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Boric acid-functionalized magnetic covalent organic frameworks (Fe 3 O 4 -TpBD-B) with large surface area and high porosity were prepared and applied for magnetic solid-phase extraction adsorbent of gentamicin from milk before UPLC-MS/MS detection. By utilizing a new HILIC chromatographic column with zwitterionic sulfoalkyl betaine stationary phase based on ethyl bridged hybrid particles (BEH), isomers of gentamicin (C 1 , C 1a , and C 2 +C 2a components). The developed methods demonstrated good linearity (R2 > 0.99), acceptable accuracy and good precision (<10 %), and low limit of quantitation (1.59 ng mL⁻1 for C 1 , 1.52 ng mL⁻1 for C 1a and 2.72 ng mL⁻1 for C 2 +C 2a). In addition, this method has been effectively applied to the analysis of real milk samples. [Display omitted] • Fe 3 O 4 -TpBD-B, a novel adsorbent, was prepared for MSPE of gentamicin in milk. • Selective extraction of gentamicin was achieved via interactions with Fe 3 O 4 -TpBD-B. • An advanced HILIC LC-MS/MS method was developed for the determination of gentamicin. • Ion-pairing reagents are avoided and ion suppression is reduced by the method. • The method is characterized by high sensitivity and excellent accuracy. [ABSTRACT FROM AUTHOR]

Disinfection byproducts (DBPs) have been extensively investigated during the chlorination of water and wastewater. Although over 700 DBPs have been identified, more than 50% of the total organic halogen remains unknown. Solid phase extraction (SPE) has been emerged as a popular pretreatment approach for enrichment and desalting of unknown DBPs prior to the mass spectrometry analysis. However, the effects of SPE conditions on unknown DBPs in real wastewater have not yet been reported. Herein, three factors (acid types, pH values, and sorbent types) influencing the composition of DBPs in chlorinated municipal wastewater were systematically investigated by Fourier transform ion cyclotron resonance mass spectrometry and statistical analysis. The results indicated that the number of DBPs in different SPE conditions ranged from 280 to 706, and the majority ones were Br-DBPs and CHOX compounds. Compared with H 2 SO 4 , more common DBPs were found when using HCl and HCOOH to adjust the pH values of samples. The unique DBPs extracted at pH 1.0 and 2.0 generally owned higher modified aromaticity index (AI mod) value and C number than at pH 3.0. The effect of acid types on the extracted DBPs was pH dependent, and the total number of extracted DBPs increased with the increasing of pH value. In terms of sorbent types, the unique DBPs in C18 sorbent possessed low O/C ratios (O/C < 0.6), whereas the unique ones in HLB sorbent owned high O/C ratios (O/C > 0.6). Compared with C18 and HLB sorbents, the unique DBPs extracted in PPL sorbent were characterized by relatively high AI mod and DBE values. Based on mass difference analysis, 1496 precursors-DBPs pairs were identified in all extracted samples, with the highest number of bromine substitution reaction. Overall, the effects of SPE conditions on the composition of unknown DBPs should not be overlooked, and the amount and diversity of DBPs may be underestimated under a single SPE condition. This study provides new methodological references for the accurate identification of unknown DBPs with different characteristics in real wastewater. [Display omitted] • The composition of unknown DBPs was obviously affected by SPE conditions. • The larger amount of DBPs was extracted at pH 3.0 using H 2 SO 4 and HCOOH. • DBPs extracted in C18 sorbent had low O/C, while ones in HLB sorbent owned high O/C. • Based on mass difference analysis, 1496 precursors-DBPs pairs were identified. [ABSTRACT FROM AUTHOR]

As a new type of porous crystalline composite material, MOF-COF has shown great advantages in metal separation. Herein, a CoMOF-COF was designed for highly selective separation of trace Pb2+ ions. The designed CoMOF-COF has a high density of nitrogen-oxygen functional groups and can selectively separate metal ions. There is a strong affinity between the designed CoMOF-COF material and metal Pb2+ ions, which can be attributed to the ordered heterogeneous porous structure and large amounts of nitrogen-and oxygen-containing functional groups. The composite showed high adsorption selectivity for Pb2+ ions and had adsorption capacity of 33 mg g−1, with high chemical stability. Based on this solid phase extraction material, a high sensitivity detection method for Pb2+ ions was established, which has the detection limit of 37.3 ng L−1, precision of 1.9 %. Linear detection range is 0.2–10 ng mL−1, and the detection of Pb2+ ions in actual water samples was realized. Through this study, it is proved that the strong affinity between the designed CoMOF-COF materials and metal Pb2+ ions can be attributed to the soft and hard acid-base theory, which reveals the structure-activity relationship between the porous heterostructure of such materials and metal separation, providing a highly selective separation material for the separation of other environmental pollutants. For TOC Only. [Display omitted] • A heterogeneously connected CoMOF-COF was designed for highly selective separation of lead ions. • Compared with individual COF and MOF materials, CoMOF-COF exhibits synergistic enhancement of lead ions enrichment. • The lead ions detection system exhibits high sensitivity and strong anti-interference ability. • SPE method based on CoMOF-COF was applied for the analysis of lead ions in environmental water samples. [ABSTRACT FROM AUTHOR]

Owing to their incomplete digestion in the human body and inadequate removal by sewage treatment plants, antiepileptic drugs (AEDs) accumulate in water bodies, potentially affecting the exposed humans and aquatic organisms. Therefore, sensitive and reliable detection methods must be urgently developed for monitoring trace AEDs in environmental water samples. Herein, a novel phenylboronic acid-functionalized magnetic cyclodextrin microporous organic network (Fe 3 O 4 @CD-MON-PBA) was designed and synthesized via the thiol-yne click post-modification strategy for selective and efficient magnetic solid-phase extraction (MSPE) of trace AEDs from complex sample matrices through the specific B–N coordination, π-π, hydrogen bonding, electrostatic, and host-guest interactions. Fe 3 O 4 @CD-MON-PBA exhibited a large surface area (118.5 m2 g−1), rapid magnetic responsiveness (38.6 emu g−1, 15 s), good stability and reusability (at least 8 times), and abundant binding sites for AEDs. Under optimal extraction conditions, the proposed Fe 3 O 4 @CD-MON-PBA-MSPE-HPLC-UV method exhibited a wide linear range (0.5–1000 μg L−1), low limits of detection (0.1–0.5 μg L−1) and quantitation (0.3–2 μg L−1), good anti-interference ability, and large enrichment factors (92.2–104.3 to 92.3–98.0) for four typical AEDs. This work confirmed the feasibility of the thiol-yne click post-synthesis strategy for constructing novel and efficient multifunctional magnetic CD-MONs for sample pretreatment and elucidated the significance of B–N coordination between PBA and N-containing AEDs. [Display omitted] • Thiol-yne click post-modification is developed to construct novel Fe 3 O 4 @CD-MON-PBA. • B–N coordination interaction plays significant role in AEDs enrichment. • Determination of AEDs from complex samples is realized. [ABSTRACT FROM AUTHOR]

Tobacco-specific alkaloids and nitrosamines are important biomarkers for the estimation of tobacco use and human exposure to tobacco-specific nitrosamines that can be monitored by wastewater analysis. Thus far their analysis has used solid phase extraction, which is costly and time-consuming. In this study, we developed a direct injection liquid chromatography-tandem mass spectrometry method for the quantification of two tobacco-specific alkaloids and five nitrosamines in wastewater. The method achieved excellent linearity (R 2 > 0.99) for all analytes, with calibration ranging from 0.10 to 800 ng/L. Method limits of detection and quantification were 0.17 ng/L (N-nitrosonornicotine, NNN) and 1.0 ng/L (N-nitrosoanatabine (NAT) and NNN), with acceptable accuracy (100 % ± 20 %) and precision (± 15 %). Analyte loss during filtration was < 15 %, and the relative matrix effect was < 10 %. The method was applied to 43 pooled wastewater samples collected from three wastewater treatment plants in Australia between 2017 and 2021. Anabasine and anatabine were detected in all samples at concentrations of 5.0 – 33 ng/L and 12 – 41 ng/L, respectively. Three of the five tobacco-specific nitrosamines (NAT, NNN, and (4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol) (NNAL)) were detected, in < 50 % of the wastewater samples, with concentrations nearly ten times lower than the tobacco alkaloids (< 1.0 – 6.2 ng/L). In-sewer stability of the nitrosamines was also assessed in this study, with four (NAT, NNAL, NNN, and N-nitrosoanabasine (NAB)) being stable (i.e. < 20 % transformation over 12 h in both control reactor (CR) and rising main reactor (RM) and 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) being moderately stable (< 40 % loss over 12 h in RM). This direct injection method provides a high-throughput approach in simultaneous investigation of tobacco use and assessment of public exposure to tobacco-specific nitrosamines. [Display omitted] • New sensitive direct injection methods developed for tobacco-specific biomarkers. • Limit of detections for target analytes ranged between 0.17 and 1.9 ng/L. • Tobacco-specific nitrosamines are relative stable in laboratory-scale sewer reactors. • First detection of NNN and NNAL in actual wastewater samples. • Five analytes were detected in wastewater samples from different populations. [ABSTRACT FROM AUTHOR]

Bisphenols and benzophenones are two typical kinds of endocrine-disrupting compounds (EDCs) that have been extensively detected in water environments, posing unanticipated risks to aquatic organisms and humans. It is urgent to develop efficient sample pretreatment methods for precise measurement of such EDCs. In this study, a magnetic and multi-shelled metal-organic framework derivative material has been prepared to extract and enrich trace bisphenols and benzophenones from water. Via a solvothermal reaction induced by sodium citrate followed by a carbonization treatment, a ZIF-67@ZIF-8 derived CoZn-magnetic hierarchical carbon (CoZn-MHC) material has been synthesized as a high-performance magnetic solid-phase extraction (MSPE) adsorbent. This adsorbent exhibited a good specific surface area (213.80 m2⋅g−1) and a saturation magnetization of 63.2 emu·g−1. After the optimization of several parameters (including adsorbent dosage, extraction time, pH, ionic strength, desorption solvent, and solvent volume), an efficient MSPE method for several EDCs (comprising bisphenols and benzophenones) was developed with a good linear range (R2 ≥ 0.990), a high sensitivity range (LODs: 0.793–5.37 ng⋅L−1), and good reusability (RSD ≤4.67 % in five consecutive tests). Furthermore, the material exhibited commendable resistance to matrix interference in natural water samples with the recovery rates of target compounds ranging from 74.8 % to 107 %. We envision that the preparation strategy of this functional metal-organic framework (MOF)-based adsorbent for EDCs may provide insights for relevant research in the future. [Display omitted] • Synthesized a porous and magnetic Zn-Co MOF derivative in a few simple steps. • A high saturation intensity (63.2 emu⋅g−1) of CoZn-MHC ensured fast analyte separation with magnet. • CoZn-MHC-based MSPE procedure exhibited great analytical performance, with recoveries ranging from 74.8 % to 107 %. • The developed method was applied to detect EDCs in real water, with the extraction efficiencies being 94.0–100 %. [ABSTRACT FROM AUTHOR]

To address the under-researched risk of bisphenols (BPs) in e-cigarette liquids, comprehensive studies have been conducted to propose optimum sample preparation and analysis methods. To determine twelve BPs in refill liquids for e-cigarettes, three sample preparation methods based on distinct operational and working principles were employed. These included fabric phase sorptive extraction (FPSE), ultrasound-assisted solvent extraction of porous membrane-packed samples (UASE-PMS) and solid phase extraction (SPE) utilizing molecularly imprinted polymers (MIPs) technology. Each extraction method was combined with ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS). Key parameters of FPSE and UASE-PMS procedures were optimized. This optimization included selection of the FPSE membrane types, durations of extraction and the choice solvents. Comprehensive validation was conducted, demonstrating linearity across a range from 2 to 60 ng/mL for all BPs (BPS, BPA, BPF, BPE, BPB, BPC, BPZ, BPFL, BPBP, BPP, BPG and BPM). Determination coefficients were above 0.9913, signifying linear relationship. The limits of detection (LODs) were established below 0.90 ng/mL, while the limits of quantification (LOQs) were lower than 2.5 ng/mL. Notably, the method based on UASE-PMS was successfully applied to the analysis of refill liquids for e-cigarettes samples. A comparative analysis of the methods highlighted variances in precision, accuracy, and applicable aspects, such as adjustment of parameters, sample preparation time, cost, handling, availability and possible limitations. Three methods have been identified as suitable for analysing BPs in e-cigarette refill liquids, highlighting the necessity to examine their presence in these products., 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 Elsevier B.V. All rights reserved.)

N-nitrosamines (NAs) are potentially highly carcinogenic compounds that have recently been detected in traces in various drug products (DPs). Due to the different physicochemical properties of NAs and active pharmaceutical ingredients (APIs), there is a lack of appropriate analytical methods for simultaneously determining multiple NAs in various DPs. To overcome these limitations, a versatile and innovative analytical approach was developed using a unique sample clean-up procedure by solid phase extraction based on hydrophilic interaction chromatography, which retains high amounts of APIs and polar excipients while allowing NAs of interest to pass through. The samples were analyzed by liquid chromatography coupled with electrospray ionization high-resolution mass spectrometry. The proposed highly sensitive, selective, and robust method was successfully validated, resulting in excellent linearity (R 2  > 0.999), accuracy (85-115 %), and precision (RSD <10 %) with adequate recoveries (>80 %), achieving limits of quantitation of at least 42.5 % of regulatory limits. Furthermore, robustness was confirmed for ten DPs (recoveries >80 % and RSD <15 % for all NAs), including those containing up to three APIs. The analytical approach was utilized to examine 26 commercially available and expired DPs. Three NAs (N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine, and N-nitroso-di-n-butylamine) were detected, only NDMA exceeded the limits in expired DPs by up to 32-fold. It was found that special care should be taken when handling samples as NDMA content can be decreased by almost 50 % if samples are not prepared immediately. The approach was tested on 59 different APIs and was confirmed as reliable tool for routine monitoring of 15 NAs in various DPs. Due to its flexibility, the method can be further adapted to the specific API of interest or extended to the newly emerging NA drug substance-related impurities to ensure the safety of DPs and thereby mitigate potential health risks., 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 The Authors. Published by Elsevier B.V. All rights reserved.)

In this study, an ultrasonic assisted dispersive magnetic solid phase extraction leveraging Fe 3 O 4 @nitrogen-doped carbon@Pd core-double shell nanotubes was developed for the extraction of organophosphorus pesticides (OPPs) in trace levels from real samples. Incorporation of Pd species into the structure of the nanosorbent could enhance its interactions with sulfur groups in the structure of OPPs. X-ray photoelectron spectroscopy and X-ray diffraction, brunauer-emmett-teller, field emission scanning electron microscopy, and high-resolution transmission electron microscopy were used to characterize the nanosorbent after its synthesis. Then, effective variables on the extraction efficiency of OPPs using the nanosorbent were optimized. These parameters included 2-propanol as the adsorption solvent; the sample pH of 7.0; the sorbent quantity of 10 mg; and the extraction and desorption times of 3 min. Under optimized conditions, linear ranges with determination coefficients (R2) higher than 0.99, low detection limits of 0.30 ng mL−1, high preconcentration factors (423–470) and relatively high extraction recoveries (84–94 %) were obtained. The proposed extraction system was then successfully applied to the analysis of OPPs in fruits, vegetables, water, and agricultural soil samples, yielding relative recoveries from 90.4 to 107 %. [Display omitted] • Fe 3 O 4 @N-dC@Pd core-double shell nanotubes was introduced as a new magnetic nanosorbent for SPE purposes. • The method was applied to the determination of some organophosphorus pesticides (OPPs) in a wide range of real samples. • The proposed magnetic nanosorbent could be reused at least five times. • Extraction recoveries were obtained in the range 84–94 % for OPPs. [ABSTRACT FROM AUTHOR]

Surface Enhanced Raman Scattering (SERS) has been extensively utilized in therapeutic drug monitoring (TDM) due to its rapid detection speed, high sensitivity and straightforward sample pretreatment. In this study, Au/AgNPs were obtained through the reduction of AgNO 3 on the surface of AuNPs. Subsequently, Au/AgNPs were embedded into the tetrahedral lattice of ZIF-8 MOFs, resulting in the formation of Au/Ag@ZIF-8 nanocomposites. The Au/Ag@ZIF-8 nanocomposites exhibit a robust electromagnetic enhancement of Au/Ag bimetallic nanoparticles and a considerable adsorption capacity of ZIF-8 MOFs. This enables the pre-enrichment of target molecules in the vicinity of the electromagnetic field of the Au/AgNPs, thereby enhancing the sensitivity of SERS detection. The SERS substrate also exhibits high stability and reproducibility, as well as molecular sieving effects, due to the fact that Au/AgNPs are embedded into the tetrahedral lattice of ZIF-8. A TDM method for tacrolimus (FK506) in human serum was developed by using Au/Ag@ZIF-8 nanocomposites as solid phase extraction (SPE) adsorbent and SERS substrates. The results showed that under the optimized conditions, tacrolimus exhibited satisfactory linearity within the concentration range of 10−5-10−11 mol L−1, with a correlation coefficient (R2) of 0.9944, and the limit of detection (LOD) was as low as 6.4 pg mL−1. The recoveries were observed to range between 92 % and 105 %, with an RSD of below 8 %. The method is highly sensitive, exhibiting a sensitivity that is 3-6 orders of magnitude higher than that of existing analytical techniques. It has the potential to be applied in a clinical setting to biological samples. [Display omitted] • Synthesis of Au/Ag@ZIF-8 by embedding Au/Ag in the ZIF-8 tetrahedral lattice. • The detection limit of Au/Ag@ZIF-8 SERS substrate was as low as 6.4 pg mL−1. • Au/Ag@ZIF-8 SERS substrates showed high stability and molecular sieving effects. • Quantification of trace FK506 in human serum by an ultrasensitive TDM method. [ABSTRACT FROM AUTHOR]

Because of rapid industrialization and agriculturalization, solving the pressing problems of environment pollution, especially water and food quality, requires innovative solutions. In this paper, a novel and versatile metal-organic framework (ZIF-8)-hybrid monolithic column (ZIF-HMC) was prepared for in-tube solid-phase microextraction (IT-SPME) of organic nitrogen pesticides (ONPs). The prepared monolithic columns had superior adsorption sites, high porosity, excellent permeability, and ideal specific surface area based on Fourier Transform Infrared Spectroscopy (FT-IR), X-ray Diffraction (XRD), Thermal Field Emission Scanning Electron Microscopy (SEM), Energy Dispersive Spectrometry (EDS), X-ray Photoelectron Spectroscopy (XPS), and N 2 adsorption-desorption. The ZIF-HMC contained a large number of nitrogen and oxygen atoms, benzene rings and ZIF-8, which could synergistically promote the adsorption efficiency of ONPs through multiple interactions, such as hydrogen bonding, π-π accumulation, hydrophobic interactions, cation-π interactions, and pore adsorption by MOFs. Under the optimal conditions, a simple, efficient, and sensitive method for the analysis of six organic pesticides in environmental water samples was developed by using the ZIF-HMC as the extraction medium coupled with high performance liquid chromatography-ultraviolet (HPLC-UV). The method had a wide linear range (0.63–1000 μg L−1), a low detection limit (0.19–1.91 μg L−1) and satisfactory recoveries (87.4 %–110.2 %), the linear correlation coefficient was (R2) 0.9972–0.9995 and the relative standard deviation (RSD) was less than 2.64 %. The study had demonstrated the potential application of the developed method for the enrichment and analysis of organic pesticides in complex matrices of environmental samples, as well as the feasibility of MOFs materials for IT-SPME sample preparation. [Display omitted] • An in-situ radical polymerization method was employed to prepare ZIF-8 hybrid monolithic column (ZIF-HMC). • The versatile ZIF-HMC was used to detect six organic nitrogen pesticides (ONPs) in combination with HPLC. • The ZIF-HMC contained a large number of nitrogen and oxygen atoms, benzene rings and large specific surface area of ZIF-8. • The proposed method exhibit excellent stability, durability, extraction capacity, and promoting adsorption efficiency. [ABSTRACT FROM AUTHOR]

Magnetic solid-phase extraction (MSPE) technology for tetracycline (TCC) was developed by employing the novel and pre-designed Fe 3 O 4 –COOH@hydrogen-bonded organic frameworks (HOFs) adsorbents in complex food samples. The HOF shell was grown onto the Fe 3 O 4 –COOH core by in-situ self-assembled method. The excellent MSPE performances with less solvent, less adsorbent and time consumption were derived from the hydrogen bonding, π-π and hydrophobic interactions between HOF shell and TCC. Combined with HPLC analysis, Fe 3 O 4 @ HOFs adsorbent reduced matrix effects and the established MSPE-HPLC method for TCC gave the linearity of 0.001–6 μg mL−1 with the limit of detection 0.0003 μg mL−1. The recoveries in pure milk, canned yellow peach and carrot were 82.4–103.7 %. The method provided a simple, efficient and dependable alternative to monitor trace TCC antibiotics in food or environmental samples. [Display omitted] • Magnetic Fe 3 O 4 @HOFs adsorbent were first prepared by in-situ self-assembled method. • Effective extraction for TCC on Fe 3 O 4 @HOFs was performed because of the hydrogen bonding, π-π and hydrophobic interactions. • Fe 3 O 4 @HOFs -MSPE-HPLC method was validated and applied in the analysis of TCC in real food samples. [ABSTRACT FROM AUTHOR]

The effective method for trypsin purification should be established because trypsin has important economic value. In this work, a novel and simple strategy was proposed for fabricating micron-sized magnetic Fe 3 O 4 @agarose-benzamidine beads (MABB) with benzamidine as a ligand, which can efficiently and selectively capture trypsin. The micro-sized MABB, with clear spherical core-shell structure and average particle size of 6.6 μm, showed excellent suspension ability and magnetic responsiveness in aqueous solution. The adsorption capacity and selectivity of MABB towards target trypsin were significantly better than those of non-target lysozyme. According to the Langmuir equation, the maximum adsorption capacity of MABB for trypsin was 1946 mg g−1 at 25 °C, and the adsorption should be a physical sorption process. Furthermore, the initial adsorption rate and half equilibrium time of MABB toward trypsin were 787.4 mg g−1 min−1 and 0.71 min, respectively. To prove the practicability, MABB-based magnetic solid-phase extraction (MSPE) was proposed, and the related parameters were optimized in detail to improve the purification efficiency. With Tris-HCl buffer (50 mM, 10 mM CaCl 2 , pH 8.0) as extraction buffer, Tris-HCl buffer (50 mM, 100 mM CaCl 2 , pH 8.0) as rinsing buffer, acidic eluent (0.01 M HCl, 0.5 M NaCl, pH 2.0) as eluent buffer and alkaline buffer (1 M Tris-HCl buffer, pH 10.0) as neutralization solution, the MABB-based MSPE was successfully used for trypsin purification from the viscera of grass carp (Ctenopharyngodon idella). The molecular weight of purified trypsin was determined as approximate 23 kDa through sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). The purified trypsin was highly active from 30 °C to 60 °C, with an optimum temperature of 50 °C, and was tolerant to pH variation, exhibiting 85 % of maximum enzyme activity from pH 7.0 to 10.0. The results demonstrated that the proposed MABB-based MSPE could effectively purify trypsin and ensure the biological activity of purified trypsin. Therefore, we believe that the novel MABB could be applicable for efficient purification of trypsin from complex biological systems. [Display omitted] • Magnetic Fe 3 O 4 @agarose-benzamidine beads (MABB) were fabricated for trypsin purification. • MABB had fast magnetic responsiveness and excellent suspension ability in aqueous solution. • MABB was used for trypsin purification from viscera of grass carp (Ctenopharyngodon idella). • MABB could effectively purify trypsin and ensure the biological activity of purified trypsin. [ABSTRACT FROM AUTHOR]

The approaches to matrix effects determination and reduction in ultra-high performance supercritical fluid chromatography with mass spectrometry detection have been evaluated in this study using different sample preparation methods and investigation of different calibration models. Five sample preparation methods, including protein precipitation, liquid-liquid extraction, supported liquid extraction, and solid phase extraction based on both "bind and elute" and "interferent removal" modes, were optimized with an emphasis on the matrix effects and recovery of 8 forms of vitamin E, including α-, β-, γ-, and δ-tocopherols and tocotrienols, from plasma. The matrix effect evaluation included the use and comparison of external and internal calibration using three models, i.e., least square with no transformation and no weighting (1/x0), with 1/x2 weighting, and with logarithmic transformation. The calibration model with logarithmic transformation provided the lowest %-errors and the best fits. Moreover, the type of the calibration model significantly affected not only the fit of the data but also the matrix effects when evaluating them based on the comparison of calibration curve slopes. Indeed, based on the used calibration model, the matrix effects calculated from calibration slopes ranged from +92% to – 72% for α-tocopherol and from −77% to +19% in the case of δ-tocotrienol. Thus, it was crucial to calculate the matrix effect by Matuszewski's post-extraction approach at six concentration levels. Indeed, a strong concentration dependence was observed for all optimized sample preparation methods, even if the stable isotopically labelled internal standards (SIL-IS) were used for compensation. The significant differences between individual concentration levels and compounds were observed, even when the tested calibration range covered only one order of magnitude. In methods with wider calibration ranges, the inappropriate use of calibration slope comparison instead of the post-extraction addition approach could result in false negative results of matrix effects. In the selected example of vitamin E, solid-phase extraction was the least affected by matrix effects when used in interferent removal mode, but supported liquid extraction resulted in the highest recoveries. We showed that the calibration model, the use of a SIL-IS, and the analyte concentration level played a crucial role in the matrix effects. Moreover, the matrix effects can significantly differ for compounds with similar physicochemical properties and close retention times. Thus, in all bioanalytical applications, where different analytes are typically determined in one analytical run, it is necessary to carefully select the data processing in addition to the method for the sample preparation, SIL-IS, and chromatography. [Display omitted] • 5 sample preparation methods for vitamin E extraction from plasma were optimized. • The effect of a calibration model in quantitation was evaluated in detail. • High matrix effect noted for linear regression without transformation and weighting. • Matrix effects from calibration curve slope and post-extraction approach differ. • Post-extraction addition confirmed concentration dependence of matrix effects. [ABSTRACT FROM AUTHOR]

Development of fresh solid phase extractant is critical for selective separation and purification of special proteins. Herein, we demonstrated a recombinant Staphylococcal Protein G (rSPG) with a His-tag modified the novel single-metal organic framework (rSPG@Ni-MOF-74). The proposed solid-phase extraction material possessed a uniform spindle-shaped structure, large surface area (709.60 m2 g−1) and pore volume (0.08 m3 g−1), high metal content (22.57 wt%), which facilitated the interaction between host and guest. As results, the composite displayed outstanding selective recognition and adsorption of IgG, due to synergistic effect of the binding ability of rSPG with the Fc region of IgG, maintained through hydrogen bonding and electrostatic attraction, as well as hydrophobic interaction. The adsorption performance and mechanism of rSPG@Ni-MOF-74 have been fully investigated. Additionally, the rSPG@Ni-MOF-74 composite could effectively separate IgG from serum obtained from healthy humans, with the purity of the separated IgG verified through SDS-PAGE analysis. Furthermore, LC-MS/MS analysis identified a high content of IgG (55.3 %) in the eluate from rSPG@Ni-MOF-74, suggesting the great potential of rSPG@Ni-MOF-74 in IgG separation and enrichment from complex matrix. [Display omitted] • A novel recombinant Staphylococcal Protein G (rSPG) modified the novel single-metal organic framework (rSPG@Ni-MOF-74) is developed. • The proposed rSPG@Ni-MOF-74 as absorbent offer new strategies for selective adsorption of IgG with a high adsorption capacity. • The proposed strategies realize selective isolation and purification of IgG from healthy human whole blood. [ABSTRACT FROM AUTHOR]

N-myristoylation is one of the most widespread and important lipidation in eukaryotes and some prokaryotes, which is formed by covalently attaching various fatty acids (predominantly myristic acid C14:0) to the N-terminal glycine of proteins. Disorder of N-myristoylation is critically implicated in numerous physiological and pathological processes. Here, we presented a method for purification and comprehensive characterization of endogenous, intact N-glycine lipid-acylated peptides, which combined the n egative s election method for N-terminome and the n ano g raphite f luoride-based s olid- p hase e xtraction method (NeS-nGF SPE). After optimizing experimental conditions, we conducted the first global profiling of the endogenous and heterogeneous modification states for N-terminal glycine, pinpointing the precise sites and their associated lipid moieties. Totally, we obtained 76 N-glycine lipid-acylated peptides, including 51 peptides with myristate (C14:0), 10 with myristoleate (C14:1), 6 with tetradecadienoicate (C14:2), 5 with laurate (C12:0) and 4 with lauroleate (C12:1). Therefore, our proteomic methodology could significantly facilitate precise and in-depth analysis of the endogenous N-myristoylome and its heterogeneity. [Display omitted] • This study presented a strategy, NeS-nGF SPE, to direct analysis of the intact N-myristoylated peptides in mammalian cells. • Both the modification site and its endogenously attached lipid composition was obtained simultaneously in one identification. • We conducted the first global profiling of the endogenous and heterogeneous modification states for N-terminal glycine. [ABSTRACT FROM AUTHOR]

In this work, sulfhydryl (SH) functionalized magnetic covalent organic framework (COF) was synthesized by using 4-aldehyde phenyl butadiyne (DEBD) and 1,3,5-tris(4-aminophenyl) benzene (TAPB) as the monomers and ethanedithiol as the modifier, with the aid of thiol-alkyne "click" reaction. The prepared Fe 3 O 4 @COF TAPB-DEBD @SH exhibited relatively strong magnetism (32.8 emu g−1), good stability and selectivity to target analytes with a high sulfhydryl content (0.24 mmol g−1). Based on Fe 3 O 4 @COF TAPB-DEBD @SH, a method combining magnetic solid phase extraction with inductively coupled plasma mass spectrometry (ICP-MS) was developed for the quantitative analysis of trace metals. Under the optimal conditions, the method merited fast desorption kinetics (<2 min), adsorption kinetics (<20 min), fast phase separation (<1 min), high enrichment factor (100), and the detection limits for Cd, Hg, Pb and Bi were determined to be 1.18, 0.51, 4.91 and 0.39 ng L−1, respectively. A good resistance to complex matrices was demonstrated for the method in the analysis of soil, atmospheric particles and simulated pulmonary fluids samples. Certified reference materials (coal fly ash GBW08401 and soil GBW07427) were employed to validate the accuracy of the method. Four target metals in the range of 12.9–215 ng L−1, 0.06–24.6 μg g−1 and 0.52–33.1 ng m−3 were found in local water, soil and atmospheric particulates (PM), respectively. Additionally, artificial lysosome solution and gamble's solution were used to simulate human pulmonary fluid and the bioaccessibility of Cd, Hg, Pb and Bi in PM 2.5 was evaluated to be 58.6–73.1 % and 1.3–7.1 %, respectively. [Display omitted] • Fe 3 O 4 @COF TAPB-DEBD @SH shows good stability and selective adsorption performance. • The method merits good resistance to complex matrix with high enrichment factor. • Cd, Hg, Pb and Bi were detected in local lake/river water, soil and PM samples. • Metals show different bioaccessibility in GS and ALF simulated lung fluid. [ABSTRACT FROM AUTHOR]

Alkyl imidazolium ionic liquids (Cn[MIM]), initially heralded as eco-friendly green solvents for diverse industrial applications, have increasingly been recognized fortheir biodegradability challenges and multiple biotoxicity. Despite potential health risks, research into the effects of Cn[MIM] on human health remains scarce, particularly regarding their detection in biological serum samples. This study validated a matrix-matched calibration quantitative method that utilizes solid-phase extraction (SPE) coupled with ultrahigh-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The method was used to analyze the presence of 10 ionic liquids (ILs) with varying alkyl carbon chain lengths (C 2 –C 12) across 300 human serum samples. Efficient separation was achieved using optimized SPE conditions and a BEH C18 column with an appropriate mobile phase. Results demonstrated a strong linear relationship (0.05–100 ng/mL; R2 = 0.995–0.999), with detection and quantification limits with detection and quantification limits ranging from 0.001 to 0.107 ng/mL and 0.003–0.355 ng/mL, respectively. Intraday and inter-day precisions were 0.85–6.99 % and 1.50–7.46 %, with recoveries between 82 and 113 %. The validated method detected C 6 MIM in 19 % of samples and C 8 MIM in 8.3 % of samples, with concentrations ranging from 0.02 to 111.70 μg/L and 0.09–16.99 μg/L, respectively, suggesting a potential risk of human exposure. This underscores the importance of robust detection methods in monitoring environmental and human health impacts of alkyl imidazolium compounds. [Display omitted] • A sensitive method was developed for determining 10 Cn[MIM] in biological matrices. • Phosphoric acid dissociates Cn[MIM] from plasma proteins to enhance analytes recovery. • Optimized WCX column conditions are used for high-sensitivity LC-MS/MS analysis. • C6[MIM] and C8[MIM] detected in 19 % and 8.3 % of 300 serum samples, respectively. [ABSTRACT FROM AUTHOR]

N-nitrosamines (NAs) are highly carcinogenic compounds commonly found in food, beverages, and consumer products. Due to their wide polarity range, it is challenging to find a suitable carbon adsorbent that can simultaneously adsorb and enrich both polar and nonpolar NAs with good recovery. In this study, nitrogen-doped magnetic mesoporous carbon nanospheres (M-MCN) were prepared and employed as an adsorbent for magnetic solid-phase extraction (MSPE) to extract and concentrate four NAs. The introduction of nitrogen functional groups enhanced the hydrophilicity of the carbon material, allowing M-MCN to achieve a balance between hydrophilicity and hydrophobicity, resulting in good recovery for both polar and nonpolar NAs. A method combining MSPE with gas chromatography-mass spectrometry (GC-MS) was developed for the determination of NAs in processed meat and alcoholic beverages. The method exhibited a good linear range (1–100 ng g−1, r2 > 0.9967) and trace-level detection (0.53–6.6 ng g−1). The recovery rates for the four NAs ranged between 85.7 and 110.7 %, with intra-day precision expressed as relative standard deviation (RSD) between 4.1 and 10.7 %, and inter-day precision between 4.8 and 12.9 %. The results demonstrated not only good accuracy and precision but also provided a new adsorbent for the enrichment of trace-level NAs in processed meat and alcoholic beverage samples. [Display omitted] • M-MCN was conveniently prepared using a dual template induced self-assembly method. • A rapid and efficient MSPE sample pre-treatment technique was employed. • M-MCN exhibited excellent adsorption capacity for both highly polar and nonpolar NAs. • A sensitive method for the determination of NAs in food products was established. [ABSTRACT FROM AUTHOR]

Three-dimensional sponge-architecture covalent organic frameworks (COFs)-aerogel was successfully designed and synthesized via a freeze-drying template approach, and utilized as an efficient sorbent in solid-phase extraction (SPE). A method for selective enrichment of pharmaceutical contaminants including tetracycline, chlortetracycline, methacycline and oxytetracycline in the environment and food samples was proposed by combining with high performance liquid chromatography (HPLC). To understand the adsorption mechanism, selectivity test and molecular dynamics (MD) simulated calculation were both carried out. The experimental and in-silico results demonstrated that the COFs-aerogel possessed high selectivity for contaminants with H bond acceptors/donors and good efficiency with maximum adsorption capacity up to 294.1 mg/g. The SPE-based HPLC method worked well in the range of 8–1000 ng/mL, with the need of little dose of adsorbent and sample volume while no need of spectrometer, outgoing the reported adsorbents. Under the optimized conditions, the intra-day and inter-day relative standard deviations (RSD) of repeatability were within 2.78–6.29 % and 2.44–8.42 % (n = 5). The results meet the current detection requirement for practical applications, and could be extended for further design of promising adsorbents. [Display omitted] • Ultralight COFs-aerogel are designed and fabricated. • COFs-aerogel served as a solid-phase extraction adsorbent for adsorption and determination of tetracycline antibiotics. • The established COFs-aerogel-SPE liquid chromatography method illustrated wide linear range, low dose, no spectrometer needed and good regeneration capacity for tetracycline antibiotics. • Experimental data combined with Molecular Dynamics (MD) simulated calculation were used to investigate the adsorption mechanism. [ABSTRACT FROM AUTHOR]

Metal-organic frameworks (MOFs) are good adsorbents for targeted chemicals with their adjustable properties. Herein, we prepared a zirconium based MOF (MOF-808(Zr)) and functionalized it employing 2-mercapto-4-methyl-5-thiazolacetic acid (MOF-808(Zr)-Tz). The prepared MOFs were characterized by XRD, FTIR, SEM-EDX, TGA, N 2 sorption, zeta potential measurements, and elemental analysis. The surface area of MOF-808(Zr)-Tz was 1348 m2/g. Dispersive solid-phase micro-extraction (D-SPµE) method based on MOF-808(Zr)-Tz was firstly developed and applied to the extraction of chromium, silver, and rhodium in waters. The determination of the analytes was done by FAAS. The optimal pH and eluent for analytes were 7.0 and 3 mL of 2 mol L−1 HCl, respectively. The contact times were 1 min for adsorption and 3 min for elution. The LOD and PFs of the D-SPμE for analytes were 2.3 μg L−1 and 13.3 for chromium, 2.1 μg L−1 and 13.3 for silver, and 3.1 μg L−1 and 13.3 rhodium, respectively. The D-SPμE method was verified with analyses of NW-TMDA-54.6 Lake water and SPS-WW1 Batch 114 Wastewater and with spiked dam water, river water, well water, sea water, and wastewater. The recoveries of the analytes changed from 89 to 108 %. The results indicated that the method is selective, simple, effective, and rapid for extracting chromium(III), silver(I) and rhodium(III) in waters. [Display omitted] • A MOF-808(Zr) and MOF-808(Zr)-Tz functionalized by 2-mercapto-4-methyl-5-thiazolacetic acid were synthesized. • It was utilized for the first time as a sorbent for the D-SPμE of Cr(III), Ag(I) and Rh(III). • The surface area of MOF-808(Zr)-Tz is rather high to be 1348 m2/g. • Contact times of 1 min for adsorption and 3 min for elution of analytes on adsorbent were enough. • Analysis of analytes was done in dam water, river water, well water, sea water, and wastewater. [ABSTRACT FROM AUTHOR]

Covalent organic polymers (COPs) have garnered considerable attention as promising adsorbents of online solid phase extraction (online SPE). Morphology modulation provides an appealing solution to enhance adsorption efficiency and reduce back-pressure in the absorbent. However, the synthesis of COPs with regular geometric shapes and specific adsorption selectivity remains challenging. In this study, a uniform spherical fluorinated COP (F-sCOP, average diameter: 2.14 μm) was successfully synthesized by Schiff base reaction of 1,3,5-triformylphoroglucinol (TP) and 2,2'-bis(trifluoromethyl)benzidine (TFMB). The F-sCOP had a large surface area (BET: 346.2 m2 g−1), remarkable enrichment capacity (enrichment factors: 186–782), high selectivity toward fipronil and its metabolites (adsorption efficiency >93.1%), and admirable service life (>60 times). Based on the adsorbent, a novel μ-matrix cartridge extraction-online-μ-solid phase extraction-high performance liquid chromatography-mass spectrometry (μ-MCE-online-μ-SPE-HPLC-MS) method was constructed and used to track trace fipronil and its metabolites in soil. The proposed method exhibited a wide linear range (0.05–1000 ng g−1), low quantitation limits (LOQs: 0.0027–0.011 ng g−1), high recoveries (90.1–119.6%) and good repeatability (RSD ≤10.5%, n = 3) for fipronil analysis. This study paves the way for pesticide analysis in soil risk assessment. [Display omitted] • A novel μ-MCE-online-μ-SPE-HPLC-MS method was developed. • F-sCOP was employed to selectively capture fipronil and its metabolites. • F-sCOP exhibited superiority in surface area, enrichment capacity, selectivity and reusibility. • The method possesses the potential application prospect in soil risk assessment. [ABSTRACT FROM AUTHOR]

The utilization of deep eutectic solvents (DES) in sustainable extracting and separating of phytochemicals shows promising prospect. An exceptionally fast, eco-friendly, and sustainable approach was proposed for extracting bioactive compounds from Coptidis Rhizoma based on deep eutectic solvent-based ultrasound-assisted matrix solid phase dispersion (DES-UA-MSPD). Single-factor experiments and Box-Behnken design were utilized to explore the optimal extraction conditions. The analysis indicated that the acidic DES, especially betaine-acrylic acid (Bet-Aa 1:4 mol/mol) with 50% water content, was proved to be the most effective medium for the extraction of alkaloids (magnoflorine, groenlandicine, coptisine, epiberberine, berberine and palmatine) and organic acid (chlorogenic acid). With the parameters optimized, the total maximum extraction yield of alkaloids and organic acids reached 128.83 mg g−1 applying the optimal DES, which was 1.33–5.33 folds higher than conventional extraction solvents. Additionally, through microstructure analysis using scanning electron microscopy, density functional theory , and frontier molecular orbitals theory, a deeper understanding of the extraction principle was gained, and the molecular mechanism of DES synthesis and the interactions between target compounds were systematically elucidated. The sustainable and green potential of the DES-UA-MSPD method was demonstrated through Green Analytical Procedure Indexanalysis. The overall results of this investigation revealed that the proposed technology was a highly promising and sustainable alternative for effective extraction and quantification of natural products. [Display omitted] • Deep eutectic solvent was used as a sustainable, adjustable and versatile solvent. • A DES-UA-MSPD method was utilized to analyze alkaloids in Coptidis Rhizoma. • Simulation calculations revealed the mechanism of high extraction efficiency using DES. • This strategy proved DES suitability for extracting alkaloids from natural products. [ABSTRACT FROM AUTHOR]

In this study, a novel three-dimensional hierarchical porous deep eutectic solvents-modified graphene aerogel (3D DES-GA) was synthesized for use as a solid-phase microextraction (SPME) fiber coating. The SPME fiber was characterized by its fluffy and hierarchical porous structure, uniform thickness, and rapid mass transfer capabilities. This fiber demonstrated a lifetime (≥160 uses) and excellent precision (with relative standard deviations of 2.4–6.6% for single fiber and 6.0–9.8% for fiber-to-fiber repeatability). The SPME fiber also exhibited remarkable extraction performance for polycyclic aromatic hydrocarbons and polychlorinated biphenyls, which are common persistent organic pollutants in environmental samples. When combined with gas chromatography-tandem mass spectrometry, the method allowed for high-efficiency extraction (enrichment factors ranging from 1225 to 4652 folds) and sensitive determination (limit of detection ranging from 0.010 to 0.056 pg g−1) of polychlorinated naphthalenes (PCNs) in complex samples. To validate this method, we applied it to the determination of four PCNs in five types of fish tissues. The results revealed the presence of 1-chloronaphthalene at concentrations of 7.0 ± 2.9–34.8 ± 2.1 pg g−1 and 1,4-dichloronaphthalene at concentrations of 6.0 ± 0.3–10.9 ± 1.4 pg g−1 in three fish species. Compared with reported sample pretreatment methods reported in the literature, this proposed headspace SPME method offers additional advantages, including simplicity of operation and reduced sample and organic solvent consumption. [Display omitted] • Hierarchical porous graphene aerogel was prepared by deep eutectic solvent modifying. • The functional graphene aerogel was synthesized for a new fiber coating of SPME. • The fiber coating exhibits fast mass transfer and high enrichment capacity. • As-prepared fiber coating exhibited excellent applicability for PCNs, PCBs and PAHs. • The proposed method was applied for sensitive detection of PCNs in complex samples. [ABSTRACT FROM AUTHOR]

Aromatic disinfection by-products (DBPs) have garnered considerable interest in recent years for their potential carcinogenicity. However, efficient separation and enrichment of DBPs in complex samples is a challenge due to the extremely low content of aromatic DBPs and the complexity of sample matrices. In this study, a MIL-101(Cr)–NH 2 @TAPB-DVA-COF hybrid material was prepared as the enrichment medium of membrane solid-phase extraction (M-SPE) to efficiently determine trace emerging aromatic DBPs. This medium exhibited excellent enrichment capacity and selectivity for aromatic DBPs because of the strong hydrogen bonding, π-π stacking and hydrophobic interactions. An efficient analytical method for five aromatic DBPs in juice drinks was successfully established by use of this hybrid material as the enrichment medium for M-SPE in combination with liquid chromatography tandem mass spectrometry (LC-MS/MS). The limits of detection of the established method were from 0.50 to 3.00 ng/L. Moreover, the method had been successfully used in real juice drinks to determine trace five aromatic DBPs with the spiked recoveries ranging from 84.1% to 125%. The method possessed high analytical sensitivity and accuracy for these five aromatic DBPs in juice drinks with the aid of the efficient M-SPE technology proposed. [Display omitted] • A MIL-101(Cr)–NH 2 @TAPB-DVA-COF based membrane solid-phase extraction. • High extraction selectivity and capacity to aromatic disinfection by-products. • Sensitive and accurate quantification of aromatic disinfection by-products in juice. [ABSTRACT FROM AUTHOR]

Heterocyclic aromatic hydrocarbons are concerned pollutants with carcinogenic toxicity, which exist universally in various environmental matrices and have great harm to environmental and human health. In present work, magnetic resorcinol-formaldehyde composites (Fe 3 O 4 @SiO 2 @R–F) were fabricated via aldol condensation reaction under alkaline condition. The prepared magnetic materials were examined and analyzed with Fourier transform infrared spectroscopy and other related instruments. The Fe 3 O 4 @SiO 2 @R–F composites were utilized to develop an efficient magnetic solid phase extraction (MSPE) method for extracting six heteropolyclic aromatic hydrocarbons from environmental water samples including carbazole (CB), 7-methylquinoline (7-MQL), 9-methylcarbazole (9-MCB), dibenzothiophene (DBT), 4-methyldibenzothiophene (4-MDBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT). The analytes were analyzed by high performance liquid chromatography-ultraviolet variable wavelength detector (HPLC-VWD). The main factors affecting MSPE were optimized. With the optimal parameters, 9-MCB and 4-MDBT have good linearity over the concentration range of 0.1–300 μg L−1, and 7-MQL, CB, DBT and 4,6-DMDBT have good linearity over the concentration range of 0.5–300 μg L−1. The limits of detection were over the concentration range of 0.012–0.031 μg L−1. This method was successfully employed to measure real waters, and the spiked recoveries ranged from 89.4% to 99.9%. The results confirmed that the developed method was reliable, robust and could be employed as a usefully alternate way for analyzing such pollutants in waters. [Display omitted] • Fe 3 O 4 @R–F were fabricated with resorcinol and formaldehyde by facile aldol reaction. • Fe 3 O 4 @R–F provided better adsorption ability for heterocyclic aromatic hydrocarbons. • The adsorption abided by pseudo-second order kinetic and Freundlich isotherm models. • A MSPE-HPLC method was established to detect six heterocyclic aromatic hydrocarbons. • The developed method earned good sensitivity with LODs of 0.012–0.031 μg L−1. [ABSTRACT FROM AUTHOR]

The refinement and optimization of a method combining headspace solid-phase microextraction (HS-SPME) with gas chromatography-mass spectrometry (GC-MS) was successfully performed for the first time to determine seven carbonyl and dicarbonyl compounds, including glyoxal, methylglyoxal, dimethylglyoxal, and malondialdehyde in infant formulae, related to lipid peroxidation. HS-SPME was utilized for simultaneous extraction and derivatization with pentafluorophenylhydrazine (PFPH). Critical parameters such as temperature, pH, extractive phase, and salting-out were meticulously investigated and fine-tuned by an asymmetrical 2232//9 screening design to ensure the method's efficacy and reliability. Optimal conditions included a PFPH concentration of 5 g/L, pH 5.0, head-space extraction at 60 °C within 10 min, utilizing a DVB/CAR/PDMS coating, and a 20% w/w salting-out. The analytical validation of this method, compliant with FDA guidelines, demonstrated exceptional linearity, sensitivity, specificity, precision (RSD ≤13.8%), and accuracy (84.8% ≤ recovery ≤111.5%). The metric approach AGREEprep confirms its eco-friendliness, marking a significant step towards an environmentally conscious approach in infant formula analysis. An occurrence study conducted on 25 infant formula samples revealed widespread carbonyl and dicarbonyl compounds in both powdered and liquid variants. ANOVA results exhibited variations in compound concentrations among different sample groups. Clustering analyses delineated distinct groups based on carbonyl content, indicating the potential of these compounds as markers for lipid peroxidation and food quality assessment. This method serves as a valuable tool for evaluating infant formula quality, stability towards oxidation, and safety. [Display omitted] • GC-MS determination of seven carbonyl and α-dicarbonyl compounds in infant formulae. • Simultaneous microextraction and PFPH derivatization within 10 min. • Cost-effective, time-saving, and greener infant formulae analysis. • Clustering analysis categorizes infant formulae by carbonyl content. • Carbonyl and α-dicarbonyl compounds as oxidative stability and food quality markers. [ABSTRACT FROM AUTHOR]

2-ethylhexyl salicylate (EHS) is used as a UV filter in personal-care products, such as sunscreen, to prevent skin damage through UV radiation. The application of EHS-containing products leads to systemic EHS absorption, metabolization and excretion. To measure EHS and its corresponding metabolite levels in urine, a comprehensive analytical procedure based on an extended enzymatic hydrolysis, on-line-SPE, and UPLC-MS/MS was developed. The method covers a large profile of seven metabolites (including isomeric structures) as well as EHS itself in a run time only of 18 min. Easy sample preparation, consisting of a 2-h hydrolysis step, followed by on-line enrichment and purification, add to the efficiency of the method. An update, compared to a previous method for the determination of EHS and metabolites in urine, is that, during hydrolysis, both glucuronide and sulfate conjugates are considered. The method was furthermore applied to urine samples after a real-life exposure scenario to EHS-containing sunscreen. The method is highly sensitive with limits of detection ranging from 6 to 65 ng/L. Moreover, it is characterized by good precision data, accuracy, and robustness to matrix influences. Application of the method to urine samples following dermal exposure to an EHS-containing sunscreen revealed EHS as the main biomarker after dermal exposure, followed by the major biomarkers 5OH-EHS, 5cx-EPS, 4OH-EHS and 5oxo-EHS. The expansion and optimization of this method decisively contributes to the research on the dermal metabolism of EHS and can be applied in exposure studies and for human biomonitoring., 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 The Authors. Published by Elsevier B.V. All rights reserved.)

Pyroxasulfone is a selective, systemic, pre-emergence herbicide which acts to inhibit weeds in potato, coffee, sugar cane, eucalyptus, and soybean plantations, among others. This active ingredient was classified by Brazilian legislation as a very dangerous product for the environment, and to date there are no studies involving the development of extraction methods for monitoring this compound in environmental matrices. Therefore, the objective of this study was to optimize and validate liquid-liquid extraction with low temperature purification followed by a gas chromatography coupled to mass spectrometry analysis to determine this herbicide in honey samples. The results showed that the best extractor phase was acetonitrile and ethyl acetate (6.5 mL:1.5 mL), with recovery rates close to 100% and relative standard deviations below 11%. The validation proved that the extraction method was selective, precise, accurate and linear in the range of 3-225 μg kg -1 , reaching a limit of quantification of 3 μg kg -1 , with a -25.95% matrix effect. Monitoring on real samples did not reveal episodes of environmental contamination with pyroxasulfone residue., 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 Elsevier B.V. All rights reserved.)

Designing modified therapeutic antibodies with enhanced FcRn-binding affinity holds promise in the extension of circulation half-lives and potential refinement of pharmacokinetics. During the development of these new-generation therapeutic antibodies, FcRn binding affinity of IgGs is emphasized and monitored as a critical quality attribute (CQA), alongside other critical assessments including titer and aggregation level. However, the traditional workflow for assessing the overall quality of expressed IgGs in harvested cell culture fluid (HCCF) is blamed to be cumbersome and time-consuming. This study presents an integrated methodology for the rapid quality assessment of IgGs in HCCF by selectively extracting IgGs with favorable high FcRn affinity for subsequent analysis using size exclusion chromatography (SEC). The approach utilizes innovative adsorbents known as FcRn immobilized hydrophilic magnetic graphene (MG@PDA@PAMAM-FcRn) in a magnetic solid-phase extraction (MSPE) process. To simulate the in vivo binding dynamics, MSPE binding and dissociation was performed at pH 6.0 and 7.4, respectively. The composite have demonstrated enhanced extraction efficiency and impurity removal ability in comparison to commercially available magnetic beads. The SEC monomer peak area value provides the output of this method, the ranking of which enabled the facile identification of superior HCCF samples with high overall quality of IgG. Optimization of MSPE parameters was performed, and the method was validated for specificity, precision, sensitivity, and accuracy. The proposed method exhibited an analytical time of 0.6 h, which is 7–22 times shortened in comparison to the conventional workflow. [Display omitted] • FcRn immobilized magnetic graphene with polydopamine and hydrophilic dendrimer coating was designed and synthesized for the first time. • IgG with different FcRn-affinity levels were differentially extracted from harvested cell culture fluid using FcRn immobilized material as magnetic adsorbents. • By leveraging the advantage of stepwise operation in MSPE technology, binding and dissociation at particular pH values were achieved, thus to accurately simulate the intricate pH-dependent binding dynamics in vivo between IgG and FcRn. • Purification procedure and FcRn-affinity evaluation were combined, thus only desired IgG species with high FcRn-affinity were selectively purified for further quality analysis. • The superior clones with desired overall quality of IgG could be quickly identified through simply ranking of the SEC monomer peak value (method read-out). [ABSTRACT FROM AUTHOR]

In this work, a sensitive fluorescent sensor toward p-nitrophenol (4-NP) integrating magnetic molecularly imprinted materials and carbon dots (CDs) was proposed. Magnetic material and CDs derived from K 3 [Fe(CN) 6 ] and glucose were simultaneously obtained through simple one-step hydrothermal process. Introducing of molecularly imprinted materials based magnetic solid phase extraction (MSPE) endowed the constructed fluorescent sensor with higher sensitivity and selectivity. The significant factors affecting the sensitivity of the sensor toward 4-NP were optimized. Good linearity was obtained between fluorescent intensity of CDs and different concentration of 4-NP from 0.08 to 62.5 μg L−1. The sensitivity of constructed sensor was very low with detection limit of 0.02 μg L−1. Reliable applicability was also proved by the well-pleasing recoveries of 94.2–97.8% with different spiked concentrations of 4-NP in real environmental waters. [Display omitted] • MMIPs based MSPE was integrated with CDs for constructing FL sensor toward 4-NP. • CDs and magnetic core were simultaneously prepared via one step hydrothermal process. • The constructed sensor exhibited good sensitivity and reliability for detecting 4-NP. [ABSTRACT FROM AUTHOR]

Imidazoline-linked cationic covalent triazine framework (IM-iCTF) was facilely prepared through the Debus-Radziszewski reaction, involving 4,4′,4''-(1,3,5-triazine-2,4,6-triyl)trianiline, formaldehyde and methylglyoxal. The IM-iCTF was applied as a sorbent for cartridge solid-phase extraction (SPE). It provided good adsorption performance for estrogen and estrogen mimics including bisphenol F, bisphenol A, 7β-estradiol, bisphenol B and estrone. The adsorption isotherm, adsorption kinetic model, thermodynamic calculations and adsorption mechanism were investigated to reveal the adsorption behavior. The IM-iCTF was employed for the extraction of the estrogens and estrogen mimics from water, fish and shrimp (fish and shrimp samples were extracted with acetonitrile before the SPE). The analytes were then determined by high-performance liquid chromatography with diode array detection. The limits of detection were 0.008–0.05 ng mL−1 for water, 0.015–0.11 μg g−1 for fish, and 0.012–0.10 μg g−1 for shrimp samples. This research not only offers a new approach to construct cationic covalent triazine framework, but also provides a reliable strategy for the adsorption/enrichment trace level of organic pollutants. [Display omitted] • Imidazoline-linked cationic covalent triazine framework (IM-iCTF) was prepared. • IM-iCTF displayed exceptional sorption performance for environmental estrogens (EEs). • Sorption mechanism was proved to be the synergistic effect of multiple interactions. • A IM-iCTF-based SPE-HPLC method was developed to assay EEs in water, fish and shrimp. [ABSTRACT FROM AUTHOR]

Unmodified hairy basil seed mucilage (Ocimum basilicum L.), with attractive features as structural functionality and adsorption capacity, was employed as a green biosorbent for dispersive solid phase extraction and enrichment of oxytetracycline, tetracycline, and doxycycline before quantitation by HPLC-UV for the first time. Hairy basil crushed seed increased the contacting surface area and was completely dispersed in the sample solution to extract tetracyclines under acidic condition with the assistance of ultrasonic waves. The analytes in the extraction phase were separated on a C 18 column under isocratic condition with a mobile phase consisted of acetonitrile and trifluoroacetic acid. Influence of chemical and physical variables on the extraction efficiency of the developed method was investigated and optimized systematically. Under the optimal condition of all experimental parameters, good linear ranges were obtained at 15.0–500 μg L−1 for tetracyclines with determination coefficients more than 0.9994. Limits of detection (LODs) and limits of quantitation (LOQs) ranged 5.0–7.0 and 15.0 μg L−1, respectively. Relative standard deviations (RSDs) of the proposed method at 100 and 300 μg L−1 for TCs were less than 13 % and 10 %, respectively with percentage TC recoveries from spiked standard ranging 83.1–109.9 %. This simple, reliable, cost-effective, and environmentally friendly method was successfully applied for the analysis of tetracycline residues in milk. The greenness of the proposed method was assessed using the Analytical Eco-Scale and AGREE protocol. [Display omitted] • Unmodified HBSM was used as a green biosorbent for DSPE for the first time. • Alternative DSPE based on biosorbent was utilized to enrich TC residues in milk. • UAE was synergized with DSPE to enhance extraction efficiency. • After preconcentration using the developed method TCs were quantified by HPLC-UV. • This method is simple, reliable, cost-effective, and environmentally friendly. [ABSTRACT FROM AUTHOR]

This study presents a novel, eco-friendly composite adsorbent material designed for the magnetic solid-phase extraction of diamide insecticides from vegetable samples. The membrane, denoted as Fe-MMm, was incorporated with a cellulose framework embedded with Metal-Organic Frameworks (MOFs) and Multi-Walled Carbon Nanotubes (MWCNTs) magnetized with Fe 3 O 4. This innovative material streamlined the conventional solid-phase extraction process, simplifying the sample pre-treatment. By combining it with liquid chromatography tandem mass spectrometry (LC-MS/MS), the method achieves significantly enhanced extraction efficiency through systematic optimization of experimental parameters, including adsorbent selection, pH, ionic strength, adsorption time, and elution time. The method had a wide linear range of 0.1–1000 ng/mL and an exceptionally low detection limit ranging from 0.023 to 0.035 ng/mL. The successful identification of diamide insecticides in vegetable samples underscores the potential of Fe-MMm as a robust material for sample pretreatment in analytical applications. [Display omitted] • The MOF and MWCNTs@Fe 3 O 4 are embedded in the skeleton of MFC. • A solid-phase extraction method based on Fe-MMms was proposed and detected using LC-MS/MS. • Fe-MMm demonstrates excellent reusability in solid-phase extraction, with minimal performance changes after 10 uses. • The method exhibits extremely high sensitivity and a wide linear range, with an exceptionally low detection limit ranging from 0.023 to 0.035 ng/mL. [ABSTRACT FROM AUTHOR]

Efficiently detecting diamide insecticides in environmental water is challenging due to their low concentrations and complex matrix interferences. In this study, we developed ionic liquids (ILs)-incorporated magnetic molecularly imprinted polymers (IL-MMIPs) for the detection of diamide insecticides, capitalizing on the advantages of ILs and quick magnetic separation through surface imprinting. Tetrachlorantraniliprole was used as the template, and a specific IL, 1-vinyl-3-ethylimidazolium hexafluorophosphate ([VEIm][PF 6 ]), was employed as the functional monomer. Various synthesis conditions were investigated to optimize adsorption efficiency. The prepared IL-MMIPs were successfully employed as adsorbents in magnetic solid-phase extraction (MSPE) to selectively extract, separate, and quantify three types of diamide insecticides from water samples using HPLC-UV detection. Under optimal conditions, the analytical method achieved low limits of detection (0.69 ng mL−1, 0.64 ng mL−1, 0.59 ng mL−1 for cyantraniliprole, chlorantraniliprole and tetrachlorantraniliprole, respectively). The method also displayed a wide linear range (0.003–10 μg mL−1 for cyantraniliprole and chlorantraniliprole, and 0.004–10 μg mL−1 for tetrachlorantraniliprole, respectively) with satisfactory coefficients (R 2 ≥0.9996), and low relative standard deviation (RSD ≤2.55%). Additionally, extraction recoveries fell within the range of 79.4%–109%. The results clearly demonstrate that IL-MMIPs exhibit exceptional recognition and rebinding capabilities. The developed IL-MMIPs-MSPE-HPLC-UV method is straightforward and rapid, making it suitable for the detection and analysis of three kinds of diamide insecticides in environmental water. [Display omitted] • Ionic liquids-incorporated magnetic molecularly imprinted polymers (IL-MMIPs) were fabricated combining the advantages of ILs and quick magnetic separation via surface imprinting. • IL-MMIPs possessed excellent adsorbability, high selectivity and fast kinetics. • IL-MMIPs were employed for enrichment of diamide insecticides in environmental water samples. [ABSTRACT FROM AUTHOR]

We developed an analytical method based on ultra-high performance liquid chromatography with UV detection, using a stir bar coated with amino/hydroxyl bifunctional microporous organic network (B-MON), for the analysis of parabens in breast milk samples. B-MON demonstrated superior performance with maximal methylparaben adsorption of 112.15 mg/g. Kinetic fitting revealed that outer diffusion was the key limiting step, and the adsorption was chemisorption. The thermodynamic analysis demonstrated that increased methylparaben adsorption was found at higher temperatures in spontaneous processes. The developed approach showed excellent linearity (R2 ≥ 0.9964) and a low detection limit (0.01 μg/L). Recoveries ranged from 85.8 to 105.5 % and the relative standard deviation was lower than 9.2 %. Based on the daily exposure assessment, these pollutants do not pose unacceptable health hazards to babies. However, the high detection frequencies (41.9%–93.5 %) suggest that breast milk still should be monitored. [Display omitted] • Stir bar sorptive extraction combined with UHPLC-UV method was established. • Adsorbent has excellent performance for the adsorption of parabens. • Trace levels of parabens in human breast milk were determined. • Parabens in human breast milk samples may pose no adverse health risks to infants. [ABSTRACT FROM AUTHOR]

Large–size spherical sorbents with particle size of 10–50 μm are widely applied in separation fields, however it is still a great challenge to synthesize such large–size spherical covalent organic framework (COF). In this work, a type of large–size porous 3D COF was size–controablly synthesized via a two–step strategy, in which a large–size porous 3D spherical polymer was prepared first through a Pickering emulsion polymerization using nano silica as the stabilizer, and subsequently it was converted into porous spherical 3D COF by a solvothermal method. The as–prepared porous spherical COF (COF–320 as a model) showed size–controllable uniform spherical morphology within 15–45 μm, large specific surface area, fine crystalline structure, and good chemical stability. When used as the sorbent for dispersive solid–phase extraction (d–SPE) of bisphenol F (BPF), the porous spherical COF–320 (15 μm) displayed high adsorption capacity (Q max = 335.6 mg/g), high enrichment factor (80 folds), and good reusability (at least five cycles). By coupling the d–SPE method to HPLC, a new analytical approach was developed and successfully applied to the determination of trace BPF in two water samples, an orange juice and a standard sample with recoveries of 96.0–102.2 % (RSD = 1.1–1.5 %), 95.7–97.4 % (RSD = 1.4–4.4 %) and 98.7 % (RSD = 2.3 %), respectively. The limit of detection (S/N = 3) and limit of quantification (S/N = 10) were 0.1 and 0.3 ng/mL, respectively. The new synthesis strategy opens a viable way to prepare large–size porous spherical COFs, and the developed analytical method can be potentially applied to sensitively detect the trace BPF in water samples and beverages. [Display omitted] • Large-size porous spherical 3D COFs were size-controllably prepared within 15–45 μm. • A Pickering emulsion polymerization and a solvothermal method used for synthesis. • Such spherical COF was used for d-SPE of BPF in water samples and orange juice. • This COF showed high binding ability, high enrichment factor and good reusability. • The d-SPE-HPLC-UV method displayed high sensitivity for detection of trace BPF. [ABSTRACT FROM AUTHOR]

This work presents a multisyringe flow injection analysis (MSFIA) system for the automatic extraction and determination of tetracyclines in wastewater samples. The sample was adjusted with Na 2 EDTA buffer before solid-phase extraction with an Oasis HLB column used for the analyte preconcentration. The europium (Eu3+)-based and citrate-mediated method (using Tris-HCl buffer) was selected for the fluorimetric analysis (λ exc/em = 400/612 nm). For fluorescence detection, a low-cost system consisting of an USB 2000 CCD detector and a 3D-printed support that holds a LED light source was used. Under optimized conditions, the proposed method provided low limits of detection (9.4 μg L−1) and quantification (31 μg L−1), and good values for intra-day (<4 %) and inter-day precisions (<6 %). Recoveries of spiked TCs in wastewater samples ranged from 87 to 106 %. The results of this work were in good agreement with the measurements obtained by liquid chromatography coupled to a fluorescence detector. [Display omitted] • MSFIA automates tetracycline extraction using novel Eu3+ method. • Achieves sensitivity with 9.4 μg L−1 detection limit. • Shows 87–106 % recovery, <4 % intra-day, <6 % inter-day variation. • Cost-effective, less intervention, ideal for routine analysis [ABSTRACT FROM AUTHOR]

N-glycans of therapeutic glycoproteins is a critical quality attribute to be addressed. We developed a sensitive method for N-glycan characterization using procainamide (ProcA) labelling and online solid phase extraction (online SPE). N-glycans were enzymatically released, then labeled with ProcA and cleaned up via the online SPE using HILIC chemistry (online HILIC SPE). Two preparation protocols were optimized: a short one (1 h 30) and a long one (18 h). Furthermore, the developed approach was compared to RapiFluor-MS (RFMS) kit (from Waters) and to InstantPC kit (from Agilent) which both include a classical HILIC μElution plate SPE purification. Samples were analyzed using HILIC separation coupled to fluorescence and MS detection (HILIC-FLD-MS) with or without the online HILIC SPE. During the validation, repeatability, intermediate precision, stability, response function and injection volume were tested. Human IgG mix (Multigam®) and NIST mAb standard were used as references as their glycoprofiles are well described. A comparison of three batches of a rituximab biosimilar (Truxima®) and one batch of its originator (MabThera®) was also performed. Online HILIC SPE sample cleanup shows a higher sensitivity and repeatability compared to the classical HILIC μElution SPE. Our online HILIC SPE approach also offers the highest MS signal compared to both commercial kits. However, InstantPC shows the highest FLD signal. The analyses of rituximab samples were in line with the literature showing the efficiency of the method for N-glycan monitoring of biotherapeutics. In conclusion, the results demonstrated the usefulness and ease of application of the developed protocol with the online HILIC SPE purification. [Display omitted] • Sensitive, repeatable and cost-effective online SPE cleanup for N-glycans analysis. • Procainamide labelling of N-glycans. • Online SPE coupled to "classical" HILIC separation with FLD and MS detections. • Approach was validated and tested on the NIST standard and biotherapeutics. • The approach is more sensitive than two commercial kits for MS detection. [ABSTRACT FROM AUTHOR]

The dominant species of vanadium (V) are V(IV) and V(V) which exhibit different toxicity and biological effects. Thus, speciation of V(IV) and V(V) is highly essential. Efficient sample preparation is the core step in the quantification of V(IV) and V(V). In the present study, a new task specific microextraction column based on monolith mingled with Fe 3 O 4 nanoparticles (MBMC) was in situ synthesized in capillary and utilized as the extraction phase of magnetic field-assisted in-tube solid phase microextraction (MA-IT-SPME) of V(IV) and V(V) species which were coordinated with ethylene diamine tetraacetic acid (EDTA). The prepared MBMC presented porous and superparamagnetic properties, and possessed abundant functional groups. Results revealed that the exertion of magnetic field during adsorption and eluting steps boosted the extraction efficiency of V(IV)-EDTA and V(V)-EDTA chelates from 65.1 % to 55.7 %–90.0 % and 80.1 %, respectively. Under the beneficial extraction parameters, the established MA-IT-SPME was online hyphenated with HPLC/DAD to perform speciation of trace vanadium in water and vegetable samples, the achieved limits of detection were 0.054–0.060 μg/L and 1.4–1.5 μg/kg in water and vegetable samples, respectively, and the spiked recoveries varied from 82.5 to 118 %. In addition, relevant extraction mechanism under magnetic field was explored. In comparison with existing methods, the developed MA-IT-SPME technique displays some attractive merits such as automation, good anti-interference ability, high extraction efficiency, low cost and less use of organic solvent, in the capture of V species. The established online MBMC@MA-IT-SPME-HPLC/DAD system can become a competitive approach for sensitive speciation of V(IV) and V(V) at trace levels in complex samples. [Display omitted] • A novel microextraction column for MA-IT-SPME was synthesized. • Application of magnetic field during extraction procedure improved the extraction efficiency. • Extraction conditions were optimized and extraction mechanism was deduced. • Online MBMC@MA-IT-SPME-HPLC/DAD was established for simultaneous analysis of V(IV) and V(V). [ABSTRACT FROM AUTHOR]

Biodegradable molecularly imprinted polymer-coated paper (MIP@paper) was effectively produced by polymerization using azinphos-methyl as a template molecule, terephthalic acid as a functional monomer, ethylene glycol dimethacrylate as a cross-linker, and aqueous ethanol as a green porogenic solvent. The material was subsequently composited onto cellulose paper, which served as the natural substrate, by dip coating with the aid of chitosan and citric acid natural adhesive. The properties, such as static and dynamic adsorption, selectivity, and reusability, were assessed. At rapid adsorption equilibrium (10 min), the MIP@paper had a high adsorption capacity in the range of 2.5–3.7 mg g−1 and good recognition with imprinting factors up to 2.1. In addition, the proposed MIP@paper was utilized efficiently as a sorbent for dispersive solid phase extraction (d -SPE) of eight organophosphorus pesticides (OPPs) prior to high-performance liquid chromatography (HPLC) analysis. The d -SPE-HPLC method displayed low detection limits of 1.2–4.5 μg kg−1 and significant enrichment factors (up to 320-fold). The proposed method was effectively applied for the determination of OPP residues in agricultural products, including fruits, vegetables, and cereal grains, with satisfactory spiked recoveries (80.1–119.1 %). Thus, the MIP@paper material provided a selective and environmentally favorable method for extracting and determining organophosphorus pesticides. [Display omitted] • A novel molecularly imprinted polymer-coated paper was proposed. • The material was synthesized in an aqueous ethanol medium under mild conditions. • A simple and rapid dispersive solid-phase extraction procedure was developed. • The method was successfully applied for quantification organophosphorus. [ABSTRACT FROM AUTHOR]

Antioxidants and UV stabilizers have some endocrine disrupting effects and liver toxicity. Both types of additives are still widely used in food contact plastics to improve the durability of plastic products. However, efficient and rapid detection of antioxidants and UV stabilizers has been a challenge due to the complexity of the plastic matrix and the low content of antioxidants and UV stabilizers. In this study, a sodium alginate/MOF-derived magnetic multistage pore carbon material (MIL-101(Fe)/SA-CAs) was developed, having the merits of abundant multistage pore structure, large specific surface area, and good magnetic separation properties. Thus, this material was selected as the sorbent for magnetic solid-phase extraction combined with a dissolution-precipitation method for the extraction and purification of antioxidants and UV stabilizers from polylactic acid food contact plastics. The extraction parameters such as sorbent type, sorbent dosage, sample solution pH, ionic strength, sorption time, elution solution type, volume, and time were investigated. Under the optimized conditions, all the analytes determined by UPLC-MS/MS showed good linear range (r > 0.99), detection limit (0.023–3.105 ng g−1), accuracy (70.6–102.3 %), and reproducibility (RSD<9.8 %). Further, the developed method was applied to determine the antioxidants and UV stabilizers in polylactic acid lunch boxes and straws, showing excellent applicability. The results showed that the antioxidants and UV stabilizers were detected in some of the samples, with a maximum detection of antioxidant 1010 at 7297 ng g−1. This study provided a sensitive, efficient, and environmentally friendly method for antioxidants and UV stabilizers in polylactic acid food contact plastics. The ideas for the design of environmentally friendly metal-organic frameworks and biomass composite multifunctional materials would promise in the sample pretreatment field for the emerging contaminants. [Display omitted] • MIL-101(Fe)/SA-CAs adsorbent was simple in preparation. • Multi-stage pore structure of the composite accomplished rapid target adsorption. • The established method allowed precise extraction from complex plastic matrices. • The adsorption of the target was a multimolecular layer with multiple interactions. [ABSTRACT FROM AUTHOR]

The current HPLC methods for the quantification of vitamin D 3 (VitD 3) and its two isomers previtamin D 3 (PreVitD 3) and trans -vitamin D 3 (trans -VitD 3) in olive oil preparations present some limitations mainly due to peak overlapping of the oily matrix components with the compounds of interest. The use of two-dimensional liquid chromatography (2D-LC) with different retention mechanism can reach higher resolving power thus allowing the analysis of complex samples. The present paper proposes a new alternative method including a solid phase extraction sample preparation step and a two-dimensional liquid chromatographic analysis using routine instrumentation, fitting the needs of quality assurance and quality control laboratories of pharmaceutical companies. The extraction protocol was demonstrated to provide a clean-up of the sample and a quantitative recovery of the species of interest. The 2D method proved its suitability in the isolation of vitamins from oil components in the first dimension and the separation and quantification of the analytes in the second dimension thanks to the orthogonal selectivities of phenyl and porous graphitic carbon (PGC) stationary phases. The method was validated following ICH guidelines and possesses an adequate sensitivity to quantify the impurity trans -VitD 3 in pharmaceuticals considering the limits imposed by regulatory agencies. The applicability of the phenyl x PGC 2D-LC-UV method to quality control of medicinal products based on VitD 3 in olive oil was confirmed by the successful quantification of vitamins in olive oil formulations. [Display omitted] • A phenyl x PGC 2D-LC-UV method was developed to separate vitamin D 3 and its isomers. • Solid phase extraction allowed to quantitatively isolate vitamins from the olive oil matrix. • Phenyl and porous graphitic carbon columns were coupled on-line for the first time. • The two-dimensional chromatographic method was validated following ICH guidelines. • The method is suitable for quality control of vitamin D 3 in olive oil formulations. [ABSTRACT FROM AUTHOR]

Pipette tip solid-phase extraction (PT-SPE) as a miniaturized solid-phase extraction technique have a wide range of applications in the field of sample pretreatment. In this study, ionic covalent organic frameworks@cotton (iCOF@cotton) were facilely synthesized by mechanochemical grinding method only in half an hour, and used as the adsorbents of PT-SPE. The synthesized iCOF@cotton not only had high specific surface area, suitable pore structure and cationic charge groups of iCOF that can extract polar targets quickly, but also reduced the problem of high back pressure of PT-SPE by the addition of cotton, thus accelerating extraction time. Combined with high performance liquid chromatographic tandem mass spectrometry (HPLC-MS/MS), an efficient and sensitive method was established for detection of domoic acid (DA, a toxin produced by algae). Under the optimal conditions, the proposed analysis method displayed excellent analytical performance, including broad range of linearity (10–1000 pg mL−1), low limit of detection (LOD, 5 pg mL−1), high correlation coefficient (0.9993), satisfactory precision (RSDs ≤6.4 %). In addition, the developed method was applied to the detection of DA in marine samples, and detected trace DA (18.6 pg mL−1) with satisfactory recovery (85.7%–107.2 %). The above results indicated that the prepared iCOF@cotton have great potential as the adsorbents for PT-SPE. [Display omitted] • Ionic covalent organic frameworks@cotton were fast and conveniently synthesized by mechanochemistry methods. • Ionic covalent organic frameworks have abundant cationic charge groups and high adsorption capacity for domoic acid. • The cotton effectively reduced high back pressure in the pipette tip solid-phase extraction. • The method was successfully applied to the enrichment of domoic acid in marine samples. [ABSTRACT FROM AUTHOR]

Hormonal drugs in biological samples are usually in low concentration and highly intrusive. It is of great significance to enhance the sensitivity and specificity of the detection process of hormone drugs in biological samples by utilizing appropriate sample pretreatment methods for the detection of hormone drugs. In this study, a sample pretreatment method was developed to effectively enrich estrogens in serum samples by combining molecularly imprinted solid-phase extraction, which has high specificity, and non-ionic hydrophobic deep eutectic solvent-dispersive liquid-liquid microextraction, which has a high enrichment ability. The theoretical basis for the effective enrichment of estrogens by non-ionic hydrophobic deep eutectic solvent was also computed by simulation. The results showed that the combination of molecularly imprinted solid-phase extraction and deep eutectic solvent-dispersive liquid-liquid microextraction could improve the sensitivity of HPLC by 33∼125 folds, and at the same time effectively reduce the interference. In addition, the non-ionic hydrophobic deep eutectic solvent has a relatively low solvation energy for estrogen and possesses a surface charge similar to that of estrogen, and thus can effectively enrich estrogen. The study provides ideas and methods for the extraction and determination of low-concentration drugs in biological samples and also provides a theoretical basis for the application of non-ionic hydrophobic deep eutectic solvent extraction. [Display omitted] • An analytical method combined dtMIPs-SPE and NIHDES-DLLME was established. • The mechanism by which deep eutectic solvents can effectively extract estrogens was explained. • Highly sensitive and highly specific enrichment separations in complex samples were realized. [ABSTRACT FROM AUTHOR]

The extraction efficiencies of thirty types of fibers produced by meltblown, alternating current electrospinning, and meltblown-co-electrospinning technologies were tested as advanced sorbents for on-line solid-phase extraction in a high-performance liquid chromatography system have been tested and compared with a commercial C18 sorbent. The properties of each fiber, which were often depended on the production process, and their applicability were demonstrated with the extraction of the model analytes nitrophenols and chlorophenols from various matrices including river water and to purify complex matrix human serum and bovine serum albumin from macromolecular ballast. Polycaprolactone fibers outperformed other polymers and were selected for subsequent modifications including (i) incorporation of hybrid carbon nanoparticles, i.e., graphene, activated carbon, and carbon black into the polymer prior to fiber fabrication, and (ii) surface modification by dip coating with polyhydroxy modifiers including graphene oxide, tannin, dopamine, hesperidin, and heparin. These novel fibrous sorbents were comparable to commercial C18 sorbent and provided excellent analyte recoveries of 70–112% even from the protein-containing matrices. [Display omitted] • Thirty polymer nano/microfibers were compared as sorbents for on-line SPE-HPLC. • Polycaprolactone fibers were comparable in extraction efficiency with common C18. • Novel hybrid nanofibers doped with activated carbon and carbon black were presented. • Surface-modified PCL fibers were prepared via dip coating with polyphenols. • Advanced coated nanofibers achieved excellent recoveries from protein matrix. [ABSTRACT FROM AUTHOR]

Herein, we designed and constructed a highly selective MIPs for bisphenol A (BPA) named Cu-MIPs@CS based on Cu(II) coordination. The synthesis of Cu-MIPs@CS employed a dummy template strategy and surface imprinting technology, with chitosan (CS) as the substrate linked to imprinted layers via Cu2+ bridging. 4-vinylpyridine acted as the functional monomer, capable of forming a complex with the template ketoprofen, while ethylene glycol dimethacrylate served as the cross linker. Cu-MIPs@CS exhibited a significantly enhanced imprinting factor of 14.78 for BPA, which was approximately 6.6 times higher than that of imprinted materials without Cu2+ (MIPs@CS). Cu-MIPs@CS exhibited a selective factor of 12.74 towards resorcinol, which possessed identical functional groups but a smaller size than BPA, representing an enhancement of selectivity by 12.25-fold compared to MIPs@CS. More importantly, Cu-MIPs@CS exhibited a superior discrimination ability between BPA and its structural analogue, diphenolic acid, with an excellent selective factor of 2.93, highlighting its significance in distinguish the structural analogue of BPA. In contrast, MIPs@CS lack sufficient selectivity to differentiate between them. Through exploration of adsorption mechanism of Cu-MIPs@CS, it was demonstrated that the incorporation of Cu2+ significantly reduced nonspecific adsorption, but also facilitated the creation of more selective imprinted cavities by introducing metal coordination, thereby notably enhancing the selectivity of Cu-MIPs@CS. Finally, the developed Cu-MIPs@CS were applied as the solid phase extraction adsorbent and combined with HPLC-DAD detection to establish an analytical method towards BPA in drinking water samples. The limit of detection of the method was 0.14 μg L−1 and recoveries ranged from 95.6 % to 101 %. This work provided broad prospects for construction of highly selective MIPs and accurate quantification of trace amounts of BPA. [Display omitted] • Highly selective molecularly imprinted polymers (Cu-MIPs@CS) were prepared. • Chitosan was employed as the substrate due to its biocompatibility and low cost. • The introduction of Cu2+ significantly reduced non-specific adsorption. • The incorporation of Cu2+ created more selective imprinted cavities. • Cu-MIPs@CS was applied for the precise analysis of BPA in drinking water samples. [ABSTRACT FROM AUTHOR]

Maleic hydrazide (MH) is a plant growth regulator, herbicide, and sprout inhibitor used to improve the growth and quality of certain vegetables and fruits, unfortunately, MH has genotoxic and carcinogenic effects; thus, MH residues in food need to be analyzed. Herein, magnetic molecularly imprinted polymers (MagMIP) were synthesized by radical polymerization in just 30 min using a microwave for rapid and selective extraction of MH. The colorimetric detection of MH using the immobilized Folin Ciocalteau's reagent (FCR) on 96-well microplate via smartphone sensor exhibits useful sensitivity for MH with a limit of detection (LOD = 0.6 ppm) which is far lower than the maximum residue limits (higher than 5 ppm). The immobilized FCR was stored dry at two different storage conditions at +4 °C and room temperature without losing its performance over six months. The coupling MagMIP-extraction/clean-up and smartphone determination were tested towards food samples (i.e., potatoes, and carrots), obtaining good recovery (79-96 %), high repeatability (RSD 4.5 %; n = 10), and high selectivity for MH determination., 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 B.V. All rights reserved.)

The harmful effects of endocrine disrupting chemicals (EDCs) to humans and other organisms in the environment have been well established over the years, and more studies are ongoing to classify other chemicals that have the potential to alter or disrupt the regular function of the endocrine system. In addition to toxicological studies, analytical detection systems are progressively being improved to facilitate accurate determination of EDCs in biological, environmental and food samples. Recent microextraction methods have focused on the use of green chemicals that are safe for analytical applications, and present very low or no toxicity upon disposal. Deep eutectic solvents (DESs) have emerged as one of the viable alternatives to the conventional hazardous solvents, and their unique properties make them very useful in different applications. Notably, the use of renewable sources to prepare DESs leads to highly biodegradable products that mitigate negative ecological impacts. This review presents an overview of both organic and inorganic EDCs and their ramifications on human health. It also presents the fundamental principles of liquid phase and solid phase microextraction methods, and gives a comprehensive account of the use of DESs for the determination of EDCs in various samples. [Display omitted] • Endocrine disruptor compounds classified under major chemical groups. • Brief overview of liquid phase microextraction methods. • Composition, categories, characterization, and mechanism of deep eutectic solvents as extractants. • Application of DESs for the determination of organic and inorganic endocrine disruptors. [ABSTRACT FROM AUTHOR]

Coffee is one of the most widely consumed beverages. It can be prepared from green or roasted beans or from instant coffee. Unfortunately, in addition to the aroma obtained in the coffee roasting process, among others, formaldehyde can be produced. In this study, thin-film solid-phase microextraction was used to preconcentrate trace amounts of formaldehyde in different types of coffee with different roasting levels. For this purpose, 18 hybrid materials based on deep eutectic solvents were synthesized and tested as sorbents in thin-film solid-phase microextraction. The coffee samples were brewed, and then formaldehyde present in them was derivatized using the Nash reagent. The sample preparation procedure was optimized for selected DES-based sorbent using a central composite design method and validated. Formaldehyde was determined in almost all samples of second-crack coffee (roasted at 240 °C) at 0.17–0.75 ng mL−1 and in darker-colored instant coffees at 0.18–0.54 ng mL−1. [Display omitted] • Preconcentration of formaldehyde by TF-SPME technique. • Determination of formaldehyde in ground and instant coffee samples. • Novel DES/PDMS hybrid material as sorbent on support mesh was studied. • For optimalization of TF-SPME, the central composite design was used. [ABSTRACT FROM AUTHOR]