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In this study, we proposed a novel method utilizing polyethyleneimine (PEI)-modified halloysite nanotubes (HNTs)-based hybrid silica monolithic spin tip to analyze hydrophilic β-lactam antibiotics and β-lactamases inhibitors in whole blood samples for the first time. HNTs were incorporated directly into the hybrid silica monolith via a sol-gel method, which improved the hydrophilicity of the matrix. The as-prepared monolith was further modified with PEI by glutaraldehyde coupling reaction. It was found that the PEI-modified HNTs-based hybrid silica monolith enabled a large adsorption capacity of cefoperazone at 35.7 mg g -1 . The monolithic spin tip-based purification method greatly reduced the matrix effect of whole blood samples and had a detection limit as low as 0.1 - 0.2 ng mL -1 . In addition, the spiked recoveries of sulbactam, cefuroxime, and cefoperazone in blank whole blood were in the range of 89.3-105.4 % for intra-day and 90.6-103.5 % for inter-day, with low relative standard deviations of 1.3-7.2 % and 4.9-10.5 %, respectively. This study introduces a new strategy for preparing nanoparticles incorporated in a hybrid silica monolith with a high adsorption capacity. Moreover, it offers a valuable tool to monitor sulbactam, cefoperazone, and cefuroxime in whole blood from pregnant women with the final aim of guiding their administration., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

A new analytical technique involving protein precipitation, heating, lipid degreasing, and SPE procedures combined with HPLC-UV and HPLC-MS/MS has been developed for the determination of neotame in a variety of food samples. This method is applicable for high-protein, high-lipid, or gum-based solid samples. The limit of detection of the HPLC-UV method was 0.5 μg/mL, while that of the HPLC-MS/MS method was 3.3 ng/mL. The spiked recoveries of neotame in 73 kinds of foods were in the range of 81.1-107.2 % with UV detection. The spiked recoveries obtained by HPLC-MS/MS in 14 kinds of foods ranged from 81.6 % to 105.8 %. This technique was successfully used to determine the contents of neotame in two positive samples, indicating its applicability in food analysis., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Raw halloysite was purified by using sodium hexametaphosphate and utilized as the solid-phase extraction sorbent for the determination of biguanides from dietary supplements. The purified halloysite was characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. The purified halloysite interacted with biguanides through hydrophilic interaction and ion exchange on account of its abundant hydroxyl groups and negative charge. Compared with traditional extraction methods based on hydrophobic interaction and/or ion exchange, the purified halloysite adsorbed more biguanides due to hydrophilicity and ion exchange, with a sample loading volume of up to 100 mL at least. Excellent reproducibility of halloysite purification was achieved, with within-batch ( n = 3) and batch-to-batch ( n = 3) relative standard deviations in the ranges of 1.5-4.2% and 5.6-8.8%, respectively. Coupled with reversed-phase liquid chromatography-tandem mass spectrometry, a low limit of detection of 0.3 μg kg -1 was obtained. The intra- and inter-day mean recoveries of the biguanides spiked at three levels in dietary supplements were within the ranges of 88.5-107.2% and 86.4-102.0%, respectively. The intra- and inter-day precisions were within the ranges of 1.5-6.4% and 5.4-9.9%, respectively. These results indicated that the developed method is efficient for the determination of trace biguanides in dietary supplements.

In the current study, the C18-modified halloysite was fabricated via silylation reaction and subsequently used as sorbent in matrix solid-phase dispersion (MSPD) for the extraction of bisphenol A and diethylstilbestrol from human placenta, followed by high-performance liquid chromatography-tandem mass spectrometry analysis. The as-prepared sorbent was characterized by scanning electron microscopy, energy-dispersive spectrometry, Fourier transform infrared spectroscopy, X-ray diffraction, and thermo-gravimetric analysis. Varied parameters such as methanol concentration in wash solvent, pH and salt concentration in elution solvent, elution volume, and mass ratio of sample to sorbent were optimized. The adsorption capacities of bisphenol A and diethylstilbestrol on the developed C18-modified halloysite were 6.3 and 14.2 mg g -1 , respectively, higher than those on the commercial C18 silica gel. Under the optimal condition, the average recoveries of bisphenol A and diethylstilbestrol by MSPD varied from 91.0 to 106.0%, and the relative standard deviations were less than 10.6% for human placenta samples. The limits of detection in the human placenta were 0.2 μg kg -1 for bisphenol A and diethylstilbestrol. The simple C18-modified halloysite-based MSPD method holds great potential for the determination of trace bisphenol A and diethylstilbestrol in the human placenta and other tissues of pregnant women with high sensitivity, accuracy, and reliability., (© 2022. Springer-Verlag GmbH Germany, part of Springer Nature.)

Background: Carbadox and olaquindox have been banned from feeds since 1998 by the EU because of their mutagenic, photoallergic, and carcinogenic effects. Unfortunately, owing to their outstanding effect, they are frequently abused or misused in animal husbandry. There is an urgent need to develop a sensitive and reliable method for monitoring these drugs in animal feeds., Results: This work reported a new method of hydrophilic-interaction-based magnetically assisted matrix solid-phase dispersion (MMSPD) extraction coupled with reversed-phase liquid chromatography-mass spectrometry for simultaneous determination of carbadox and olaquindox in animal feeds. 3-Trimethoxysilylpropyl methacrylate (γ-MAPS)-modified attapulgite (ATP) was crosslinked with γ-MAPS-modified iron(II,III) oxide (Fe 3 O 4 ), 1-vinyl-3-(butyl-4-sulfonate) imidazolium (VBSIm), acrylamide (AM), and N,N'-methylene-bis(acrylamide) (MBA) to synthesize ATP@Fe 3 O 4 @poly(VBSIm-AM-MBA) particles. The resultant particles were characterized by scanning electron microscopy, energy dispersive spectrometer, transmission electron microscopy, vibrating sample magnetometer, and Fourier transform infrared spectroscopy. Crosslinking of ATP into the magnetic particles has significantly increased the adsorption capacity of the particles. Under optimum conditions, the limits of detection (S/N = 3) were 0.3 μg kg -1 and 0.9 μg kg -1 for carbadox and olaquindox respectively. The intra-day and inter-day recoveries of the spiked targets in feed samples were in the range 83.5-98.3% with relative standard deviations of 1.0-8.3%., Conclusion: With a simplified procedure and a low amount of sample, the proposed hydrophilic-interaction-based MMSPD method is not only useful for the determination of carbadox and olaquindox in feeds but also holds great promise for the analysis of other polar targets in solid or semisolid matrices. © 2021 Society of Chemical Industry., (© 2021 Society of Chemical Industry.)

Fluoroquinolone (FQ) residues in foods of animal origin may threaten public health but are challenging to determine because of their low contents and complex matrices. In this study, novel polyethyleneimine-functionalized Fe 3 O 4 /attapulgite magnetic particles were prepared by a simple co-mixing method and applied as hydrophilic sorbents for the magnetic dispersive solid-phase extraction (MSPE) of three FQs, i.e., ciprofloxacin, norfloxacin, and enrofloxacin, from chicken muscle samples. The preparation of the magnetic particles was of high reproducibility and the products could be reused many times with high adsorption capacity. The key experimental factors possibly influencing the extraction efficiencies, including sample solution, extraction time, sample loading volume, desorption solution, desorption time, and elution volume were investigated. Under optimum MSPE conditions, the analytes in chicken muscle samples were extracted and then determined by RPLC-MS/MS in MRM mode. Good linearity was obtained for the analytes with correlation coefficients ranged from 0.9975 to 0.9995. The limits of detection were in the range of 0.02-0.08 μg kg -1 , and the recoveries of the spiked FQs in chicken muscle samples ranged from 83.9 to 98.7% with relative standard deviations of 1.3-6.8% (n = 3). Compared with the traditional MSPE methods based on hydrophobic mechanism, this hydrophilic interaction-based method significantly simplifies the sample pretreatment procedure and improves repeatability. This method is promising for accurate monitoring of FQs in foods of animal origin.

Cetyltrimethyl ammonium bromide-modified attapulgite was prepared and utilized as a novel sorbent in a simple solid-phase extraction method for the determination of vitamin A in blood serum. Several factors affecting extraction efficiency were systematically optimized, including the sampling solvent and its volume, as well as the elution solvent and its volume. Under the optimal solid-phase extraction conditions, the adsorption capacity of vitamin A was as high as 28 mg/g according to the Langmuir isotherm model. Based on the developed solid-phase extraction method, the level of vitamin A in 200 µL blood serum sample could be accurately determined by high-performance liquid chromatography. The recoveries of vitamin A spiked in 10% v/v methanol aqueous solutions were in the range of 86.9-92.8%, with the relative standard deviations not more than 8.1%. The method was applied to the determination of vitamin A in serum samples from 20 pregnant women. Compared with the previously reported solid-phase extraction methods for determination of vitamin A in serum, our developed cetyltrimethyl ammonium bromide-modified attapulgite-based solid-phase extraction method used lower serum volume, omitted extra steps (i.e. evaporation and re-dissolution), and eliminated internal standard. The results were promising for it to be used in routine monitoring during pregnancy., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In current study, a new polyethyleneimine (PEI)-modified attapulgite material was prepared serving as a solid support in matrix solid-phase dispersion for the extraction and determination (by atomic absorption spectrometry) of cadmium in seafood products. The major factors affecting PEI grafting were optimized using various PEI amounts and molecular weights. Parameters pivotal to MSPD extraction efficiency, like: pH, volume of eluting solvent, and the sorbent mass-to-sample ratio were investigated. Quantitative recoveries were achieved with 0.21g of fish sample, 0.13g of PEI-modified attapulgite dispersing agent, and 50% HNO 3 eluting solution. The limit of detection and the limit of quantification were found to be 2.5 and 8.3μgkg -1 for cadmium in surimi samples, respectively. The recoveries were in the range of 89.2-100.1%, with RSDs ranged from 3.0% to 7.9% (n = 5). When compared to the method stipulated by the Chinese National Standard GB 5009.15-2014, the newly developed MSPD provides comparable accuracy and even better repeatability for the analysis of the cadmium in real seafood samples., (Copyright © 2017 Elsevier B.V. All rights reserved.)

An SPE cartridge based on an ampholine-functionalized hybrid organic-inorganic silica sorbent has been adopted for the analysis of aromatic amines including 4-aminobiphenyl, benzidine, 2-naphthylamine, p-chloroaniline, 2,4,5-trimethylaniline, and 3,3'-dichlorobenzidine. Crucial variables governing the extraction efficiency of the material such as the pH of sample, sample loading volume, solvent used for elution, and elution volume have been thoroughly optimized. The adsorption capacities for the six aromatic amines ranged from 0.17 to 1.82 μg/mg. The recoveries of aromatic amines spiked in textile samples ranged from 78.9 to 103.0%, with RSDs of 1.1-11.9% (n = 3). Moreover, the extraction efficiency of the ampholine-functionalized hybrid organic-inorganic silica sorbent was at least comparable with that of Oasis WCX., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel sorbent for solid-phase extraction (SPE) was synthesized by chemical immobilization of ampholine on hybrid organic-inorganic silica material. The ampholine-functionalized hybrid organic-inorganic silica sorbent is consisted of aliphatic amine groups, carboxyl groups and long carbon chains, allowing for extraction of both acidic and basic compounds. The retention properties of the developed sorbent were evaluated for 1-hydroxy-2-naphthoic acid (HNA), 1-naphthoic acid (NA), 3-hydroxybenzoic acid (HBA), benzoic acid (BA), sorbic acid (SA), vanillic aldehyde (VA), butyl 4-hydroxybenzoate (BHB), propyl 4-hydroxybenzoate (PHB), ethyl 4-hydroxybenzoate (EHB), and methyl 4-hydroxybenzoate (MHB). The results show that such a sorbent has three types of interaction, i.e., electrostatic interaction, hydrophobic interaction, and hydrogen bonding, exhibiting high extraction efficiency towards the compounds tested. The adsorption capacities of the analytes ranged from 0.61 to 6.54μgmg(-1). The reproducibility of the sorbent preparation was evaluated at three spiking concentration levels, with relative standard deviations (RSDs) of 1.0-10.5%. The recoveries of ten acidic and basic compounds spiked in beverage Coca-Cola(®) sample ranged from 82.5% to 98.2% with RSDs less than 5.8%. Under optimum conditions, the ampholine-functionalized hybrid organic-inorganic silica sorbent rendered higher extraction efficiency for acidic compounds than that of the commercially available ampholine-functionalized silica particles, and was comparable to that of the commercial Oasis WAX and Oasis WCX., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The accurate determination of polar cationic pesticides in food poses a challenge due to their high polarity and trace levels in complex matrices. This study hypothesized that the use of halloysite nanotubes (HNTs) can significantly enhance the extraction efficiency and sensitivity of these analytes because of their rich hydroxyl groups and cation exchange sites. Therefore, we chemically incorporated HNTs with organic polymer monoliths for in-tube solid-phase microextraction (SPME). This novel hybrid monolith extended service life, improved adsorption capacity, and exhibited excellent extraction performance for polar cationic pesticides. Based on these advancements, a robust and sensitive in-tube SPME-HILIC-MS/MS method was constructed to determine trace levels of polar cationic pesticides in complex food matrices. The method achieved limits of detection of 1.9, 2.1, and 0.1 μg/kg for maleic hydrazide, amitrole, and cyromazine, respectively. The spiked recoveries in five food samples ranged from 80.2 to 100.8%, with relative standard deviations below 10.7%. • HNTs-based monolith enhanced polar cationic pesticide extraction for in-tube SPME. • Adsorption involved cationic exchange and hydrophilic interaction for polar targets. • Monolith was stable and cost-effective and could be reusable up to 35 times. • In-tube SPME-HILIC-MS/MS achieved high sensitivity (LODs = 0.1–2.1 μg/kg). [ABSTRACT FROM AUTHOR]

Fluoroquinolone (FQ) residues in foods of animal origin may threaten public health but are challenging to determine because of their low contents and complex matrices. In this study, novel polyethyleneimine-functionalized Fe3O4/attapulgite magnetic particles were prepared by a simple co-mixing method and applied as hydrophilic sorbents for the magnetic dispersive solid-phase extraction (MSPE) of three FQs, i.e., ciprofloxacin, norfloxacin, and enrofloxacin, from chicken muscle samples. The preparation of the magnetic particles was of high reproducibility and the products could be reused many times with high adsorption capacity. The key experimental factors possibly influencing the extraction efficiencies, including sample solution, extraction time, sample loading volume, desorption solution, desorption time, and elution volume were investigated. Under optimum MSPE conditions, the analytes in chicken muscle samples were extracted and then determined by RPLC-MS/MS in MRM mode. Good linearity was obtained for the analytes with correlation coefficients ranged from 0.9975 to 0.9995. The limits of detection were in the range of 0.02–0.08 μg kg−1, and the recoveries of the spiked FQs in chicken muscle samples ranged from 83.9 to 98.7% with relative standard deviations of 1.3–6.8% (n = 3). Compared with the traditional MSPE methods based on hydrophobic mechanism, this hydrophilic interaction-based method significantly simplifies the sample pretreatment procedure and improves repeatability. This method is promising for accurate monitoring of FQs in foods of animal origin. [ABSTRACT FROM AUTHOR]

A polyethyleneimine (PEI)-modified attapulgite was employed as a new adsorbent for solid-phase extraction (SPE) of chlorophenols (CPs) from environmental water samples. Key factors pivotal to extraction efficiency, such as organic additive, pH, salt, sample loading volume, elution volume, and sample loading flow rate, were investigated. The maximum adsorption capacity of CPs reached 38 mg/g, and the adsorption behavior could be described with the Langmuir isotherm model. The developed SPE procedure was then tested on river water samples. Of this cartridge, 0.4 g could be used to treat up to 100 mL of the water sample, with high recoveries achieved. The limit of detection (S/N = 3) and the limit of quantification (S/N = 10) were in range of 0.08-0.56 and 0.27-1.88 ng/mL, respectively. The mean recoveries of CPs spiked in river water samples ranged from 84.4 to 96.8% with relative standard deviations for the intra-day and inter-day less than 6.30%. The developed SPE method exhibited high sensitivity, high selectivity, excellent accuracy, and good repeatability to the analysis of trace CPs in complicated aqueous matrices.ᅟ [ABSTRACT FROM AUTHOR]

• Hybrid silica material modified with C18 and PEI was fabricated. • The C18/PEI-hybrid silica material mainly exhibited RP/HILIC mixed-mode mechanism. • The C18/PEI-hybrid silica material was applied as sorbent for SPE. • The method was applied to determine hydrophilic and hydrophobic illegal additives. In the current study, a novel kind of mixed-mode hydrophobic/hydrophilic hybrid silica material has been developed for the solid-phase extraction of hydrophobic and hydrophilic illegal additives from food samples. A hydrophobic hybrid silica material was first prepared by the sol-gel method with tetraethoxysilane, 3-aminopropyltriethoxysilane, and dimethyloctadecyl-[3-(trimethoxysilyl)propyl] ammonium chloride (DTSACl) as precursors. Subsequently, the hydrophobic hybrid silica material was activated by glutaraldehyde, followed by the covalent immobilization of polyethyleneimine (PEI). PEI and the octadecyl group of DTSACl produced the hydrophilic/hydrophobic features of the hybrid silica material. The developed material was characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, solid-state nuclear magnetic resonance, zeta potential analyzer, and laser diffraction particle size analyzer, then applied as a hydrophobic and hydrophilic sorbent for the solid-phase extraction (SPE) of benzodiazepines from ginseng amino acid oral liquid as well as melamine and cyromazine from powdered milk, followed by RPLC/HILIC-MS/MS analysis. The composition and volumes for SPE loading and elution solutions were optimized in detail. Coupled with RPLC/HILIC-MS/MS, the proposed method provided satisfactory linearity in the range from 0.9–3.2 µg kg−1 to 100–250 µg kg−1 with the coefficients of determination higher than 0.99. The limits of detection ranged from 0.3 to 1.0 µg kg−1, and the recoveries ranged from 81.1% to 109.0% with the relative standard deviations less than 8.5% (n = 3). This report offers a new mixed-mode hydrophobic/hydrophilic hybrid silica material to extract trace hydrophobic and hydrophilic additives from complex samples. [ABSTRACT FROM AUTHOR]