit of quantification of 0.3–5.0 ng/g. The recovery rates of these typical toxic aldehydes (i.e., 4-HHE, 4-HNE) and their d3-labeled analogues were 91.54%–105.12% with a low matrix effect. Furthermore, this proposed method was successfully applied to a real frying system and a simulated digestion system, wherein the contents of 4-HHE and 4-HNE were determined for both. Overall, the obtained results provide strong support for further research into the production of 4-HHE and 4-HNE resulting from foods during oil digestion and frying.

Selective determination of 2-aminobenzothiazole in environmental water and organic extracts from fish and dust samples

In the present study, a homemade mixed-mode ion-exchange sorbent based on silica with embedded graphene microparticles is applied for the selective extraction of 2-aminobenzothiazole (NH2BT) followed by determination through liquid chromatography coupled to high-resolution mass spectrometry. The sorbent was evaluated for the solid-phase extraction of NH2BT from environmental water samples (river, effluent wastewater, and influent wastewater), and NH2BT was strongly retained through the selective cation-exchange interactions. Therefore, the inclusion of a clean-up step of 7 mL of methanol provided good selectivity for the extraction of NH2BT. The apparent recoveries obtained for environmental water samples ranged from 62 to 69% and the matrix effect from −1 to −14%. The sorbent was also evaluated in the clean-up step of the organic extract for the extraction of NH2BT from organic extracts of indoor dust samples (10 mL of ethyl acetate from pressurized liquid extraction) and fish (10 mL of acetonitrile from QuEChERS extraction). The organic extracts were acidified (adding a 0.1% of formic acid) to promote the cation-exchange interactions between the sorbent and the analyte. The apparent recoveries for fish samples ranged from 22 to 36% depending on the species. In the case of indoor dust samples, the recovery was 41%. It should be highlighted the low matrix effect encountered in such complex samples, with values ranging from −7 to 5% for fish and dust samples. Finally, various samples were analyzed. The concentration in river samples ranged from 31 to 136 ng/L; in effluent wastewater samples, from 55 to 191 ng/L; in influent wastewater samples, from 131 to 549 ng/L; in fish samples, from 14 to 57 ng/g dried weight; and in indoor dust samples, from <MQL to 114 ng/g.

Inline phase transition trapping-selective supercritical fluid extraction-supercritical fluid chromatography: A green and efficient integrated method for determining prohibited substances in cosmetics

BackgroundDeveloping an environmentally friendly and efficient integrated analytical approach is a cutting-edge topic in current analytical science. Due to the unique properties of supercritical carbon dioxide (sc-CO2), online supercritical fluid extraction-supercritical fluid chromatography (SFE-SFC) is developing rapidly and has been widely applied in many fields. However, it still faces several challenges such as peak broadening and matrix interference. In order to solve the problems, we developed an inline phase transition trapping-selective supercritical fluid extraction-supercritical fluid chromatography (PTT-SSFE-SFC)-tandem mass spectrometry (MS/MS) method in this study. ResultsThis method integrated extraction, purification, separation, and detection, which was applied to determine 114 prohibited substances in cosmetics within 33 min, covering ten categories. The PTT strategy trapped the extracts on the head of the column by transforming CO2 from a supercritical state to a gaseous state, preventing peak spreading and improving sensitivity. Several adsorbents were tested when analyzing aqueous samples to reduce matrix interference and absorb water. Compared with conventional online SFE-SFC, this method improved the matrix effects of 93 and 87 target substances in the toner and mask matrix, respectively. Because the integrated method reduced sample loss, it achieved high sensitivity with LODs ranging from 0.00104 μg L−1 to 3.09 μg L−1. Furthermore, compared with other reported green methods, the inline method showed advantages in automation, efficiency, sample amount, and waste volume. Significance and noveltyWith the introduction of the PTT strategy and the adsorbent, the system obtained good peak shapes, high sensitivity, low matrix effect, and good recovery. Based on the results, inline PTT-SSFE-SFC-MS/MS as a green and efficient integrated method has great potential for analyzing low abundance and multiple categories of targets in complex samples.

Simultaneous quantification of donafenib, sorafenib, and their N-oxide metabolites in rat plasma using a HPLC-MS/MS method

Donafenib and sorafenib are small molecule chemotherapy drugs for the management of hepatocellular carcinoma, with donafenib being a deuterated derivative of sorafenib. To date, a high liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method that quantify donafenib, sorafenib, and their main metabolites has not yet been developed. The objective of this study was to establish a HPLC-MS/MS method for the simultaneous detection of donafenib, donafenib-N-oxide, sorafenib, and sorafenib-N-oxide and for the pharmacokinetic studies in rat. The extraction of all analytes was achieved by simple protein precipitation utilizing acetonitrile. The Waters XBridge C18 column (2.1 × 100 mm, 3.5 µm) was selected, and the analytes could be efficiently separated and quantitated during a 2.8 min gradient elution procedure. The method was linear within the predefined quantification ranges and provided acceptable precision (%CV < 9.4%), reproducible extraction recovery (99.4%–111.5%), and low matrix effect (88.1%–98.6%). The hemolysis effect did not interfere with the quantification of all analytes, and similar results were obtained by changing the anticoagulant K2-EDTA to heparin or sodium citrate. Plasma pharmacokinetics revealed that the values of t1/2, Cmax, and AUC0-t of donafenib were 1.4-, 6.2-, and 3.1-fold higher than those of sorafenib, respectively. In conclusion, the proposed bioassay was successfully applied to pharmacokinetic studies in rat after administration of donafenib and sorafenib. Our work not only improves the bioanalytical method for determining the plasma concentrations of donafenib, sorafenib, and their N-oxide metabolites, but also provides a scientific reference for clinical pharmacokinetic studies.

A modified QuEChERS method based on a reduced graphene oxide-coated melamine sponge for multiresidue analysis of veterinary drugs in mutton by UPLC–MS/MS

The development of different matrix adsorbents is a research focus in the multiresidue analysis of veterinary drugs in foods. In this study, a novel elastic matrix adsorbent based on a reduced graphene oxide-coated melamine sponge was prepared and applied in matrix purification for the simultaneous determination of 52 veterinary drugs in mutton by UPLC–MS/MS. Efficient and convenient matrix removal was achieved through simple soaking and squeezing. Good linearities with determination coefficients ≥0.999 and low matrix effects ≤±13% were obtained in the range of 10–500 μg·kg−1. The obtained recoveries ranged from 63.7% to 109.5% at three spiked levels (10, 50, and 100 μg·kg−1), with relative standard deviations ≤8.1%. Low LODs and LOQs were obtained in ranges of 0.02–2.0 μg·kg−1 and 0.05–5.0 μg·kg−1, respectively. Based on the comprehensive results, our developed method showed good applicability in the analysis of multiresidues in various foods.