Complex Matrices Research Articles

Online Supercritical Fluid Chromatography Hyphenated to Fourier Transform Ion Cyclotron Resonance Mass Spectrometry with Quadrupole Detection for Microalgae Bio-Oil Characterization.

Microalgae are an attractive feedstock for biofuel production thanks to their renewable nature, high growth rate, and ability to use anthropogenic CO2. The conversion of microalgae by hydrothermal liquefaction (HTL) leads to a solid residue, a gaseous phase, and a biocrude. However, the bio-oil is rich in heteroatoms and requires upgrading processes to be used as biofuels. For these treatments to be effective, detailed knowledge of the sample is crucial. The bio-oil was characterized by direct introduction into a Fourier transform ion cyclotron resonance mass spectrometer (DI-FTICR MS) with an electrospray ionization source (ESI). Thousands of molecular formulas were assigned with a high level of confidence, mainly compounds with nitrogen and oxygen atoms. Additionally, the bio-oil was analyzed by coupling supercritical fluid chromatography (SFC) and FTICR to combine the separation power of SFC to the high performances of a 12 T FTICR. Quadrupole detection (2ω) was used in FTICR to have a high resolving power with a lower transient time. The coupling allowed the separation of many isomers along the chromatogram, showing the isomeric complexity of microalgae bio-oils. Moreover, classes of compounds were separated according to their heteroatom class thanks to the SFC separation. In this work, the advantages of DI-FTICR MS and SFC-FTICR MS proved complementary, and DI was useful to study the bio-oil at the molecular scale thanks to the high performances, while SFC proved useful for the characterization at the isomeric scale. This demonstrated the significant potential of this new online hyphenated technique for the characterization of complex matrices.

An all-in-one smartphone-assisted ratiometric fluorescent device for visual and quantitative detection of glutathione

The daily consumption of foods abundant in Glutathione (GSH) can be supplemented to maintain the homeostasis of GSH in human health and alleviate pathologies resulting from abnormal GSH levels. The fluorescence-based visual determination of GSH has gradually attracted the attention of researchers due to its robust performance and versatile implementation. However, the current GSH visual strategy primarily relies on variations in fluorescence intensity at a single emission wavelength, which poses challenges for naked-eye and portable readout, as well as distorted signals caused by complex matrix effects in real samples. Herein, a ratiometric fluorescence sensor based on carbon dots (CDs) combined with an all-in-one 3D-printed smartphone-based device was successfully developed for low-cost, visual and rapid detection of GSH without the need for an external excitation light source. The ratiometric fluorescent materials were synthesized by conjugating blue carbon dots (B-CDs) with yellow carbon dots (Y-CDs) through the utilization of selected Cu2+ ions. The resulting mechanism demonstrated that the coordination interaction between Cu2+ and residual aromatic amino groups in Y-CDs (Y-CDs-Cu2+) contributed to a newly emitted peak at 580 nm, thereby inducing fluorescence resonance energy transfer from B-CDs to Y-CDs-Cu2+. A linear correlation was found between GSH concentrations and R/B values in the range of 10–100 μM, with a limit of detection observed at 4.8 μM. By utilizing this portable device in combination with RGB analysis, the quantitative detection of GSH can be achieved even in complex food matrices such as tomatoes and grapes. The universality of this all-in-one device was further validated by pre-spraying CDs onto a paper strip for visual measurement of GSH. This work offers a portable, visual, and accessible approach to evaluating food safety and nutrition, thereby demonstrating significant economic value and holding profound implications for human health.

Boosting Photogenerated Electrons Transfer from FeVO4 to Peroxymonosulfate via Cu Doping for Stable Degradation of Organic Contaminants

Comprehensive SummaryElectron transfer is an important way to activate persulfate. Currently, the electrons for persulfate activation mainly originate from organic contaminants or the catalyst itself, which can lead to selective activation of persulfate or oxidation of the catalyst, respectively, and thus become a bottleneck restricting its application. In this work, Cu−doped FeVO4 (Cu−FVO) was prepared, and the results showed that Cu doping can significantly improve the photocatalytic activity and stability of FVO for peroxymonosulfate (PMS) activation. The optimized Cu−FVO/PMS/light system exhibited a high BPA degradation rate that is 4.3 times higher than that of the FVO/PMS/light. This system manifested a broad applicability to various organic contaminants even with complex matrix. Photoelectrochemical analysis and DFT theoretical calculations revealed that Cu doping boosted the photogenerated charge separation and the adsorption of PMS on FVO. Furthermore, Cu doping led to the establishment of an electron transfer channel from Cu−FVO to PMS, through which photogenerated electrons achieved an efficient PMS activation. Meanwhile, holes were consumed by organic contaminants to avoid the oxidation of catalyst. These collectively enhanced the photocatalytic activity and stability of Cu−FVO, which also maintained high catalytic activity even after 20 cycling degradation reactions.

Current trends and patterns of PFAS in agroecosystems and environment: A review.

Per- and polyfluoroalkyl substances (PFASs) are one of the more well-known highly persistent organic pollutants with potential risks to agroecological systems. These compounds are of global concern due to their persistence and mobility, and they often lead to serious impacts on environmental, agricultural, and human health. In the past 20 years, the number of science publications on PFAS has risen; despite this, certain fundamental questions about PFAS occurrence, sources, mechanism of transport, and impacts on agroecosystems and the societies dependent on them are still open and evolving. There is a lack of systematic and comprehensive analysis of these concerns in agroecosystems. Therefore, we reviewed the current literature on PFAS with a focus on agroecosystems; our review suggests that PFASs are nearly ubiquitous in agricultural systems. We found the current research has limitations in analyzing PFAS in complex matrices because of their small size, distribution, and persistence within various environmental systems. There is consistency in the properties and composition of PFAS in and around agroecosystems, suggesting evidence of shared sources and similar components within different tropic levels. The introduction of new and varied sources of PFAS appear to be growing, adding to their residual accumulation in environmental matrices and leading to possible new types of chemical compounds that are difficult to assess accurately. This review determines existing research trends, understands mechanisms and incidence of PFAS within agroecosystems and their impact on human health, and thereby recommends further studies to remedy research gaps.

Design and optimization of a colorimetric biosensor using functionalized gold nanoparticles and bi-functional linker for agriculture and food industry

This study aims to develop a highly sensitive colorimetric detection system utilizing functionalized gold nanoparticles (f-AuNPs) and bifunctional linkers (BLs) for the detection of pathogens and contaminants in food matrices. The primary objective was to explore and optimize key parameters, including reaction time, system volume and the concentration of bifunctional linkers, in order to enhance the system’s detection capabilities. The core mechanism of the bi-functional linker-based detection system is based on the aggregation of streptavidin-functionalized AuNPs (stAuNPs), which varies in accordance with the concentration of the bifunctional linkers (BLs) and reflects the quantity of effective linkers (EALs) available in the system. The process comprises the binding of the targets and BLs, a reduction in EAL concentration, an increase in the BLs concentration required for the aggregation of the stAuNPs, and a shift in the range exhibiting a visible color change (REVC). In systems without a target, all BLs induce aggregation. In contrast, in systems with a target present, some BLs are bound by the target, reducing EAL concentration and altering the optimal BLs concentration for stAuNP aggregation. The system was shown to be capable of detecting protein in PBS at concentrations as low as 2 nM, as well as Salmonella at 101 CFU/mL. In whole milk, the detection limits were 20 nM for protein and 102 CFU/mL for Salmonella. The principal conclusion is that the BLs-based system provides a robust and adaptable platform for pathogen detection, even in complex food matrices, obviating the need for preprocessing. The findings demonstrate the system’s potential for practical applications in the fields of food safety and agricultural contaminant detection, offering clear visual signals and high sensitivity.

Parallel reaction monitoring targeted mass spectrometry as a fast and sensitive alternative to antibody-based protein detection

The reliable, accurate and quantitative targeted detection of proteins is a key technology in molecular and cell biology and molecular diagnostics. The current golden standard for targeted protein detection in complex mixtures such as complete cell lysates or body fluids is immunoblotting, a technology that was developed in the late 1970s and has not undergone major changes since. Although widespread, this methodology suffers from several disadvantages, such as the inability to detect low-abundant proteins or specific posttranslational modifications, the requirement for highly specific antibodies, the lack of quantitative power and the often-tedious practical procedures. Mass spectrometry (MS) based targeted protein detection is an alternative technology that could circumvent these caveats. Here, we compare immunoblotting with targeted protein mass spectrometry using a parallel reaction monitoring (PRM) regime on the Orbitrap mass spectrometer. We show that PRM based MS has superior sensitivity and quantitative accuracy over immunoblotting. The limit of detection for proteolytic peptides of a purified target protein was found to be in the mid- to low-attomole range and approximately one order of magnitude higher when embedded in a complex biological matrix. The incorporation of synthetic heavy isotope labeled (AQUA) peptides as internal calibrants into the PRM workflow allows for even higher accuracy for both the relative and absolute quantitation of tryptic target peptides. In conclusion, PRM is a versatile and sensitive technology, which can overcome the shortcomings of immunoblotting. We argue that PRM based MS could become the method of choice for the targeted detection of proteins in complex cellular matrices or body fluids and may eventually replace standard methods such as Western blotting and ELISA in biomedical research and in the clinic.

Efficient protein extraction for assessing food allergy risk in complex alternative protein matrices

Allergy to novel food proteins, due to diverse ingredients and innovative food processing technologies employed to achieve desired functional properties, is a major safety concern. Current allergy testing methods (ELISA and mass spectrometry) depend on high-quality protein extracts, meaning existing methods are often tailored to specific matrices. Therefore, a more efficient and general protein extraction method is desirable for comprehensive allergy risk assessment. Here, we developed a highly efficient and reproducible protein extraction method which achieved at least 80 % efficiency across several food matrices. Proteomics analysis of a plant-based meat using our optimized extraction method showed that higher extraction efficiency improved reproducibility of identified proteins. Moreover, higher protein extraction efficiency resulted in increased abundances of individual allergenic proteins. This underscores the relevance of our method for more accurate measurements of allergenic protein concentrations in allergy risk assessments.

Picolinic acid-mediated Mn(II) activated periodate for ultrafast and selective degradation of emerging contaminants: Key role of high-valent Mn-oxo species

The utilization of periodate (PI, IO4-) in metal-based advanced oxidation processes (AOPs) for the elimination of emerging contaminants (ECs) have garnered significant attention. However, the commonly used homogeneous metal catalyst Mn(II) performs inadequately in activating PI. Herein, we exploited a novel AOP technology by employing the complex of Mn(II) with the biodegradable picolinic acid (PICA) to activate PI for the degradation of electron-rich pollutants. The performance of the Mn(II)-PICA complex surpassed that of ligand-free Mn(II) and other Mn(II) complexes with common aminopolycarboxylate ligands. Through scavenger, sulfoxide-probe transformation, and 18O isotope-labeling experiments, we confirmed that the dominant reactive oxidant generated in the Mn(II)-PICA/PI system was high-valent manganese-oxo species (Mn(V)=O). Due to its reliance on Mn(V)=O, the Mn(II)-PICA/PI process exhibited remarkable selectivity and strong anti-interference during EC oxidation in complex water matrices. Nine structurally diverse pollutants were selected for evaluation, and their lnkobs values in the Mn(II)-PICA/PI system correlated well with their electrophilic/nucleophilic indexes, EHOMO, and vertical IP (R2 = 0.79–0.94). Additionally, IO4- was converted into non-toxic iodate (IO3-) without producing undesired iodine species such as HOI, I2, and I3-. This study provides a novel protocol for metal-based AOPs using PI in combination with chelating agents and high-valent metal-oxo species formation during water purification.

Nanozyme coating-gated multifunctional COF composite based dual-ratio enhanced dual-mode sensor for highly sensitive and reliable detection of organophosphorus pesticides in real samples

The reliable detection of organophosphorus pesticides (OPs) in complex matrices remains an enormous challenge due to inevitable interference of sample matrices and testing factors. To address this issue, we designed a nanozyme-coated mesoporous COF with guest molecule loading, and successfully used it to construct a dual-ratio dual-mode sensor through target-regulated signal generation. The multifunctional COF-based composite (MB/COF@MnO2, MCM) featured high loading of methylene blue (MB), oxidase-like MnO2 coatings as gatekeepers, and specific recognition of thiocholine (TCh). TCh, a regulator produced from acetylcholinesterase (AChE)-catalyzed hydrolysis of acetylthiocholine, could decompose MnO2 coatings, triggering the release of abundant MB and oxidation of few o-phenylenediamine (OPD). OPs, strong inhibitors of AChE, could restrain TCh production and MnO2 decomposition, thereby controlling the release of less MB and oxidation of more OPD. This regulation boosted the dual-ratio dual-mode assay of OPs by using the released MB and oxidized OPD in the solution as testing signals, measured by both fluorescent and electrochemical methods. Experimental results demonstrated the sensitive detection of dichlorvos with LODs of 0.083 and 0.026 ng/mL via the fluorescent/electrochemical mode, respectively. This study represented a creative endeavor to develop dual-ratio dual-mode sensors for OPs detection in complex samples, offering high sensitivity, excellent selectivity, and good reliability.

Quantification of mycolic acids in different mycobacterial species by standard addition method through liquid chromatography mass spectrometry

Mycobacteria possess unique and robust lipid profile responsible for their pathogenesis and drug resistance. Mycolic acid (MA) represents an attractive diagnostic biomarker being absent in humans, inert and known to modulate host-pathogen interaction. Accurate measurement of MA is significant to design efficient therapeutics. Despite considerable advances in Liquid chromatography coupled with tandem mass spectrometry (LC–MS/MS) based approaches, quantification of mycobacterial lipids including MA is still challenging mainly because of ion suppression effects due to complex matrix and non-availability of suitable internal standards for MA. The current study demonstrates the use of standard addition method (SAM) to circumvent this problem and provides a reliable and exhaustive analytical method to quantify mycobacterial MA based on reversed-phase ultra-high-performance liquid chromatography- mass spectrometry data acquisition. In this method, multiple reaction monitoring (MRM) has been applied, wherein 16 MRM channels or transitions have been chosen for quantification of alpha-, methoxy- and keto-MAs with C-24 and C-26 hydrocarbon chains that are actually best suited for TB diagnostics. We found that the overall methodological limit of detection and limit of quantification were in the range 0.05–0.71 ng/µl and 0.16–2.16 ng/µl. Taken together, SAM quantitative technique could serve as promising alternative for relative concentration determination of MA to aid medical research.

Electrical Bioimpedance in Milk Adulterated with Water: Measurement Methodology for Quantification, Influence of Temperature, and Mathematical Modelling

Milk has a high nutritional value and is also one of the most versatile products in the food industry. Unfortunately, fraud involving the product is constant and needs to be combated. This work presents a measurement methodology to perform the electrical impedance analysis in food. The influence of temperature on the measurements has been evaluated through mathematical models specially developed for identifying the fraudulent activity of adding water to milk. The bioimpedance measurements have been performed in a sample container with a four-electrode measurement system and a digital oscilloscope. Samples of 150 mL were analysed, prepared using whole UHT milk adulterated with distilled water in different % by volume (V/V), at temperatures of 16, 28, and 37 °C. The proposed measurement methodology has been validated and showed sensitivity for analysis in milk, revealing the influence of temperature on the impedance values; from the results mathematical models were proposed for investigating adulteration in milk. This work deals with the design of a device capable of measuring bioimpedance in milk with a view to its application in physicochemical analyses. The influence of temperature on the impedance values was also evaluated to propose mathematical models to facilitate analysis with complex factors and matrices.

Portable cell imprinted polymer-based microfluidic sensor for bacteria detection in real water

Cell-imprinted polymer (CIP) based optical biosensors have transformed point-of-care detection. However, challenges remain in their portability and detection sensitivity, time, and cost. Herein, we present an imprinted polymer-based low-cost microfluidic device integrated into a portable enclosure that enables rapid and sensitive bacteria detection in real water. A portable 3D-printed platform was custom-designed, housing all essential detection components, i.e., pumping and fluorescent imaging units and the microfluidic sensor. CIP coated magnetic microparticles (MPs) with affinity to bacteria were manipulated inside the magnetophoretic microfluidic device at an optimized flow rate of 0.01 mL/min for bacteria capturing. Fluorescent imaging pre- and post-bacteria capture facilitated quantification of fluorescence intensity changes as bacteria were trapped by the CIP-MPs. The sensor’s dose–response curve established limits of detection (LOD) and quantification (LOQ) at 8 × 103 and 6 × 105 CFU/mL, respectively, within a dynamic range of 103 to 109 CFU/mL. It specifically detected E. coli, distinguishing it from non-specific bacteria like Salmonella and Sarcina. In real pond water tests, our sensor detected 2 × 10⁶ CFU/mL, matching a central lab’s result of 2.33 × 10⁶ CFU/mL, demonstrating its effectiveness for real-water monitoring. While further enhancements are needed for improving the specificity in complex environmental matrices and broader bacterial strain detection, the sensor’s simplicity and portability highlight its potential for practical potential.

Study of authenticity, quality characteristics and bioactivity in honey samples from different botanical origins and countries

Honey is a widely consumed commodity featuring beneficial nutritional properties resulting in a high market price. Therefore, honey is a target of fraudulent practices and analytical strategies to assess honey quality and origin are highly needed. Within this context, we performed a comprehensive analytical testing for 39 honey samples originating from Greece and other countries. Analytical parameters related to honey quality control (Directive 2001/110/EC) were monitored. In detail, hydroxymethylfurfural (HMF) and diastase activity were measured using spectrophotometric assays. Importantly, 6 samples imported by the American market exceeded the regulatory limit (40 mg/kg). The content of the main honey sugars was monitored using an accredited ultra-high-performance liquid chromatography coupled to evaporative light scattering detector (UHPLC-ELSD) and all samples were in line with the regulatory standards. In addition, chromatographic analysis was performed to determine 23 phenolic compounds as these are bioactive compounds contributing towards the health promoting effects of honey. Besides chemical characterisation, in vitro testing was also performed by monitoring the inhibitory effect of the honey samples towards acetylcholinesterase (AChE) and pancreatic lipase (PNLIP). Indeed, inhibition was noticed and in the case of PNLIP the monitored differences between Greek and samples from other countries were statistically significant. To assess honey sample authenticity, chemometric tools were employed, namely, principal component analysis (PCA), hierarchical cluster analysis (HCA) and linear discriminant analysis (LDA). The multivariate analysis revealed that the taxifolin content may be used as a marker for thyme honey from Cyprus while the total content of gallic and protocatechuic acids could be used as a marker for oak honeys. All in all, implementing several different methods based on different principles (both physicochemical and bioanalytical) in a complex analytical matrix such as honey is a great analytical challenge that we successfully faced and comprehensively demonstrated in this study.

Employment of MQ gas sensors for the classification of Cistus ladanifer essential oils

The chemical composition of essential oils (EOs) from Cistus ladanifer has a huge variability throughout the year, impacting the oil quality. Nowadays, EO analytic chemistry techniques, which are expensive and destroy the sample, are utilized to measure the chemical composition. In the paper, we propose a combination of low-cost sensors and machine learning based system. As low-cost sensors, seven gas sensors are combined to obtain up to 36 features. Regarding machine learning, 31 multiclass classification algorithms are applied. Data from sensors were collected for 33 samples of EO from Cistus ladanifer. The generated dataset was split into training and test datasets, with 75 % of the data for training. The datasets were created to ensure a homogeneous chemical composition distribution on both training and test datasets. There were three target chemical compounds: Alpha-pinene and Viridiflorol as individual compounds and Terpenic Hydrocarbons as a group of chemical compounds. The value of the percentage of each targeted compound is converted into a categoric variable with 5 possible values, 1 being the lowest concentration and 5 being the maximum one. The data of the MQ-sensors were included as the input for the models, and each one of the targeted chemical compounds was selected as an output for different models. The input features were ranged using different algorithms for the feature selection process. The results indicate that there is no valid classification model for Viridiflorol, and limited accuracy is achieved for Alpha-pinene. Meanwhile, for Terpenic Hydrocarbons, an accuracy of 91.6 % is achieved. It is important to highlight that these accuracies were attained when a reduced number of features were included, ranging the number of features from 11 to 13. This is the first case in which MQ-based gas sensors, or other metal oxide sensors, are used to correctly determine the concentration of a chemical compounds in a complex matrix formed by dozens of compounds. This system will provide a cheap method to determine the quality of EOs and confirm the benefits of combining low-cost sensors with machine learning.

Cow's Milk Bioactive Molecules in the Regulation of Glucose Homeostasis in Human and Animal Studies.

Obesity disrupts glucose metabolism, leading to insulin resistance (IR) and cardiometabolic diseases. Consumption of cow's milk and other dairy products may influence glucose metabolism. Within the complex matrix of cow's milk, various carbohydrates, lipids, and peptides act as bioactive molecules to alter human metabolism. Here, we summarize data from human studies and rodent experiments illustrating how these bioactive molecules regulate insulin and glucose homeostasis, supplemented with in vitro studies of the mechanisms behind their effects. Bioactive carbohydrates, including lactose, galactose, and oligosaccharides, generally reduce hyperglycemia, possibly by preventing gut microbiota dysbiosis. Milk-derived lipids of the milk fat globular membrane improve activation of insulin signaling pathways in animal trials but seem to have little impact on glycemia in human studies. However, other lipids produced by ruminants, including polar lipids, odd-chain, trans-, and branched-chain fatty acids, produce neutral or contradictory effects on glucose metabolism. Bioactive peptides derived from whey and casein may exert their effects both directly through their insulinotropic effects or renin-angiotensin-aldosterone system inhibition and indirectly by the regulation of incretin hormones. Overall, the results bolster many observational studies in humans and suggest that cow's milk intake reduces the risk of, and can perhaps be used in treating, metabolic disorders. However, the mechanisms of action for most bioactive compounds in milk are still largely undiscovered.

Study of the Chemical Recovery and Selectivity against U in the Radiochemical Separation of Th with Tri-n-butyl Phosphate by Varying the Proportion of Xylene and HCl Concentration.

Thorium is a radionuclide used in various environmental studies such as dating, sediment movement, soil-plant transfer studies, and contamination of waste from the natural fuel cycle. The liquid-liquid extraction method using tri-n-butyl phosphate (TBP) allows for the separation of Th from the accompanying actinides. However, the separation of Th and U present in the same sample is not trivial. This separation is influenced by the starting acid (HCl or HNO3), the concentration of TBP in an organic solvent, and the concentration of the acid used for re-extracting Th, which is typically HCl. Therefore, it is necessary to study these factors to ensure that the method has sufficient chemical yield and selectivity in complex matrices. This study presents a systematic investigation of the aforementioned parameters, making the necessary variations to select an optimal method for the radiochemical separation of Th. The ideal conditions were obtained using 4 M HCl as the acid prior to extraction, a 1:4 solution of TBP in xylene, and 4 M HCl as the re-extracting agent. The accuracy and precision were studied in four intercomparison exercises conducted in quadruplicate, using the parameters Enumbers, RB(%), and RSD(%) for 232Th and 230Th. The sensitivity of the method was experimentally studied and the limit of detection (LoD) was determined according to ISO 11929:2005. Additionally, the linearity of the method showed that the experimental and theoretical activity concentrations of 232Th and 230Th had slopes of 1 with an intercept close to 0.

Optimization and Validation of a Cheaper, Safer, and More Sustainable Methodology for Aflatoxins Determination in Rich-Lipidic Matrices (Pistachio Nuts) Using Deep Eutectic Solvent Extraction and UHPLC-FLD Analysis.

Aflatoxins pose a major health concern and require strict monitoring in food products. Existing methods rely on hazardous organic solvents for extraction, prompting the development of a greener alternative. This study explores deep eutectic solvents (DESs) for aflatoxin extraction from pistachios, a valuable food product prone to aflatoxin contamination. The proposed method utilizes DES extraction followed by solid-phase extraction cleanup and ultrahigh-performance liquid chromatography coupled with fluorescence detector analysis. Recovery rates ranged from 85.5 to 99.1% for pistachios spiked with 1-8 ng/g aflatoxins, in compliance with EU regulations, with coefficients of variation less than 2.94%. The method demonstrates good sensitivity with limits of detection and quantification in the range of 0.02-0.22 ng/g and 0.05-0.72 ng/g, respectively. Greenness assessment using AGREEPrep and White Analytical Chemistry metrics confirms its environmental sustainability. This approach offers a promising, safer, and more eco-friendly alternative for aflatoxin extraction from complex food matrices like pistachios.

Squaraine-Linked Magnetic Covalent Organic Framework as a Solid-Phase Extraction Absorbent to Determine Trace Phenylpyrazoles.

Phenylpyrazoles are widely used pesticides in the food industry. It is highly desirable to develop efficient pre-treatment and analysis methods to extract and detect phenylpyrazoles in complex food matrices. Herein, the study reports novel squaraine-linked zwitterionic core-shell magnetic covalent organic frameworks (MCOFs), which are found to be excellent pretreatment materials for the detection of trace phenylpyrazoles in samples. By coupling MCOFs to magnetic solid-phase extraction (MSPE) with Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry (UPLC-MS/MS) analysis, the detection of phenylpyrazoles (fipronil, fipronil sulfone, fipronil sulfide, fipronil de-sulfoxide, fipronil desulfinyl, ethiprole, and flufiprole) is achieved and shows good linearity at concentrations of 1-800µg L-1 (R2 ≥ 0.9930). The limit of detection (LOD), limit of quantification (LOQ), and recovery rates are 0.01-0.50µg kg-1, 0.04-1.72µg kg-1, and 70.96-115.32%, respectively. More importantly, this method is successfully applied to determine the phenylpyrazoles in commercial egg, poultry, milk, jujube, cabbage, tea, and rice with a detection rate of ≈0.04%. Therefore, the developed method may contribute to a new strategy for the purification and multi-target extraction of complex food matrices.

Detection and health implications of phthalates in tea beverages in market: Application of novel solid-phase microextraction fibers

Assessment and control of emerging organic pollutants in food have become critical for global food safety and health. The European Union has set standards for certain emerging organic pollutants, such as phthalic acid esters (PAEs) in food. Because of being endocrine disruptors, PAEs are toxic and carcinogenic to humans. Release of PAEs from packaging materials poses a potential risk to human health and causes environmental pollution. In this study, a highly sensitive analytical method for the detection of PAE contents in tea beverages was established using hydroxyl-functionalized covalent organic frameworks (COFs) as solid-phase microextraction (SPME) coating. Results indicate that functionalization with hydroxyl groups enhances the adsorption of PAEs. The proposed method exhibits a wide linear range (1–20,000 ng L−1), low limits of detection (> 0.048 ng L−1), and satisfactory recovery (72.8 %–127.3 %). To investigate the PAE contamination in beverages, contamination levels of six typical PAEs and their health impacts were surveyed across various brands/types/packaging materials of tea beverages sold in China. Results of the hazard quotient and hazard index approaches suggest no or extremely low health concerns regarding PAE levels. We observe that hydroxyl groups functionalized on COFs enhance the adsorption of PAEs. Moreover, an important outcome of this study is development of an efficient and sensitive direct detection method for PAEs in complex tea matrices, providing a reliable approach for the assessment of PAEs in other complex matrices.

Carboxy-PEG-thiol functionalized gold nanoparticle conjugates for the detection of SARS-CoV-2: Detection tools and analytical method development

Addressing the need for accessible SARS-CoV-2 testing, carboxy-PEG 12-thiol functionalized gold nanoparticles conjugates were developed for rapid point-of-care (POC) detection against SARS-CoV-2 spike protein, pseudo-SARS-CoV-2, and authentic Beta SARS-CoV-2 virus particles. These conjugates leverage gold nanoparticles (AuNPs) as signal transducers, cross-linked to either angiotensin-converting enzyme 2 (ACE2) or SARS-CoV-2 spike protein receptor-binding domain (RBD) antibodies as bioreceptors and showed a distinct color shift from pink to blue. To assess their POC feasibility, the conjugates were integrated into facemasks and breathalyzers, wherein aerosolized SARS-CoV-2 antigens were successfully detected, producing a color change within 10 and 30 minutes for the breathalyzer and facemask prototypes, respectively. Furthermore, we explored quantitative analysis using varying concentrations of SARS-CoV-2 spike protein. Both conjugates demonstrated a linear relationship between blue color intensity and virus concentration, with linear ranges of 0.08–0.6 ng/mL and 0.04–0.5 ng/mL, respectively. Low limits of detection and quantification were also achieved. They exhibited specificity, responding solely to SARS-CoV-2 even in complex matrices containing diverse proteins, including the SARS-CoV-1 spike protein. Precision tests yielded coefficient of variations below 2 %, showcasing their remarkable reproducibility. This work presents a promising approach for rapid, sensitive, and specific POC detection of SARS-CoV-2 paving the way for improved pandemic response and management.