JOURNAL OF CHROMATOGRAPHY A

Surface engineering of cell membrane biomimetic nanocomposites for enhanced drug lead discovery and evaluation
Jiang X, Zhang C, Qin Y, Wang H, Liu Y, Xiong Z and Zhao L
Cell membrane-coated nanoparticles (CMNPs) have garnered significant attention in drug lead discovery due to their superior biochemical properties and distinctive ability to target biological interfaces. However, designing nanocarriers that can expand the applicability of these emerging nanomaterials while preserving the biological functionality of the cell membrane remains a significant challenge. Herein, nucleus pulposus (NP) cell membrane biomimetic FITC-loaded poly-amidoamine (PAMAM) modified NiFeO-GO (NFGPFPs-NP) nanocomposites were prepared by purposeful surface engineering to facilitate the efficient screening of drug leads from Yaobitong capsule (YBTC) that target membrane receptors. By employing NFGPFPs magnetic fluorescent nanoparticles as cell membrane carrier materials, the synthesized NFGPFPs-NP were endowed with capabilities for magnetic separation and fluorescence in-situ imaging, thereby realizing the rapid screening of active compounds and the visual evaluation of their pharmacological activities. Meanwhile, the validation including adsorption capacity, selectivity and stability of this biomimetic screening platform had been evaluated, and demonstrated satisfactory results. Notably, the platform exhibited a high adsorption capacity, reaching up to 12.88 mg·g for the target bioactive compounds. Eventually, eight potentially bioactive compounds were screened out from YBTC, and their proliferative activity on NP cells were subsequently validated by pharmacological experiments and cell morphology fluorescence imaging assays. In conclusion, this purposeful surface engineering endowed CMNPs with significantly enhanced versatility, thereby expanding the application scope of cell membrane biomimetic platform.
Disaccharide/UiO-66(Zr) composites for selective dye adsorption: synergistic mechanisms
Chen J, Cao W, Xu S, Liu L, Tang H, Hu N and Zhang W
The global water crisis demands the use of efficient adsorbents to remove carcinogenic synthetic dyes from industrial wastewater. This study developed composites of disaccharides (lactose, maltose, sucrose) with UiO-66(Zr) and systematically evaluated their adsorption performance towards both cationic (methylene blue, MB; malachite green, MG; rhodamine B, RhB) and anionic (methyl orange, MO; and Congo red, CR) dyes. Comprehensive characterization, including PXRD, FT-IR, BET, TGA, XPS and zeta potential, confirmed the successful formation of the disaccharide/UiO-66(Zr) composites. Compared to the removal of cationic dyes, the disaccharide/UiO-66 composites showed superior performance in adsorbing anionic dyes. Sucrose/UiO-66 showed particularly outstanding results, exhibiting adsorption capacities of 54, 56, 37, 154 and 287 mg/g for MB, MG, RhB, MO and CR, respectively. This is likely because lactose and maltose are reducing disaccharides, while sucrose is non-reducing. The reducing property governs the adsorption capacity for anionic dyes. Furthermore, based on adsorption kinetics data, the dye adsorption process of these materials follows the pseudo-second-order kinetic model, with adsorption mechanisms involving electrostatic interactions, π-π stacking, size-selective, and dual-mode regenerability. Thus, disaccharide/UiO-66(Zr) exhibits immense application potential in environmental pollutant removal and also provides a valuable reference for the preparation and application of other MOF composites.
Computational study and synthesis of multi-template molecularly imprinted polymer for isolating ethyl p-methoxycinnamate and ethyl cinnamate using bulk methods
Susanti I, Hasanah AN, Pratiwi R and Rosandi Y
In recent years, research into molecularly imprinted polymers (MIPs) has expanded significantly, particularly for separation or isolation of analytes from extracts. MIPs designed for the simultaneous isolation of ethyl p-methoxycinnamate (EPMC) and ethyl cinnamate (EC) from Kaempferia galanga L. extract or multi-template molecularly imprinted polymer (MT-MIP) have been developed. However, the percentage recovery and purity have remained low. In this study, molecular modelling of MT-MIP for EPMC and EC was conducted using the semi-empirical Parametric Method 3 (PM3) to select functional monomers and determine the ratio of template molecule (TM) to functional monomer (FM). Geometry optimisation revealed that the HEMA formed a stable complex with the template molecule (ΔE of -92.33 kcal/mol). MT-MIPs were synthesised using HEMA at TM:FM molar ratios of 1:4 (MT-MIP-1) and 1:13 (MT-MIP-2), with an EPMC to EC ratio of 3:2, via bulk polymerisation. These polymers were employed as solid-phase extraction (SPE) adsorbents to isolate EPMC and EC from Kaempferia galanga L. extract. MT-MIP-2 exhibited a higher imprinting factor (IF) for both EPMC and EC compared to MT-MIP-1. The percentage recovery of EPMC using MT-MIP-2 for n-hexane, ethanol, and ethyl acetate extract were 65.89 %, 71.31 %, and 71.97 %. In addition, the percentage recovery of EC for n-hexane, ethanol, and ethyl acetate extract were 52.27 %, 60.79 %, and 63.36 % for the ethyl acetate extract. The purity of both EPMC and EC isolated using MT-MIP-2 exceeded 90 %. These findings demonstrate that MT-MIP-2 offers improved efficiency in the simultaneous isolation of EPMC and EC, making it a promising SPE adsorbent for natural product analysis. The separation step using MT-MIP-2 as SPE sorbent can replace the fractionation and sub-fractionation stages in EPMC and EC conventional isolation methods with high purity.
Theoretical and experimental evaluation of biosolvents with different degrees of hydrophobicity for the extraction of safranal and crocins from saffron
Rivas-Piña M, Mena-García A, Ruiz-Matute AI, Lebrón-Aguilar R, Luz M and Quintanilla-López JE
Saffron (Crocus sativus) is a rich source of safranal and crocins, compounds responsible for its organoleptic and bioactive properties. Currently, there is a growing interest in obtaining saffron-based bioactive ingredients using sustainable technologies to develop functional products. This study explores the use of green biosolvents, including natural deep eutectic solvents (NADESs), for the extraction of safranal and crocins. Solvent selection was guided by COSMO-RS (COnductor-like Screening MOdel for Real Solvents) predictions, also considering solvent polarity, toxicity level, and commercial availability. These predictions were also validated through σ-profile analysis and molecular dynamics simulations. Selected solvents, namely verbenone, carvacrol, and NADESs based on thymol and choline chloride, were evaluated against conventional solvents (H₂O and MeOH:H₂O). Saffron extracts were analysed using HPLC-DAD-MS, with choline chloride:ethylene glycol emerging as the most effective extractant for safranal (2.55 mg g⁻¹), comparable to MeOH:H₂O (2.56 mg g⁻¹), and superior to H₂O (1.29 mg g⁻¹). These solvents also provided the highest crocin recoveries (114.76-117.16 mg g⁻¹). Among the terpenoid-based solvents, carvacrol exhibited a higher selectivity for safranal (1.04 mg g⁻¹), with only 0.91 mg g⁻¹ for crocins. Overall, the hydrophilic solvents were more efficient than the hydrophobic ones, finding a clear relationship between polarity and extraction capacity. These findings suggest the potential application of choline chloride:ethylene glycol NADES in the food industry for the extraction of bioactives from saffron, providing ecological benefits with low health risks and environmental impact.
On the intrinsic effect of the particle size distribution on the permeability of particulate liquid chromatography columns. A theoretical overview
Gritti F
This study presents a theoretical investigation into the intrinsic influence of particle size distribution (PSD) on the permeability of packed beds in liquid chromatography columns. Using a log-normal PSD derived from experimental data on 2μm BEH 66Å Particles, the work explores how different definitions of average particle size, number-, volume-, and surface-area-weighted (Sauter mean), affect the comparison between monodisperse and polydisperse particle packings when estimating the solid-to-fluid surface area in various models of column permeability. By normalizing permeability to a constant void fraction and average particle size, it is shown that the calculation of the permeability of columns packed with polydisperse particles is found to be either higher or lower than that of monodisperse packings, depending on the chosen reference particle size. Notably, for the same void fraction and Sauter mean diameter, the width of the particle size distribution (PSD) of any chromatographic packing material has no intrinsic impact on the column permeability. This confirms that, in addition to void fraction, the Sauter mean diameter or the specific surface area is the second most critical parameter for fair and meaningful comparison. These findings are supported by analytical derivations and validated against published fluid dynamics simulations across a broad range of microstructures composed of both highly polydisperse and strictly monodisperse non-overlapping sphere packings as well as few simulated and measured permeability data of liquid chromatography columns. Overall, the results offer a robust framework for interpreting column permeability and guiding particle design strategies aimed at maximizing chromatographic speed and performance.
Purification-free immobilization of dopamine D2 receptor and glucocorticoid receptor by alkyne-azide cycloaddition for affinity chromatography-based drug screening
Bai R, Li M, Zhang Y, He J, Lin Y, Zhang H, Shu P, Yan X, Wang B, Huang T, Zhao X and Zhao X
Immobilized protein-based affinity chromatography offers a promising alternative for high-throughput drug screening, yet its effectiveness is often hampered by conventional immobilization techniques as they result in functional loss of the protein due to random orientation and multi-step purification. Herein, we developed a universal strategy for fabricating highly efficient chromatographic methods by integrating genetic code expansion with alkyne-azide click cycloaddition in the immobilization of dopamine D2 receptor (DRD2) and glucocorticoid receptor (GR) strain-promoted alkyne-azide cycloaddition (SPAAC). The site-specific incorporation of p-azidophenylalanine (pAzF) into the two receptors using an engineered E. coli C321.ΔA strain enabled direct, oriented, and covalent immobilization of them onto dibenzocyclooctyne (DBCO)-functionalized silica by a copper-free click reaction without the need for prior purification. The resulting immobilized DRD2 and GR stationary phases were thoroughly characterized by XPS, SEM/EDS, and immunofluorescence, confirming successful immobilization and preserved receptor activity. These exhibited exceptional specificity, stability (>30 days), and reproducibility (RSD<1 %). Applications immobilized DRD2 and GR in analyzing Wendan Decoction identified liquiritigenin, neohesperidin, and naringin as active components of the prescription. Among them, liquiritigenin, neohesperidin were characterized as dual-target ligands. Determination of their binding affinities to the receptors by frontal analysis enables calculation of drug-like efficiency indices (SEI, BEI, LLE). Cellular assays in HT22 cells further confirmed their bioactivities and target specificity to the receptors. This work is possible to advance the discovery of potential leads from natural products as it has the properties of streamlining the construction of reliable receptor chromatography methods, integrating the screening with binding affinity measurement, and preliminary drug-likeness evaluation.
Analysis of N-methyl-2-pyrrolidone and its hydroxy metabolite at low concentration level in water samples using liquid chromatography tandem mass spectrometry
Tölgyesi Á, Gonçalves C, Benes E, Simon A and Sharma VK
N-methyl-2-pyrrolidone (NMP) is a synthetic organic compound used as a solvent in several industrial processes such as battery and cosmetics production. There are growing concerns regarding the toxicity of NMP in the environment. We present for the first time a liquid chromatography tandem mass spectrometric (LC-MS/MS) method for the determination of NMP and its hydroxy metabolite (5‑hydroxy-N-methyl-2-pyrrolidone, 5-OHNMP) in water at trace concentration (< 1.0 ng/mL). The HPLC separation was carried out on an aqueous mixed-mode column packed with C18 and anion exchange particles that enabled appropriate retention for both compounds. Quick sample preparation was performed by mixing isotopically labelled internal standards with the samples, followed by extraction with ethyl acetate in the presence of a QuEChERS salt mixture. After eliminating the use of plasticware from the entire sample treatment process, the target analytes could be detected at the 0.1 ng/mL level. The further reducing of the limit of quantification (LOQ) in real samples was limited by the cross contamination of NMP originating from the equipment used for the analysis. The method was validated between the 0.1 ng/mL and 10 ng/mL levels and the recovery ranged from 101 % to 109 % with high precision (RSD = 1.69 % - 7.34 %), with the exception for NMP at 0.10 ng/mL (RSD% = 24.7 %). The method was applied to the analysis of NMP in thirty-five surface and groundwater samples.
A review of pretreatment and analytical methods for phenoxyacetic acid herbicides in food
Zhang CY, Zhang Y, Wei YJ, Liang XR, Yu L, Feng XS and Dan Liu X
Phenoxyacetic acid (POA) herbicides are globally utilized in agriculture for managing broad-leaved and budding weeds due to their effectiveness and cost efficiency. Nevertheless, their irrational application has been associated with residues in agricultural products, which pose a threat to human health through direct consumption or bioaccumulation within the food chain. Exposure to POAs, whether direct or indirect, can elicit adverse health effects including skin irritation, nausea, and elevated blood pressure. However, the analysis of POA in food matrices is challenged by complex matrix effects, the requirement for trace-level detection, and the need for efficient sample pretreatment, making it crucial to develop fast, sensitive, and accurate determination methods. Hence, this study offers a thorough examination of recent developments in pretreatment techniques and analytical methods for POAs since 2017, pretreatment methods for POAs include liquid-liquid extraction (LLE), solid-phase extraction (SPE) and different microextraction methods. Analytical methods involve liquid chromatography-based methods, gas chromatography-based methods and sensor methods. Furthermore, development prospects in pretreatment and analytical methods for POAs are also deliberated.
Application of design of experiments to optimize the separation of lipid-related compounds in supercritical fluid chromatography-mass spectrometry
Kazmouz MY, Mayer M and Felinger A
The response surface methodology (RSM) was used to optimize the separation conditions in a supercritical fluid chromatography-mass spectrometry (SFC/MS) analysis. This optimization was applied on data obtained from a central composite design (CCD). The target compounds were two fatty acids - arachidonic acid (AA) and docosahexaenoic acid (DHA) - along with various lipid classes, including phosphatidylcholines (PC), phosphatidylglycerols (PG), and phosphatidylethanolamines (PE). Three operational variables - gradient time, pressure, and modifier percentage - were investigated to evaluate their influence on the resolution between AA and DHA and the symmetry factor of their respective peaks. The CCD included 3 levels for each variable within a range of gradient time between 1 and 2 min, the pressure between 125 and 225 bar, and the modifier percentage from 2 to 5 %. The data of RSM for the critical pair of acids indicated that pressure and modifier percentage were the parameters that most influenced both the resolution and symmetry factor, whereas gradient time was not a significant variable. The importance of this study lies in the capability of the response surface to show not only a linear interaction (relationship) but also a non-linear interaction between the significant variables - pressure and modifier percentage. Consequently, small changes in one of the significant variables affected the resolution AA/DHA and symmetry factors of their respective peaks significantly. This type of interaction between variables can only be elucidated by the design of experiments (DOE) approach employed in this work, which is not demonstrated in similar work of lipid anbalysis.
Method development for plutonium detection in seawater: Selective extraction and sample preparation using actinide resin
Park JY, Lee D, Park R, Kim H and Kim J
A rapid and efficient analytical method was developed for the determination of plutonium in large-volume seawater to overcome the limitations of conventional coprecipitation techniques, which typically require an analysis time of 1-2 d and involve multiple labor-intensive steps. The proposed method integrates microwave-assisted acid digestion, CaF/LaF coprecipitation, and TEVA extraction chromatography with actinide-selective resin (AN-resin) to enable high recovery and significantly reduce the analysis time. Additionally, a key challenge was overcome through method optimization using seawater pre-equilibrated with Pu and Pu as an internal tracer, namely the efficient and rapid separation of Pu from the AN-resin eluate while maintaining its oxidation state. Validation using 20 L seawater samples spiked with Pu achieved recoveries of 86.2 ± 4.4% and 90.5 ± 4.5% for Pu, with an analytical accuracy of 96.7% and precision (relative standard deviation) of 3.1%. The total pretreatment time, including a 2 h preconcentration step, was reduced to ∼7 h, while achieving detection limits of 0.03-0.05 μBq/kg. Interlaboratory comparisons confirmed the robustness of the developed method, while field application to Korean coastal waters yielded Pu activities and isotopic ratios consistent with regional monitoring data. This study presents a high-throughput and reliable alternative to conventional methods, offering a versatile platform for emergency response and environmental monitoring of plutonium and other actinides in marine systems.
Shilajit-analytical study to understand the phyto complex present in shilajit raw material, extract and resin by using hyphenated techniques
Kohli HK, Somasekhar V, Reddy MD and Prakash NS
Shilajit is an astonishing sticky tar-like resinous substance obtained from the rocks of mountains at higher altitudes. In Ayurveda, shilajit is known for its rejuvenating and adaptogenic properties, mainly due to the presence of bioactive markers like fulvic acid, hippuric acid, urolithin A. The current study aimed to develop high performance liquid chromatography (HPLC) method for quantification of these markers. Both qualitative and quantitative analysis was performed on shilajit samples. The chromatographic separation was achieved on YMC-Triart C18 column using 0.1 % orthophosphoric acid (OPA) in water as mobile phase A and acetonitrile as mobile phase B. The flow rate was maintained at 1mL/min. Furthermore, high performance thin-layer chromatography (HPTLC) and liquid chromatography-mass spectrometry (LC-MS) methods were developed to identify and confirm the mass of bioactive markers. Gravimetric analysis was performed for the quantification of total fulvic acid content present in shilajit sample. Shilajit is known to be rich in wide range of minerals and trace elements. To investigate that, 14 elements were quantified using inductively coupled plasma mass spectrometry (ICP-MS). The minerals present in shilajit helps in its vitality and may improve nutrient absorption. The developed method resulted in good resolution of targeted compounds and will help in routine quality control and biomarker analysis. The research highlights the chemical complexity of shilajit, emphasizing its dual pharmacological significance through both organic phytochemicals and mineral content. The findings provide a foundation for reliable profiling and safety assessment, paving the way for future pharmaceutical applications of Shilajit.
Preparation of a novel hollow-shaped carboxyl-functionalized microporous organic network for efficient solid-phase extraction of indoleamines from fruit juice samples
Ma CH, Cui YY, Zhang XG, Liu WS and Yang CX
Accurate quantification of indoleamines such as melatonin in complex food matrices is crucial for identifying rich dietary sources and developing potential adjuvant therapies. In this study, a novel hollow-structured, hydrophilic carboxyl-functionalized microporous organic network (H-MON-2COOH) was designed and synthesized via a sacrificial-template approach for the efficient solid-phase extraction (SPE) and determination of three typical indoleamines in fruit juice samples. The material exhibits a high surface area, excellent stability, and robust mechanical strength, along with abundant interaction sites enabling π-π stacking, hydrogen bonding, and electrostatic interactions for indoleamines. These properties collectively facilitate highly selective and sensitive analysis, demonstrated by wide linear ranges (0.9-1000 μg L), low limits of detection (0.3-0.8 μg L), high enhancement factors (94.7-96.2), satisfactory precision (RSDs < 6.5 %), excellent reusability (> 50 cycles), and outstanding chemical stability. The hollow architecture significantly improves mass transfer, leading to rapid adsorption equilibrium. Compared to commercial adsorbents including C18, activated carbon, and HLB, H-MON-2COOH showed superior extraction recovery. This study underscores the promising application of functionalized hollow MONs in sample pretreatment and food analysis.
A stable all-D peptide ligand inspires broad-spectrum affinity and high performance in the purification of COVID-19 vaccines
Ma J, Dong X, Yu L, Sun Y and Shi Q
Affinity peptides are an appealing class of ligands for affinity chromatography. However, the application of peptide ligands in biopharmaceutical manufacturing is impeded by their poor stability, susceptibility to degradation and short half-lives. Here, the affinity peptide identified previously, HWKAVNWLKPWT (L-HWK), was reformulated by substituting all the residues with their d-amino acid counterparts, and the d-enantiomer of l-HWK (D-HWK) was investigated to evaluate the binding affinity and molecular mechanism with the receptor binding domains (RBDs) on COVID-19 spike (S) proteins. The results showed that d-HWK had higher affinities than l-HWK for the wild-type (wt) RBD, trimer S protein (TrimerS), and RBDs from variants of concern. Molecular dynamics simulations further revealed that d- and l-HWK had the same binding pocket on the RBD and a more stable binding conformation was obtained in d-HWK binding, which was supported by enhanced intermolecular π-π stacking interactions and a more extensive hydrogen bond network. The chromatographic results demonstrated that Sep6FF-d-HWK chromatography had broader binding conditions for the wt-RBD and TrimerS than Sep6FF-l-HWK chromatography, and that the adsorbed targets could be efficiently eluted under mild conditions. Seng4FF-d-HWK chromatography was used to successfully purify wt-COVID-19 and Omicron vaccines. Most importantly, d-HWK exhibited great tolerance to enzymatic hydrolysis, and Seng4FF-d-HWK improved the purification performance and stability of inactivated Omicron variant vaccines across 20 purification cycles. The research is crucial for the application of broad-spectrum affinity chromatography in the purification of COVID-19 vaccines and provides a more effective strategy for accelerating the development of affinity chromatography for an unknown pandemic occurring in the future.
Hybridization liquid chromatography-mass spectrometry for quantitative bioanalysis of oligonucleotides: The upcoming paradigm shift
Yuan L
Therapeutic oligonucleotides, which are short, synthetic, single- or double-stranded oligonucleotides, have been rapidly growing in drug discovery and development as a new class of modality. Major types of approved oligonucleotide therapeutics include antisense oligonucleotide (ASO), small interfering RNA (siRNA), and aptamers. Various bioanalytical techniques, including hybridization immunoassay, liquid chromatography-mass spectrometry (LC-MS), liquid chromatography (LC)-fluorescence, and quantitative polymerase chain reaction (qPCR), have been used for the quantitative bioanalysis of oligonucleotides, but all have their own drawbacks on either specificity or sensitivity. Recently, hybridization LC-MS has been rapidly growing as a new bioanalytical technique for the quantification of oligonucleotides. This technique offers a unique advantage of achieving both high specificity and good sensitivity by integrating hybridization extraction with LC-MS. With the continued growing demands for sensitive, specific, accurate, and reliable bioanalytical methods, hybridization LC-MS has great potential to be more widely applied and to become the primary method for oligonucleotide bioanalysis. In this review, this technique will be reviewed and compared with the traditional techniques. The strategies and challenges of hybridization LC-MS for the quantification of oligonucleotides, including both single-stranded oligonucleotides (e.g., ASO) and double-stranded oligonucleotides (e.g., siRNA), will be discussed. Considerations, novel applications (e.g., microsampling, microflow LC), and future opportunities of this new technique will also be discussed.
Magnetic MON@COF composites for efficient detection of NSAIDs from water
Zhao W, Huang S, Liu W, Gan N and Xu Q
The presence of residual non-steroidal anti-inflammatory drugs (NSAIDs) in environmental water bodies has garnered increasing concern. In this study, two magnetic microporous organic networks (MONs) were synthesized by integrating them with imine-linked covalent organic frameworks (COFs), resulting in two novel magnetic MON@COF composites (MMON-Br@COF and MMON-I@COF) for the detection of NSAIDs in aquatic environments. The adsorption performance of these composites toward five commonly used NSAIDs was evaluated using high-performance liquid chromatography (HPLC). The results indicated that the adsorption process followed pseudo-second-order kinetics and the Freundlich isotherm model. Notably, MMON-Br@COF exhibited an adsorption capacity of up to 461.60 mg g for diclofenac sodium (DS). The adsorption mechanism involved π-π stacking, hydrogen bonding, and electrostatic interactions. The synergistic effect between the MON and COF components contributed to the efficient capture of NSAIDs. Thermodynamic analysis confirmed the spontaneous nature of the adsorption process. A new method for detecting NSAIDs by MSPE-HPLC was established based on MMON-Br@COF. In complex aqueous matrices, the method achieved a recovery rate exceeding 87.12 %, a low detection limit (0.045-0.110 μg l), and excellent linearity (0.10-500 μg l). This study presented a promising approach for the effective adsorption, detection, and removal of NSAIDs in water environments.
PDE-5 inhibitors in complex matrices: Recent updates on pretreatment and detection methods
Tian XY, Zhang MM and Sun FR
Phosphodiesterase-5 (PDE-5) inhibitors are a class of drugs primarily used to treat male erectile dysfunction. Common medications include sildenafil, tadalafil, and vardenafil. However, issues such as their illegal adulteration pose significant public health concerns. Furthermore, the structural ambiguity and unknown toxicity of analogues illicitly added to health products further increase the risks associated with their use. This review summarizes sample pretreatment methods and detection techniques. Pretreatment methods include common techniques such as dissolution, dilution, protein precipitation, and liquid-liquid extraction, as well as emerging methods like magnetic solid-phase extraction, dispersive liquid-liquid microextraction, and solid-phase microextraction. The application of novel materials, such as covalent organic frameworks, multi-walled carbon nanotubes, and molecularly imprinted polymers, represents a major development direction in the evolution of pretreatment methodologies. Detection methods encompass liquid chromatography-tandem mass spectrometry, gas chromatography-mass spectrometry, and high-performance thin-layer chromatography, among others. Among these, the use of high-resolution mass spectrometry is a current research hotspot. The review critically evaluates the advantages and limitations of existing methodologies, identifies future development directions, and supports the selection of efficient analytical strategies for specific sample matrices and research purposes.
Hollow zeolitic imidazolate framework-8 anchored on reduced graphene oxide aerogel as adsorbent of solid-phase extraction coupled with high-performance liquid chromatography for determination of ciprofloxacin in egg
Li C, Xue L, Cui M, An Y, Zhang X and Li C
The development of adsorbents in sample pretreatment technologies for detecting fluoroquinolone antibiotic residues remains a critical challenge in ensuring food safety. A hollow ZIF-8/reduced graphene oxide aerogel (HRA) is developed as an adsorbent of solid-phase extraction (SPE) in combination with high performance liquid chromatography (HPLC) to realize the efficient enrichment and trace detection of ciprofloxacin (CIP) in egg. Etched hollow ZIF-8 provides unsaturated Zn metal sites and abundant functional groups to specifically recognize CIP. Hollow ZIF-8 loaded onto reduced graphene oxide aerogel displays favorable formability and hierarchical structure, effectively improving the mass transfer effect. An exceptional adsorption capacity of CIP up to 893.1 mg·g realizes the effective pre-enrichment of CIP, with a low limit of detection (LOD) and limit of quantification (LOQ) are 0.042 μg·L and 0.14 μg·L, respectively. Satisfactory recovery rates of 90.7 %-108.9 % with RSD<3.4 % are obtained in detecting CIP residues in egg samples. This study provides a promising approach for detecting antibiotic residues in eggs to ensure food safety.
Development and application of automatic magnetic solid phase extraction assisted High-resolution mass spectrometry for sensitive and rapid determination of 26 fentanyl and metabolites in urine samples
Li W, Wang Y, Yu M, Zhang H and Deng X
Over the past three decades, numerous deaths caused by the illicit use of fentanyl analogues have drawn worldwide concern. However, the detection of trace levels of fentanyl compounds remains challenging due to labor-intensive sample pretreatment, low sensitivity, and limited screening efficiency. In this study, we developed and validated a rapid and sensitive method based on high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS) for the simultaneous determination of 26 fentanyl analogues and metabolites in urine samples. After automated magnetic solid-phase extraction (auto-MSPE), analytes were separated on a C18 column and detected using MRM HR mode. The limits of detection (LOD) and limits of quantification (LOQ) ranged from 0.01 to 0.05 ng/mL and 0.04 to 0.1 ng/mL, respectively. This approach required only 30 min for the pretreatment of 32 urine samples, meeting routine detection requirements while achieving a green and economical workflow. Within the concentration range of 0.1-100 ng/mL (0.5-100 ng/mL for two compounds), all analytes exhibited good linearity with correlation coefficients (R² > 0.99). Accuracy ranged from 75.1 % to 117.0 %, extraction recoveries from 72.1 % to 100 %, and matrix effects from 64.2 % to 111.7 %. The method was successfully applied to the detection and quantification of fentanyl and its major metabolite norfentanyl in authentic urine samples. These results demonstrate the potential of this method for the reliable detection of fentanyl analogues in forensic and clinical toxicology.
Development of a LC-MS/MS method for the determination of tetrabromobisphenol A-bis(2,3-dibromo-2-methylpropyl ether) and co-occurring brominated flame retardant in building insulation foam and environmental matrices
Shi Z, Liu W, Mao T, Yin F, Chen Z, Chen C and Sun Y
A robust and sensitive analytical method was developed for the simultaneous determination of a novel brominated flame retardant (BFR) Tetrabromobisphenol A-bis(2,3-dibromo-2-methylpropyl ether) (BDDMP), alongside Tetrabromobisphenol A-bis(2,3-dibromo-propyl ether) (BDDP), Tetrabromobisphenol A (TBBPA), Decabromodiphenyl ether (DBDPO), and three stereoisomers of Hexabromocyclododecane (HBCD) in diverse matrices. Analysis was performed using ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS) with an atmospheric pressure chemical ionization (APCI) source operating in negative ion mode. The method demonstrated excellent linearity (R²> 0.995), low instrument detection limits (IDLs: 0.4-1.0 µg/L), and satisfactory recoveries (75.6-98.9 %) across matrices. Successful application to industrial (expanded and extruded polystyrene, EPS/XPS) and environmental (water, sediment, air, soil) samples, utilizing solid-phase extraction (SPE) and accelerated solvent extraction (ASE), confirmed the method's reliability for quantifying BFRs over a wide concentration range (from ng/g to µg/g). This proves high suitability for monitoring both emerging and legacy BFRs.
Utilization of Pinus pumila seed scales as forestry residues: Green microwave-assisted hydrodistillation for essential oil extraction and its antibacterial activity
Mi S, Wang W, Zhu M, Mu L and Lu Q
Pinus pumila seed scales, a commonly discarded forestry residue, were utilized in this study as a raw material for essential oil (PSEO) extraction using microwave-assisted hydrodistillation (MAH). Compared with conventional hydrodistillation (HD), MAH increased the PSEO yield (1.119 and 0.886%), while reducing energy consumption (0.5004 and 2.2257 kWh/g) and CO₂ emissions (0.4003 and 1.7806 kg/g), respectively. GC-MS analysis showed that the terpenoid content in PSEO extracted by the MAH method (96.20%) was 7.93% higher than that obtained by the HD method (88.27%). Antibacterial assays demonstrated that the PSEO extracted by MAH exhibited stronger inhibitory activity against Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, and Listeria monocytogenes than that extracted by the HD method. Mechanistic studies further indicated that PSEO caused structural damage to the cell wall and membrane of E. coli, leading to the leakage of alkaline phosphatase (AKPase), nucleic acids, and proteins, as well as an increase in extracellular conductivity. PSEO obtained by the MAH method caused more significant cellular disruption than that obtained by the HD method. In addition, molecular docking analysis showed that the active compounds abundant in PSEO extracted using the MAH method exhibited strong binding affinity for the OmpF protein through van der Waals forces and hydrogen bonds. These findings supported the green and effective utilization of P. pumila seed scales as a bioactive and eco-friendly antibacterial agent.
A rapid and environmental-friendly method for characterization and determination of the major sesquiterpenoid constituents in the essential oil of Nardostachys jatamansi DC
Wang R, Zhong H, Shi J, Lai J, Yang W, Chai X, Wang Y, Zhang L and Wu H
Essential oil is a key quality marker of Nardostachys jatamansi DC. (NJ), and is one of the main application forms of NJ alone or in a prescription with efficacies such as sedative and antiarrhythmic activities. Herein, GC/EI-MS and UPC-QTOF-MS were simultaneously applied to characterize the chemical profile of the essential oil of N. jatamansi (EONJ), and a UPC-PDA method was further established to determine the contents of the major sesquiterpenones in EONJ. As a result, a total of 81 and 35 constituents were tentatively identified by GC/EI-MS and UPC-QTOF-MS, respectively. Among them, there were three major sesquiterpenones, 1,8,9,10-tetradehydroaristolan-2-one, aristolone, and kanshone H were accurately identified from EONJ. Then, the modifying agent, column temperature, backpressure, flow rate, wavelength, and injection volume were optimized for a UPC-PDA method, whose linearity, precision, repeatability, stability, and recovery were further evaluated to make sure it was accurate and feasible for quantitative determination of the 1,8,9,10-tetradehydroaristolan-2-one, aristolone, and kanshone H in 38 batches of EONJ. Their contents fell into the ranges of 0.0804-0.4876 %, 0.0201-0.0870 %, and 0.0083-0.0444 %, respectively. This study supplies a simple, rapid, and environmental-friendly UPC-PDA method dedicated to the content determination of sesquiterpenone isomers in EONJ, with a new reference for global quality control of N. jatamansi.