Multiresidue Pesticide Analysis in Tea Using GC–MS/MS to Determine 12 Pesticide Residues (GB 2763-2021)

Pesticides are widely used on tea plants, and pesticide residues are of significant concern to consumers. The National Food Safety Standard Maximum Residue Limits for Pesticides in Food (GB 2763-2021) was recently amended. However, detection methods for pesticides newly added to the list of residues in beverages have not yet been established. For that reason, this study developed a solid-phase extraction (SPE) and gas chromatography–tandem mass spectrometry (GC–MS/MS) method for determining the residues of 12 pesticides, including four newly added, in black and green tea. Sample preparation processes (sample extraction, SPE clean-up, elution solvent, and elution volume) were optimized to monitor these residues reliably. Multiple reaction monitoring (MRM) was used for GC–MS/MS electron impact (EI) mode determination. Finally, satisfactory recoveries (70.7–113.0% for green tea and 72.0–99.1% for black tea) were achieved at three concentrations (10 μg/kg, 20 μg/kg, and 100 μg/kg). The LOQs were 0.04–8.69 μg/kg, and the LODs were 0.01–3.14 μg/kg. This study provides a reliable and sensitive workflow for determining 12 pesticide residues in tea, filling a gap in the newly revised National Standards.     

Concurrent Determination of Tigecycline,Tetracyclines and Their 4-Epimer Derivatives in Chicken Muscle Isolated from a Reversed-Phase Chromatography System Using Tandem Mass Spectrometry

A quantitative and qualitative method using a high-performance liquid chromatography–tandem mass spectrometry (HPLC–MS/MS) detection approach was developed and validated for the analysis of tigecycline, four tetracyclines and their three 4-epimer derivatives in chicken muscle. Samples were extracted repeatedly with 0.1 mol/L Na₂EDTA–McIlvaine buffer solution. After vortexing, centrifugation, solid-phase extraction, evaporation and reconstitution, the aliquots were separated using a C8 reversed-phase column (50 mm × 2.1 mm, 5 µm) with a binary solvent system consisting of methanol and 0.01 mol/L trichloroacetic acid aqueous solution. The typical validation parameters were evaluated in accordance with the acceptance criteria detailed in the guidelines of the EU Commission Decision 2002/657/EC and the U.S. Food and Drug Administration Bioanalytical Method Validation 05/24/18. The matrix-matched calibration curve was linear over the concentration range from the limit of quantitation (LOQ) to 400 μg/kg for doxycycline, and the calibration graphs for tetracycline, chlortetracycline, oxytetracycline, their 4-epimer derivatives and tigecycline showed a good linear relationship within the concentration range from the LOQ to 200 μg/kg. The limits of detection (LODs) for the eight targets were in the range of 0.06 to 0.09 μg/kg, and the recoveries from the fortified blank samples were in the range of 89% to 98%. The within-run precision and between-run precision, which were expressed as the relative standard deviations, were less than 5.0% and 6.9%, respectively. The applicability was successfully demonstrated through the determination of residues in 72 commercial chicken samples purchased from different sources. This approach provides a novel option for the detection of residues in animal-derived food safety monitoring.     

Determination of Polycyclic Aromatic Hydrocarbons in Traditional Chinese Medicine Raw Material,Extracts, and Health Food Products

The four polycyclic aromatic hydrocarbon markers (PAH4) of benzo[a]anthracene (BaA), chrysene (Chr), benzo[b]fluoranthene (BbF), and benzo[a]pyrene (BaP) are indicators showing polycyclic aromatic hydrocarbon (PAH) contamination levels in Chinese medicine raw materials (CMRMs), extracts and health food products; Samples of herbal medicine, herbal extracts, and food supplements were extracted with n-hexane, then cleaned up sequentially on Florisil and EUPAH solid-phase extraction (SPE) columns. A gas chromatography–mass spectrometry method for the determination of four polycyclic aromatic hydrocarbon markers in Chinese medicine raw material, extracts, and health food products was established; In spiked-recovery experiments, the average recovery was about 78.6–107.6% with a precision of 2.3–10.5%. The limit of quantification (LOQ) and limit of detection (LOD) of the PAH4 markers in this method were 2.0 μg/kg and 0.7 μg/kg, respectively. When the developed method was utilized to determine PAH4 contents in 12 locally available health food products, 3 samples contained over 10.0 μg/kg BaP, and 5 samples contained over 50.0 μg/kg PAH4. The European Union (EU) limits for BaP and PAH4 are 10 and 50.0 μg/kg, respectively; therefore, more attention must be drawn to the exposure risk of BaP and PAH4 in CMRMs, their extracts, and health food products. According to the risk assessment based on the Margin of Exposure (MOE) method, it is recognized that the products mentioned in this study pose a low risk.     

HPLC-UV and GC-MS Methods for Determination of Chlorambucil and Valproic Acid in Plasma for Further Exploring a New Combined Therapy of Chronic Lymphocytic Leukemia

High performance liquid chromatography with ultra-violet detection (HPLC-UV) and gas chromatography–mass spectrometry (GC-MS) methods were developed and validated for the determination of chlorambucil (CLB) and valproic acid (VPA) in plasma, as a part of experiments on their anticancer activity in chronic lymphocytic leukemia (CLL). CLB was extracted from 250 µL of plasma with methanol, using simple protein precipitation and filtration. Chromatography was carried out on a LiChrospher 100 RP-18 end-capped column using a mobile phase consisting of acetonitrile, water and formic acid, and detection at 258 nm. The lowest limit of detection LLOQ was found to be 0.075 μg/mL, showing sufficient sensitivity in relation to therapeutic concentrations of CLB in plasma. The accuracy was from 94.13% to 101.12%, while the intra- and inter-batch precision was ≤9.46%. For quantitation of VPA, a sensitive GC-MS method was developed involving simple pre-column esterification with methanol and extraction with hexane. Chromatography was achieved on an HP-5MSUI column and monitored by MS with an electron impact ionization and selective ion monitoring mode. Using 250 µL of plasma, the LLOQ was found to be 0.075 μg/mL. The accuracy was from 94.96% to 109.12%, while the intra- and inter-batch precision was ≤6.69%. Thus, both methods fulfilled the requirements of FDA guidelines for the determination of drugs in biological materials.     

Simultaneous Determination of Seven Pesticides and Metabolite Residues in Litchi and Longan through High-Performance Liquid Chromatography-Tandem Mass Spectrometry with Modified QuEChERS

This study established a QuEChERS high-performance liquid chromatography/tandem triple-quadrupole mass spectrometry method for determining azoxystrobin, pyraclostrobin, picoxystrobin, difenoconazole, chlorantraniliprole, imidacloprid, and cyantraniliprole and its metabolite (IN-J9Z38) in litchi and longan, and applied this method to the real samples. The residues in samples were extracted with acetonitrile and purified with nano-ZrO₂, C₁₈, and PSA. The samples were then detected with multireactive ion monitoring and electrospray ionization in the positive ion mode and quantified using the external matrix-matched standard method. The results showed good linearities for the eight analytes in the range of 1–100 μg/L, with correlation coefficients (r²) of >0.99. The limit of quantification was 1–10 μg/kg, and the limit of detection was 0.3–3 μg/kg. Average recovery from litchi and longan was 81–99%, with the relative standard deviation of 3.5–8.4% at fortified concentrations of 1, 10, and 100 μg/kg. The developed method is simple, rapid, efficient, and sensitive. It allowed the rapid screening, monitoring, and confirming of the aforementioned seven pesticides and a metabolite in litchi and longan.     

Simultaneous Analysis for Quality Control of Traditional Herbal Medicine,Gungha-Tang,Using Liquid Chromatography–Tandem Mass Spectrometry

Gungha-tang (GHT), a traditional herbal medicine, consists of nine medicinal herbs (Cnidii Rhizoma, Pinelliae Tuber, Poria Sclerotium, Citri Unshius Pericarpium, Citri Unshius Pericarpium Immaturus, Aurantii Fructus Immaturus, Atracylodis Rhizoma Alba, Glycyrrhizae Radix et Rhizoma, and Zingiberis Rhizoma Recens). It has been used for various diseases caused by phlegm. This study aimed to develop and verify the simultaneous liquid chromatography–tandem mass spectrometry (LC–MS/MS) analysis method, using nine marker components (liquiritin apioside, neoeriocitrin, narirutin, naringin, hesperidin, neohesperidin, liquiritigenin, glycyrrhizin, and 6-shogaol) for quality control of GHT. LC–MS/MS analysis was conducted using a Waters TQ-XS system. All marker analytes were separated on a Waters Acquity UPLC BEH C₁₈ column (2.1 × 100 mm, 1.7 μm) using gradient elution with a distilled water solution (containing 5 mM ammonium formate and 0.1% [v/v] formic acid)–acetonitrile mobile phase. LC–MS/MS multiple reaction monitoring (MRM) analysis was carried out in negative and positive ion modes of an electrospray ionization source. The developed LC–MS/MS MRM method was validated by examining the linearity, limits of detection and quantification, recovery, and precision. LOD and LOQ values of nine markers were calculated as 0.02–8.33 ng/mL and 0.05–25.00 ng/mL. The recovery was determined to be 89.00–118.08% and precision was assessed with a coefficient of variation value of 1.74–8.64%. In the established LC–MS/MS MRM method, all markers in GHT samples were detected at 0.003–16.157 mg/g. Information gathered during the development and verification of the LC–MS/MS method will be useful for the quality assessment of GHT and other herbal medicines.     

Development of an Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry Method for Hydroxylated Polychlorinated Biphenyls in Animal-Derived Food

Hydroxylated polychlorinated biphenyls (OH-PCBs) are a group of metabolites biotransformed from polychlorinated biphenyls by animals with higher toxicities than their parent compounds. The present work developed and validated an analytical method for determinating penta-, hexa-, and hepta-chlorine substituted OH-PCBs in animal-derived food based on ultra-performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) with isotope-dilution. The target analytes were extracted with a 50% n-hexane/dichloromethane (v/v), purified by sulfuric acid-silica gel, and separated by 5% hydrated silica gel, achieving a final concentration of 100 times before injection to LC–MS/MS. The limits of detection (LOD) and quantification (LOQ) for target OH-PCBs were within the ranges of 0.003–0.010 μg/kg and 0.009–0.030 μg/kg, respectively. Average recoveries ranged between 76.7% and 116.5%, with relative standard deviations of less than 18.4%. The proposed method is simple, time-saving, sensitive, and accurate, making it a powerful tool for risk monitoring of OH-PCBs in animal-derived food.     

Bioactive β-Carbolines Harman and Norharman in Sesame Seed Oils in China

The β-carbolines in our diet, mainly including harman and norharman, are a group of biologically active, naturally occurring plant-derived alkaloids. Fragrant sesame seed oil is one of the most popular flavor edible oils in China. Considering that sesame seeds are roasted at 200–240 °C during the processing of flavor sesame seed oils, it is meaningful to investigate the levels of β-carboline compounds in various sesame seed oils. In this work, the levels of β-carbolines (harman and norharman) in different types of sesame seed oils in China (e.g., pressed fragrant sesame oil, ground fragrant sesame oil) have been determined systematically. The results showed that the levels of total β-carbolines in pressed fragrant sesame oils (700.5~2423.2 μg/kg) were higher than that in ground fragrant sesame oils (660.4~1171.7 μg/kg). Roasting sesame seeds at high temperatures (200–240 °C) led to higher levels of β-carbolines (660~2400 μg/kg) in fragrant sesame seed oils. In addition, the loss of tryptophan might be attributed to the formation of β-carbolines in sesame seeds during the roasting process. In general, fragrant sesame seed oils (pressed fragrant sesame oils, ground fragrant sesame oils) contain higher levels of β-carbolines due to the formation of harman and norharman during the roasting sesame seed process.     

A Capillary Electrophoresis Method Based on Molecularly Imprinted Solid-Phase Extraction for Selective and Sensitive Detection of Histamine in Foods

In this study, a sensitive capillary electrophoresis (CE) method based on molecularly imprinted solid-phase extraction (MISPE) was proposed to determine histamine in foods. A molecularly imprinted polymer (MIP) synthesized by bulk polymerization was used as the MISPE adsorbent for the selective extraction of histamine. Under the optimal conditions, the MISPE-CE method possessed good linearity for histamine detection in the concentration range of 0.1–100.0 μg/L. The limit of detection and limit of quantification of the method were calculated to be 0.087 μg/L and 0.29 μg/L, respectively. The histamine in spiked rice vinegar and liquor samples were detected by the developed method with recoveries of 92.63–111.00%. The histamine contents in fish, prawn, pork, chicken breast and soy sauce samples were determined using the developed method and a high-performance liquid chromatography method, with no significant difference found between the two methods.     

急性瘦肉精中毒检材的QuEChERS净化-液质联用快速确证方法

目前液相色谱串联质谱法测定动物源性食品中瘦肉精普遍采用酶水解提取、固相萃取净化的方式处理样品,该方法耗时长、分析成本高。 本研究采用酸水解和酶水解两种提取方式结合QuEChERS(Quick,Easy,Cheap,Effective,Rugged,Safe)净化和高效液相色谱串联质谱建立了动物性食品中特布他林、沙丁胺醇、莱克多巴胺和克伦特罗4种β2受体激动剂的快速定性确证和定量检测方法。 采用酶水解提取-QuEChERS净化处理样品,在电喷雾离子源正离子扫描(ESI+)和多反应监测(MRM)模式下,4种瘦肉精在1.0~20.0 μg/L浓度之间呈线性,线性相关系数均大于0.999,检出限和定量限分别为0.1和0.3 μg/kg,猪肉和牛肉样品中4种化合物的回收率为78.5%~112%,相对标准偏差RSD为2.8%~8.9%。 采用酸水解法代替酶水解提取时,尽管对于样品中莱克多巴胺测定结果稍偏低,但样品前处理时间大大缩短。 两种提取方法结合使用对于提高瘦肉精引起的食物中毒应急处置效率具有重要意义。     

A Comparative Study on Analysis of Ginsenosides in American Ginseng Root Residue by HPLC-DAD-ESI-MS and UPLC-HRMS-MS/MS

Ginseng (Panax quinquefolius), a popular herbal and nutritional supplement consumed worldwide, has been demonstrated to possess vital biological activities, which can be attributed to the presence of ginsenosides. However, the presence of ginsenosides in ginseng root residue, a by-product obtained during processing of ginseng beverage, remains unexplored. The objectives of this study were to develop a high-performance liquid chromatography-photodiode array detection-mass spectrometry (HPLC-DAD-ESI-MS) and an ultra-high-performance-liquid-chromatography-tandem mass spectrometry (UPLC-HRMS-MS/MS) method for the comparison of ginsenoside analysis in ginseng root residue. Results showed that by employing a Supelco Ascentis Express C18 column (150 × 4.6 mm ID, particle size 2.7 μm) and a gradient mobile phase of deionized water and acetonitrile with a flow rate at 1 mL/min and detection at 205 nm, a total of 10 ginsenosides, including internal standard saikosaponin A, were separated within 18 min and detected by HPLC-DAD-ESI-MS. Whereas with UPLC-HRMS-MS/MS, all the 10 ginsenosides were separated within six minutes by using an Acquity UPLC BEH C18 column (50 × 2.1 mm ID, particle size 1.7 μm, 130 Å) and a gradient mobile phase of ammonium acetate and acetonitrile with column temperature at 50 °C, flow rate at 0.4 mL/min and detection by selected reaction monitoring (SRM) mode. High accuracy and precision was shown, with limit of quantitation (LOQ) ranging from 0.2–1.9 μg/g for HPLC-DAD-ESI-MS and 0.269–6.640 ng/g for UPLC-HRMS-MS/MS. The contents of nine ginsenosides in the ginseng root residue ranged from <LOQ-26.39 mg/g by HPLC-DAD-ESI-MS and <LOQ-21.25 mg/g by UPLC-HRMS-MS/MS, with a total amount of 38.37 and 34.71 mg/g, respectively.     

Use of TLC-Densitometric Method for Determination of Valproic Acid in Capsules

Determination of valproic acid in the drug was carried out on the aluminum silica gel 60F₂₅₄ plates and using acetone–water–chloroform–ethanol–ammonia at a volume ratio of 30:1:8:5:11 as the mobile phase, respectively. Two methods of detection of valproic acid were used. The first was a 2% aqueous CuSO₄×5H₂O solution, and the second was a 2′,7′-dichlorofluorescein-aluminum chloride-iron (III) chloride system. The applied TLC-densitometric method is selective, linear, accurate, precise, and robust, regardless of the visualizing reagent used for the determination of valproic acid in Convulex capsules. It has low limits of detection (LOD) and limits of quantification (LOQ), which are equal to 5.8 μg/spot and 17.4 μg/spot using a 2% aqueous CuSO₄×5H₂O solution as visualizing agent and also 0.32 μg/spot and 0.97 μg/spot using a 2′,7′-dichlorofluorescein-aluminum chloride-iron (III) chloride system as visualizing reagent, respectively. The described analytical method can additionally be used to study the identity of valproic acid in a pharmaceutical preparation. The linearity range was found to be 20.00–80.00 μg/spot and 1.00–2.00 μg/spot for valproic acid detected on chromatographic plates using a 2% aqueous CuSO₄×5H₂O solution and the 2′,7′-dichlorofluorescein-aluminum chloride-iron (III) chloride system, respectively. A coefficient of variation that was less than 3% confirms the satisfactory accuracy and precision of the proposed method. The results of the assay of valproic acid equal 96.2% and 97.0% in relation to the label claim that valproic acid fulfill pharmacopoeial requirements. The developed TLC-densitometric method can be suitable for the routine analysis of valproic acid in pharmaceutical formulations. The proposed TLC-densitometry may be an alternative method to the modern high-performance liquid chromatography and square wave voltammetry in the control of above-mentioned substances, and it can be applied when other analytical techniques is not affordable in the laboratory.     

LC–MS3 Strategy for Quantification of Carbamazepine in Human Plasma and Its Application in Therapeutic Drug Monitoring

This study developed a detection method based on the strategy of HPLC/MS³ and verified its suitability by quantifying carbamazepine in human plasma. The high-performance liquid chromatography–tandem mass spectrometry (HPLC/MS³) system was performed using a Shimadzu UFLC XR liquid chromatography and a SCIEX QTRAP^® 5500 linear ion trap triple quadrupole mass spectrometer. The specific operation was as follows: the sample protein was firstly precipitated using methanol, then carbamazepine and carbamazepine-D₂N¹⁵ were separated on an ACQUITY UPLC HSS T3 column using the gradient elution with solvent A (0.1% formic acid) and solvent B (0.1% formic acid in acetonitrile) at a flow rate of 0.25 mL/min. Each sample was run for 7 min. This method was validated for various parameters including accuracy, precision, selectivity, linearity, LLOQ, etc. Only 5 μL of sample plasma could obtain the result of LLOD 0.5 µg/mL. The intra-day and inter-day precision was <8.23%, and accuracy was between −1.74% and 2.92%. This method was successfully used for monitoring the blood concentration of epilepsy patients after carbamazepine treatment.     

A Newly Developed HPLC-UV/Vis Method Using Chemical Derivatization with 2-Naphthalenethiol for Quantitation of Sulforaphane in Rat Plasma

Sulforaphane (SFN), a naturally occurring isothiocyanate, has received significant attention because of its ability to modulate multiple biological functions, including anti-carcinogenic properties. However, currently available analytical methods based on high-performance liquid chromatography (HPLC)-UV/Vis for the quantification of SFN have a number of limitations, e.g., low UV absorbance, sensitivity, or accuracy, due to the lack of a chromophore for spectrometric detection. Therefore, we here employed the analytical derivatization procedure using 2-naphthalenethiol (2-NT) to improve the detectability of SFN, followed by HPLC separation and quantification with UV/Vis detection. The optimal derivatization conditions were carried out with 0.3 M of 2-NT in acetonitrile with phosphate buffer (pH 7.4) by incubation at 37 °C for 60 min. Separation was performed in reverse phase mode using a Kinetex C18 column (150 mm × 4.6 mm, 5 μm) at a flow rate of 1 mL/min, with 0.1% formic acid as a mobile phase A, and acetonitrile/0.1% formic acid solution as a mobile phase B with a gradient elution, with a detection wavelength of 234 nm. The method was validated over a linear range of 10–2000 ng/mL with a correlation of determination (R²) > 0.999 using weighted linear regression analysis. The intra- and inter-assay accuracy (% of nominal value) and precision (% of relative standard deviation) were within ±10 and <15%, respectively. Moreover, the specificity, recovery, matrix effect, process efficiency, and short-term and long-term stabilities of this method were within acceptable limits. Finally, we applied this method for studying in vivo pharmacokinetics (PK) following oral administration of SFN at doses of 10 or 20 mg/kg. The C_max (μg/mL), T_max (hour), and AUC_0–12h (μg·h/mL) of each oral dose were 0.92, 1.99, and 4.88 and 1.67, 1.00, and 9.85, respectively. Overall, the proposed analytical method proved to be reliable and applicable for quantification of SFN in biological samples.     

Simultaneous Determination of 108 Pesticide Residues in Three Traditional Chinese Medicines Using a Modified QuEChERS Mixed Sample Preparation Method and HPLC-MS/MS

A rapid, efficient, simple, and high-throughput method for the simultaneous determination of 108 pesticide residues in three traditional Chinese medicines (TCMs) was established, comprising an improved QuEChERS method in combination with HPLC-MS/MS based on mixed samples. A quantity of 10 mL of acetonitrile was used as extraction solvent, and 10 mg of amino-modified multi-walled carbon nanotubes (MWCNTs-NH₂) and 150 mg of anhydrous magnesium sulfate (MgSO₄) were selected as sorbents for dispersive solid phase extraction. The performance of the method was verified according to the analytical quality control standards of SANTE/11813/2017 guidelines. With good linearity (R² > 0.9984) in the range of 2–200 μg/L for all pesticides in the selected matrices, and good accuracy, precision, and high sensitivity, the recoveries were in the range of 70–120% for more than 95% of the pesticides, with a relative standard deviation (RSD) of less than 16.82% for all. The limit of detection (LOD) and limit of quantification (LOQ) of the method were 0.01–3.87 μg/kg and 0.07–12.90 μg/kg, respectively, for Fritillaria thunbergii Miq (F. thunbergii), Chrysanthemum Morifolium Ramat (C. morifolium), and Dendrobium officinale Kimura et Migo (D. officinale). The method was successfully applied to 60 batches of actual samples from different regions.     

超声辅助提取-固相萃取土壤中头孢菌素C的高效液相色谱法定量检测

建立了一种采用超声辅助提取(UAE)、强阴离子交换固相萃取(SAX-SPE)净化、高效液相色谱(HPLC)测定土壤中残留头孢菌素C(CPC)简单、快速方法。 样品以超纯水为提取剂,超声辅助提取,SPE柱子以3 mL甲醇和3 mL水活化,采用5 mL的10%甲醇水溶液作为淋洗液,2 mL的5%甲酸水溶液/甲醇溶液(体积比50：50)进行洗脱,高效液相色谱紫外检测器(HPLC-PDA)测定,检测波长λ=254 nm,柱温30 ℃ ,流动相为0.1%甲酸水溶液/甲醇溶液(体积比95：5)对土壤中不同加标浓度的CPC进行检测,方法的回收率在77.9%~98.9%,标准偏差范围为5.0%~6.3%(n=5),方法检出限(LOD)为340.4 μg/kg,定量限(LOQ)为1126.8 μg/kg。 同时采用此方法检测分析新疆某药厂附近阳性土壤样品,不同批次土壤样品结果分别为:检出(低于定量限)、1532.1 μg/kg。     

Determination of Hexabromocyclododecane in Expanded Polystyrene and Extruded Polystyrene Foam by Gas Chromatography-Mass Spectrometry

A gas chromatography-mass spectrometry (GC/MS) method for the determination of hexabromocyclododecane (HBCD) in expanded polystyrene and extruded polystyrene foam (EPS/XPS) was developed. The EPS/XPS samples were ultrasonically extracted with acetone and the extracts were purified by filtration through a microporous membrane (0.22 μm) and solid-phase extraction. The samples were analyzed using a GC/MS using the selected ion monitoring mode. The ions 157, 319 and 401 were selected as the qualitative ions, while ion 239 was chosen as the quantitative ion. An HBCD standard working solution with a concentration range of 1.0–50.0 mg/L showed good linearity. The detection limit of HBCD was 0.5 mg/kg, meeting the LPC limit (<100 or 1000 mg/kg). Six laboratories were selected to verify the accuracy of the method, and 10 samples were tested. The interlaboratory relative standard deviation range was 3.68–9.80%. This method could play an important role in controlling HBCD contamination in EPS/XPS.     

Modification of Cotton Fabric with Molecularly Imprinted Polymer-Coated Carbon Dots as a Sensor for 17 α-methyltestosterone

Molecularly imprinted polymers@ethylenediamine-modified carbon dots grafted on cotton fabrics (MIPs@EDA-CDs/CF) and smartphone-based fluorescence image analysis were proposed and used for the first time for the detection of 17 α-methyltestosterone (MT). The EDA-CDs were synthesized and grafted on cotton fabric before coating with the MIPs. The MIPs were synthesized using the MT as a template molecule, methacrylic acid (MAA) as a functional monomer, ethylene glycol dimethacrylate (EGDMA) as a cross-linker, and azobisisobutyronitrile (AIBN) as an initiator. The MIPs@EDA-CDs/CF were characterized using FTIR, SEM-EDS, and RGB fluorescence imaging. The fluorescence images were also taken using a smartphone and the ImageJ program was used for RGB measurement. The Δ red intensity was linearly proportional to MT concentration in the range of 100 to 1000 μg/L (R² = 0.999) with a detection limit of 44.4 μg/L and quantification limit of 134 μg/L. The MIPs@EDA-CDs/CF could be stored at 4 °C for a few weeks and could be reused twice. The proposed method could apply for the specific determination of MT in water and sediment samples along with satisfactory recoveries of 96–104% and an acceptable relative standard deviation of 1–6% at the ppb level.     

Comparison of Different d-SPE Sorbent Performances Based on Quick,Easy, Cheap,Effective, Rugged,and Safe (QuEChERS) Methodology for Multiresidue Pesticide Analyses in Rapeseeds

Pesticide extraction in rapeseed samples remains a great analytical challenge due to the complexity of the matrix, which contains proteins, fatty acids, high amounts of triglycerides and cellulosic fibers. An HPLC-MS/MS method was developed for the quantification of 179 pesticides in rapeseeds. The performances of the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method were evaluated using different dispersive solid-phase extraction (d-SPE) sorbents containing common octadecylsilane silica/primary–secondary amine adsorbent (PSA/C18) and new commercialized d-SPE materials dedicated to fatty matrices (Z-Sep, Z-Sep⁺, and EMR-Lipid). The analytical performances of these different sorbents were compared according to the SANTE/12682/2019 document. The best results were obtained using EMR-Lipid in terms of pesticide average recoveries (103 and 70 of the 179 targeted pesticides exhibited recoveries within 70–120% and 30–70%, respectively, with low RSD values). Moreover, the limits of quantification (LOQ) range from 1.72 µg/kg to 6.39 µg/kg for 173 of the pesticides. Only the recovery for tralkoxydim at 10 μg/kg level was not satisfactory (29%). The matrix effect was evaluated and proved to be limited between −50% and 50% for 169 pesticides with this EMR-Lipid and freezing. GC-Orbitrap analyses confirmed the best efficiency of the EMR-Lipid sorbent for the purification of rapeseeds.     

A Strategy for Sample Preparation: Using Egg White Gel to Promote the Determination of Aflatoxin M1 Content in Milk Samples

The analysis of food samples is a challenging task. The high complexity of food matrices hinders the extraction and detection of analytes from them. Therefore, the correct preparation of food samples is a crucial step for their subsequent analysis, as it achieves the proper isolation and preconcentration of analytes and removes the interfering proportion of the food matrix before instrumental analysis. We aimed to develop a method that not only satisfies the requirement of detecting trace compounds in complex matrices but also achieves a “greener” approach by reducing the use of organic solvents and non-degradable materials to minimize the health hazards posed to the operators as well as pollution to the environment. In this study, we prepared egg white as a concentrated gel and used this material for the biological purification of milk samples. After the milk protein was removed by acidification and salting, the residual amount of aflatoxin M1 in milk samples was quantitatively determined by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The results showed that the novel egg white purification method possessed advantages over the immunoaffinity technique used as the reference method in extraction recovery, sensitivity, repeatability, and operability. The limit of detection (LOD) was 0.001 μg/kg. In spiked samples containing 0.01 μg/kg to 2 μg/kg of AFM1, the average recovery was 88.3–94.7%, with a precision of 6.1–11.0%. Improved repeatability was obtained by significantly reducing the operation time and resource requirements compared with the immunoaffinity technique currently used internationally. This study provides a reference for the further improvement of the relevant international standards in place for the detection of aflatoxin M1 in milk.