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1.
J Sep Sci ; 47(15): e2400415, 2024 Aug.
Article in English | MEDLINE | ID: mdl-39118576

ABSTRACT

Porous cage materials with certain dimensions, sizes, shapes, and functions have been regarded as promising materials for sample preparation, chromatographic separation, and detection process. In contrast to infinite frameworks such as metal-organic frameworks or covalent organic frameworks, porous cage materials are constructed from discrete molecules containing at least one internal cavity. The well-defined cavities in porous cage materials provide opportunities for non-covalent interactions. These interactions can be programmed into the ligand design or supramolecular cage constructing using the cages as building blocks, offering various host-guest recognition with great selectivity. In this review, we desire to elucidate the fundamental principles governing the design and fabrication of porous cage materials with well-defined cavities, good solvent processability, and modifiable groups, the applications of these porous cage materials in sample preparation, chromatographic separation, and detection were discussed. The recent advantages of porous cage materials for the analysis process were summarized. We state the potential of these materials and provide an outlook for further application strategies. We expect that this review can inspire interest in the porous cage materials research area for analysis.

2.
J Chromatogr A ; 1734: 465293, 2024 Aug 20.
Article in English | MEDLINE | ID: mdl-39181092

ABSTRACT

The analysis of biological samples is highly valuable for disease diagnosis and treatment, forensic examination, and public safety. However, the serious matrix interference effect generated by biological samples severely affects the analysis of trace analytes. Sample preparation methods are introduced to address the limitation by extracting, separating, enriching, purifying trace target analytes from biological samples. With the raising demand of biological sample analysis, a review focuses on media for biological sample preparation and analysis over the last 5 years is presented. High-performance media in biological sample preparation are first reviewed, including porous organic frameworks, imprinted polymers, hydrogels, ionic liquids, and bioactive media. Then, application of media for different biological sample preparation and analysis is briefly introduced, including liquid samples of body fluids, solid samples (hair, feces, and tissues), and gas samples of exhale breath gas. Finally, conclusions and outlooks on media promoting biological sample preparation are presented.

3.
Anal Chem ; 2024 Jul 15.
Article in English | MEDLINE | ID: mdl-39007488

ABSTRACT

Monitoring changes in the expression of marker proteins in biological fluids is essential for biomarker-based disease diagnosis. Epithelial cell adhesion molecule (EpCAM) has been identified as a broad-spectrum biomarker for various chronic diseases and as a therapeutic target. However, the development of simple and reliable methods for quantifying EpCAM changes in biological fluids faces challenges due to the variability of its expression across different diseases, the presence of soluble forms, and matrix effects. In this paper, a surface-enhanced Raman scattering (SERS)-fluorescence (FL) dual-mode sensing method was established for quantification of trace EpCAM in biological fluids based on bimetallic Au@Ag nanoparticles and nitrogen-doped quantum dots encapsulated DNA hydrogel hybrid with graphene oxide (Au@Ag-NQDs/GO). The DNA hydrogel was constructed based on three-dimensional (3D) structure DNA-mediated strategy using an aptamer DNA (AptDNA) linker. The interaction of the AptDNA with EpCAM triggered the disassembly of the DNA hydrogel. Consequently, the release of Au@Ag nanoparticles induced an "on-off" switch in the SERS signal while the weakened FL quenching effect in Au@Ag-NQDs/GO system achieved "off-on" switch of FL signal, enabling the simultaneous SERS-FL quantification of EpCAM. The established dual-mode method exhibited outstanding sensitivity and stability in quantifying EpCAM in the range of 0.5-60.0 pg/mL, with the limits of detection (LODs) of SERS and FL as 0.17 and 0.35 pg/mL, respectively. When applied for real sample analysis, the method showed satisfactory specificity and recoveries in cancer cells lysate, serum, and urine samples with RSDs of 2.8-6.3%, 4.0-6.3%, and 2.8-5.7%, respectively. The developed SERS-FL sensing method offered a sensitive, reliable, and practical quantification strategy for trace EpCAM in diverse biological fluid samples, which would benefit the early diagnosis of disease and further health management.

4.
Anal Chem ; 96(27): 11036-11043, 2024 07 09.
Article in English | MEDLINE | ID: mdl-38934556

ABSTRACT

Escherichia coli O157:H7 is one of the most susceptible foodborne pathogens, easily causing food poisoning and other health risks. It is of great significance to establish a quantitative method with higher sensitivity and less time consumption for foodborne pathogens analysis. The Raman-silent signal has a good performance for avoiding interference from the food matrix so as to achieve accurate signal differentiation. In this work, we presented a preparation-mapping all-in-one method for digital mapping analysis. We prepared a functionalized Raman-silent polymer label of Escherichia coli O157:H7, which was captured on a porous 4-mercaptophenylboric acid@Ag foam chip. To improve accuracy and widen the detection range, a digital mapping quantitative strategy was employed in data extraction and processing. By transfer mapping information into digitized statistical results, the limitation of obtaining reproducible intensity values just by randomly selected spots on the substrate can be addressed. With a wide linear range of 1.0 × 101-1.0 × 105 CFU mL-1 and a limit of detection of 4.4 CFU mL-1, this all-in-one method had good sensitivity performance. Also, this method achieved good precision and selectivity in a series of experiments and was successfully applied to the analysis of beverage samples.


Subject(s)
Beverages , Escherichia coli O157 , Polymers , Spectrum Analysis, Raman , Escherichia coli O157/isolation & purification , Spectrum Analysis, Raman/methods , Beverages/analysis , Beverages/microbiology , Polymers/chemistry , Boron Compounds/chemistry , Food Microbiology/methods , Food Contamination/analysis , Sulfhydryl Compounds/chemistry , Sulfhydryl Compounds/analysis , Boronic Acids
5.
J Chromatogr A ; 1728: 465014, 2024 Aug 02.
Article in English | MEDLINE | ID: mdl-38797135

ABSTRACT

Developing novel chiral stationary phases (CSPs) with versatility is of great importance in enantiomer separation. This study fabricated a dual-chiral covalent organic framework (PA-CA COF) via successive post-synthetic modifications. The chiral trans-1,2-cyclohexanediamine (CA) and (D)-penicillamine (PA) groups were periodically aligned within nanochannels of the COF, allowing selective recognition of enantiomers through intermolecular interactions. It can be a versatile high-performance liquid chromatography (HPLC) CSP for separating a wide range of enantiomers, including chiral pharmaceutical intermediates and chiral drugs. With separation performance comparable to commercial chiral columns and even greater versatility, the PA-CA COF@SiO2 column held promise for practical applications. Chiral separation results combined with molecular simulation indicated that the mixed mode of PA and CA resulted in the broad separation capability of PA-CA COF. The introduction of the dual-chiral COFs concept opens up a new avenue for chiral recognition and separation, holding great potential for practical enantiomer separation.


Subject(s)
Penicillamine , Stereoisomerism , Chromatography, High Pressure Liquid/methods , Penicillamine/chemistry , Penicillamine/isolation & purification , Cyclohexylamines/chemistry , Cyclohexylamines/isolation & purification , Silicon Dioxide/chemistry , Metal-Organic Frameworks/chemistry
6.
Biosensors (Basel) ; 14(4)2024 Mar 29.
Article in English | MEDLINE | ID: mdl-38667156

ABSTRACT

Covalent organic frameworks (COFs) are porous crystals that have high designability and great potential in designing, encapsulating, and immobilizing nanozymes. COF nanozymes have also attracted extensive attention in analyte sensing and detection because of their abundant active sites, high enzyme-carrying capacity, and significantly improved stability. In this paper, we classify COF nanozymes into three types and review their characteristics and advantages. Then, the synthesis methods of these COF nanozymes are introduced, and their performances are compared in a list. Finally, the applications of COF nanozymes in environmental analysis, food analysis, medicine analysis, disease diagnosis, and treatment are reviewed. Furthermore, we also discuss the application prospects of COF nanozymes and the challenges they face.


Subject(s)
Metal-Organic Frameworks , Metal-Organic Frameworks/chemistry , Biosensing Techniques , Nanostructures , Chemistry, Analytic , Food Analysis , Chemistry Techniques, Analytical/methods
7.
J Chromatogr A ; 1721: 464849, 2024 Apr 26.
Article in English | MEDLINE | ID: mdl-38564930

ABSTRACT

A novel fluorinated covalent organic polymer @ attapulgite composite (F-COP@ATP) was prepared at room temperature for in-syringe membrane solid-phase extraction (SM-SPE) of domoic acid (DA) in aquatic products. Natural ore ATP has the advantages of low cost, good mechanical strength and abundant hydroxyl group on its surface, and in-situ modified F-COP layer can provide abundant adsorption sites. F-COP@ATP combining the advantages of F-COP and ATP, becomes an ideal adsorbent for DA extracting. Moreover, a high-throughput sample preparation strategy was carried out by using the F-COP@ATP membrane as syringe filter and assembling syringes with a ten-channel injection pump. In addition, the experimental factors were optimized, such as pH of extract, amount of adsorbent, velocity of extraction and desorption, type and volume of desorption solvent. The DA analytical method was established by SM-SPE-HPLC/tandem mass spectrometry. The method had a wide linear range with low limit of detection (0.344 ng/kg) and low limit of quantification (1.14 ng/kg). F-COP@ATP membrane can be reused more than five times. The method realized the analysis of DA in scallop and razor clam samples, which shows its application prospect in practical analysis. This study provided an efficient, low-energy and mild idea for preparing other reusable natural mineral ATP-based composite materials for separation and enrichment, which reduces the experimental cost and is closer to environmental protection and green chemistry to a certain extent.


Subject(s)
Fluorocarbon Polymers , Kainic Acid/analogs & derivatives , Magnesium Compounds , Silicon Compounds , Solid Phase Extraction , Temperature , Chromatography, High Pressure Liquid/methods , Solid Phase Extraction/methods , Adenosine Triphosphate
8.
Sensors (Basel) ; 24(7)2024 Mar 24.
Article in English | MEDLINE | ID: mdl-38610279

ABSTRACT

This review introduces a micro-integrated device of microfluidics and fiber-optic sensors for on-site detection, which can detect certain or several specific components or their amounts in different samples within a relatively short time. Fiber-optics with micron core diameters can be easily coated and functionalized, thus allowing sensors to be integrated with microfluidics to separate, enrich, and measure samples in a micro-device. Compared to traditional laboratory equipment, this integrated device exhibits natural advantages in size, speed, cost, portability, and operability, making it more suitable for on-site detection. In this review, the various optical detection methods used in this integrated device are introduced, including Raman, ultraviolet-visible, fluorescence, and surface plasmon resonance detections. It also provides a detailed overview of the on-site detection applications of this integrated device for biological analysis, food safety, and environmental monitoring. Lastly, this review addresses the prospects for the future development of microfluidics integrated with fiber-optic sensors.

9.
J Chromatogr A ; 1720: 464775, 2024 Apr 12.
Article in English | MEDLINE | ID: mdl-38452559

ABSTRACT

The contents of target substances in biological samples are usually at low concentration levels, and the matrix of biological samples is usually complex. Sample preparation is considered a very critical step in bioanalysis. At present, the utilization of microextraction sampling technology has gained considerable prevalence in the realm of biological analysis. The key developments in this field focus on the efficient microextraction media and the miniaturization and automation of adaptable sample preparation methods currently. In this review, the recent progress on the microextraction sampling technologies for bioanalysis has been introduced from point of view of the preparation of microextraction media and the microextraction sampling strategies. The advance on the microextraction media was reviewed in detail, mainly including the aptamer-functionalized materials, molecularly imprinted polymers, carbon-based materials, metal-organic frameworks, covalent organic frameworks, etc. The advance on the microextraction sampling technologies was summarized mainly based on in-vivo sampling, in-vitro sampling and microdialysis technologies. Moreover, the current challenges and perspective on the future trends of microextraction sampling technologies for bioanalysis were briefly discussed.


Subject(s)
Solid Phase Microextraction , Specimen Handling , Solid Phase Microextraction/methods , Technology , Molecularly Imprinted Polymers , Automation
10.
Talanta ; 273: 125901, 2024 Jun 01.
Article in English | MEDLINE | ID: mdl-38503122

ABSTRACT

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)-NH2@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.


Subject(s)
Benzamidines , Disinfection , Metal-Organic Frameworks , Tandem Mass Spectrometry , Chromatography, Liquid , Disinfection/methods , Tandem Mass Spectrometry/methods , Solid Phase Extraction/methods , Chromatography, High Pressure Liquid/methods
11.
Anal Chem ; 96(14): 5368-5374, 2024 Apr 09.
Article in English | MEDLINE | ID: mdl-38528372

ABSTRACT

A gas membrane separation/array fluorescence visualization (GMS/AFV) device is developed by integrating hydrazine-based carbonized copolymer dots (PD-N2H4) for visual on-site analysis. The novel PD-N2H4 was synthesized using a "polymer template" approach, exhibiting strong blue fluorescence capable of visual sensing. The GMS/AFV device integrates sample preparation and detection all-in-one, consisting of a smartphone, a sample pretreatment system, and an optical system. In the detection procedure, the samples will be treated in the sample pretreatment system to create volatile gases. Therefore, any gas samples as well as solid and liquid samples that potentially produce volatile gases can be visually detected on-site by the device. H2S was utilized as a model analyte to test the practicality of the GMS/AFV device. The entire analysis can be finished in 3 min, and the limit of detection of H2S is as low as 3.4 µg/L. Surprisingly, the device is also capable of high-throughput sample detection, which can process 48 samples simultaneously in about 20 min. The device offers a quick, easy, cheap, and environmentally friendly way to analyze volatile gases, and it creates new opportunities for on-site detection of complex samples.

12.
Biosens Bioelectron ; 255: 116227, 2024 Jul 01.
Article in English | MEDLINE | ID: mdl-38552524

ABSTRACT

Food safety represents a critical global public health issue, with safety challenges posed by foodborne pathogens garnering extensive attention. Therefore, we introduce a co-recognition, enrichment and sensing (CES) all-in-one strategy for analysis of bacteria with low background and high specificity. This method employs antimicrobial peptide (AMP) functionalized magnetic nanoparticles (MNPs) to enrich bacteria and uses aptamer@Au@PBA (KxMFe(CN)6 (M = Pb and Ni)) NPs as silent SERS tags. When both S. aureus and E. coli O157:H7 are present, the silent SERS probes could specifically label the target bacteria, forming a sandwich-like structure. This binding induces silent Raman shifts (2139 cm-1 and 2197 cm-1), enabling quantification of two bacteria. Coupling with the modular flexible microfluidics and magnetic control slider device, this platform facilitates rapid switching between magnetic loading and elution. The CES SERS method demonstrated linear relationships for both S. aureus and E. coli O157:H7 at 50-1600 cfu mL-1, with detection limits of 14 and 18 cfu mL-1, respectively. The method achieved recovery rates of 85.6-112% and relative standard deviations of 1.5-8.6%. Validation using the ELISA method revealed relative errors between -7.5 and 4.3%. The CES approach has potential applications in food safety, environmental monitoring, and biomedical diagnosis.


Subject(s)
Biosensing Techniques , Metal Nanoparticles , Metal Nanoparticles/chemistry , Staphylococcus aureus , Escherichia coli , Microfluidics , Biosensing Techniques/methods , Bacteria , Magnetic Phenomena , Spectrum Analysis, Raman/methods , Gold/chemistry
13.
Anal Chem ; 2024 Feb 09.
Article in English | MEDLINE | ID: mdl-38335969

ABSTRACT

The combined application of nanozymes and surface-enhanced Raman scattering (SERS) provides a promising approach to obtain label-free detection. However, developing nanomaterials with both highly efficient enzyme-like activity and excellent SERS sensitivity remains a huge challenge. Herein, we proposed one-step synthesis of Mo2N nanoparticles (NPs) as a "two-in-one" substrate, which exhibits both excellent peroxidase (POD)-like activity and high SERS activity. Its mimetic POD activity can catalyze the 3,3',5,5'-tetramethylbenzidine (TMB) molecule to SERS-active oxidized TMB (ox-TMB) with high efficiency. Furthermore, combining experimental profiling with theory, the mechanism of POD-like activity and SERS enhancement of Mo2N NPs was explored in depth. Benefiting from the outstanding properties of Mo2N NPs, a versatile platform for indirect SERS detection of biomarkers was developed based on the Mo2N NPs-catalyzed product ox-TMB, which acts as the SERS signal readout. The feasibility of this platform was validated using glutathione (GSH) and target antigens alpha-fetoprotein antigen (AFP) and carcinoembryonic antigen (CEA) as representatives of small molecules with a hydroxyl radical (·OH) scavenging effect and proteins with a low Raman scattering cross-section, respectively. The limits of detection of GSH, AFP, and CEA were as low as 0.1 µmol/L, 89.1, and 74.6 pg/mL, respectively. Significantly, it also showed application in human serum samples with recoveries ranging from 96.0 to 101%. The acquired values based on this platform were compared with the standard electrochemiluminescence method, and the relative error was less than ±7.3. This work not only provides a strategy for developing highly active bifunctional nanomaterials but also manifests their widespread application for multiple biomarkers analysis.

14.
Anal Chem ; 96(9): 3933-3941, 2024 Mar 05.
Article in English | MEDLINE | ID: mdl-38359085

ABSTRACT

Accurate discrimination of metal species is a significant analytical challenge. Herein, we propose a novel methodology based on liquid-phase cyclic chemiluminescence (CCL) for the identification of cobalt speciation. The CCL multistage signals (In) of the luminol-H2O2 reaction catalyzed by different cobalt species have different decay coefficients k. Thereby, we can facilely identify various cobalt species according to the distinguishable k values, including the complicated and structurally similar cobalt complexes, such as analogues of [Co(NH3)5X]n+ (X = Cl-, H2O, and NH3), Co(II) porphyrins, and bis(2,4-pentanedione) cobalt(II) derivatives. Especially, the number of substituent atoms also influences the k value greatly, which allows excellent discrimination between complexes that only have a subtle difference in the substituent group. In addition, linear discriminant analysis based on In provides a complementary solution to improve the differentiating ability. We performed density functional theory calculations to investigate the interaction mode of H2O2 over cobalt species. A close negative correlation between the adsorption energy and the k value is observed. Moreover, the calculation of energy evolutions of H2O2 decomposition into a double hydroxide radical shows that a high level of consistency exists between the activation energy barrier and the k value. The results further demonstrate that the decay coefficient of the CCL multistage signal is associated with the catalytic reactivity of the cobalt species. Our work not only broadens the application of chemiluminescence but also provides a complementary technology for speciation analysis.

15.
Animal Model Exp Med ; 2024 Jan 15.
Article in English | MEDLINE | ID: mdl-38225728

ABSTRACT

BACKGROUD: Thoracic Trauma and Limb Fractures Are the Two most Common Injuries in Multiple Trauma. However, there Is Still a Lack of Mouse Models of Trauma Combining Tibial Shaft Fracture (TSF) and Thoracic Trauma. In this Study, we Attempted to Develop a Novel Mouse Model of TSF Combined with Blunt Chest Trauma (BCT). METHODS: A total of 84 C57BL/6J male mice were used as the multiple trauma model. BCT was induced by hitting the chests of mice with heavy objects, and TSF was induced by hitting the tibia of mice with heavy objects after intramedullary fixation. Serum specimens of mice were received by cardiac puncture at defined time points of 0, 6, 12, 24, 48, and 72 h. RESULTS: Body weight and body temperature tended to decrease within 24 h after multiple trauma. Hemoglobin analyses revealed a decrease during the first 24 h after multiple trauma. Some animals died by cardiac puncture immediately after chest trauma. These animals exhibited the most severe pulmonary contusion and hemorrhage. The level of lung damage varied in diverse mice but was apparent in all animals. Classic hematoxylin and eosin (H&E)-stained paraffin pulmonary sections of mice with multiple trauma displayed hemorrhage and an immunoinflammatory reaction. Bronchoalveolar lavage fluid (BALF) and serum samples of mice with multiple trauma showed an upregulation of interleukin-1ß (IL-1ß), IL-6, and tumor necrosis factor-1α (TNF-1α) compared with the control group. Microimaging confirmed the presence of a tibia fracture and pulmonary contusion. CONCLUSIONS: The novel mouse multiple trauma model established in this study is a common trauma model that shows similar pathological mechanisms and imaging characteristics in patients with multiple injuries. This study is useful for determining whether blockade or intervention of the cytokine response is beneficial for the treatment of patients with multiple trauma. Further research is needed in the future.

16.
Anal Chem ; 96(3): 1380-1389, 2024 Jan 23.
Article in English | MEDLINE | ID: mdl-38197385

ABSTRACT

In enantiomer recognition and separation, a highly enantioselective approach with universal applicability is urgently desired but hard to realize, especially in the case of chiral molecules. To resolve the trade-off between enantioselectivity and universality, a glutathione (GSH) and methylated cyclodextrins (MCD)-functionalized covalent organic framework (GSH-MCD COF) with porosity and abundant chiral surfaces is presented that was designed and synthesized for recognition and separation of various enantiomers. As expected, the GSH-MCD COF can be used as chiral stationary phases for the separation of various enantiomers, including aromatic alcohols, aromatic acids, amides, amino acids, and organic acids, with performance and versatility even superior to some widely used commercial chiral chromatographic columns. Furthermore, the synthesized GSH-MCD COF shows high enantioselectivity for the rapid recognition and identification of enantiomers and chiral metabolites when coupling to Raman spectroscopy. Molecular simulations suggest that the COF provides a confined microenvironment for cyclodextrins and peptides that dictates the separation and recognition capability. This work provides a strategy to synthesize synergetic multichiral COF and achieve separations and recognitions of enantiomers in complex samples.

17.
Talanta ; 271: 125653, 2024 May 01.
Article in English | MEDLINE | ID: mdl-38218057

ABSTRACT

In analysis of complex samples, the stability and sensitivity of surface-enhanced Raman scattering (SERS) substrates may be compromised by matrix interference. To address this issue, a membrane substrate was prepared for fast enrichment, separation, and detection of chrysoidine all-in-one. The silver nanoparticles modified sulfur-containing POSS polymer (AgNPs/POSS-P-S) SERS membrane substrate was fabricated using polyhedral oligomeric silsesquioxane (POSS) as support materials. Through in-situ growth, AgNPs were uniformly modified on POSS-P-S to ensure the stability and SERS activity of the membrane substrate. The enhancement factor of the malachite green was up to 5.3 × 105. By loading the AgNPs/POSS-P-S on membrane, on the other hand, the SERS membrane substrate can also serve as an adsorption medium for separating chrysoidine from sample matrix. Furthermore, the specific sensing mechanism of AgNPs/POSS-P-S for chrysoidine was investigated and a fast, sensitive, and selective method for its quantification was established, with a linear range of 0.010-2.0 mg/L and the limits of detection at 3.7 µg/L. In addition, the SERS method was successfully applied for the analysis of chrysoidine in beverages and chili products with the recoveries in the range of 83.5%-113.4 % and the relative standard deviations in 3.2%-9.0 %. The proposed AgNPs/POSS-P-S membrane based SRES method has great potential for rapid chrysoidine analysis in food samples.


Subject(s)
Metal Nanoparticles , Silver , p-Aminoazobenzene/analogs & derivatives , Spectrum Analysis, Raman/methods , Adsorption , Sulfur
18.
J Hazard Mater ; 465: 133084, 2024 03 05.
Article in English | MEDLINE | ID: mdl-38039811

ABSTRACT

Per- and polyfluoroalkyl substances (PFASs) and polychlorinated naphthalenes (PCNs) are of growing concern due to their toxic effects on the environment and human health. There is an urgent need for strategies to monitor and analyze the coexistence of PFASs and PCNs, especially in food samples at trace levels, to ensure food safety. Herein, a novel ß-cyclodextrin (ß-CD) derived fluoro-functionalized covalent triazine-based frameworks named CD-F-CTF was firstly synthesized. This innovative framework effectively combines the porous nature of the covalent organic framework and the host-guest recognition property of ß-CD enabling the simultaneous extraction of PFASs and PCNs. Under the optimal conditions, a simple and rapid method was developed to analyze PFASs and PCNs by solid-phase extraction (SPE) based simultaneous extraction and stepwise elution (SESE) strategy for the first time. When coupled with liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) and gas chromatography-tandem mass spectrometry (GC-MS/MS), this method achieved impressive detection limits for PFASs (0.020 -0.023 ng/g) and PCNs (0.016 -0.075 ng/g). Furthermore, the excellent performance was validated in food samples with recoveries of 76.7-107 % (for PFASs) and 78.0-108 % (for PCNs). This work not only provides a simple and rapid technique for simultaneous monitoring of PFASs and PCNs in food and environmental samples, but also introduces a new idea for the designing novel adsorbents with multiple recognition sites.


Subject(s)
Fluorocarbons , Tandem Mass Spectrometry , Humans , Tandem Mass Spectrometry/methods , Gas Chromatography-Mass Spectrometry/methods , Naphthalenes , Chromatography, High Pressure Liquid/methods , Solid Phase Extraction/methods , Fluorocarbons/analysis
19.
J Chromatogr A ; 1713: 464499, 2024 Jan 04.
Article in English | MEDLINE | ID: mdl-37983987

ABSTRACT

Supramolecular macrocycle-based covalent organic frameworks (COFs) are promising adsorbents for adsorption of hazards due to their host-guest recognition property. However, most supramolecular macrocycles are conformationally flexible, making them challenging to introduce into COFs. In this work, a calix[6]arene-based COF (CX6-BD COF) was fabricated with a unique flower-like morphology and high crystallinity. Especially, the cavity of CX6 exhibited host-guest inclusion interaction for sulfonamides (SAs), which was verified by quantum chemistry calculation. The integration of the porosity of COFs with the recognition cavity of CX6 made CX6-BD COF display excellent enrichment performance for SAs, with good enrichment factors (EFs) between 77 and 96. The material was employed as an adsorbent for COF membrane filter extraction, coupled with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) to simultaneously enrich and determine seven SAs in animal-derived food. The analytical method showed a wide linear range (0.01-100 µg/L and 0.05-100 µg/L) and low detection limits (3-10 ng/L). The established method was successfully applied to sensitively determine SAs in chicken, pork and beef samples, which achieved satisfactory recoveries (73.8-113%). These results demonstrated CX6-BD COF has good application potential in determination of trace and ultra-trace SAs in complex food matrices as an adsorbent.


Subject(s)
Metal-Organic Frameworks , Animals , Cattle , Chromatography, High Pressure Liquid , Metal-Organic Frameworks/chemistry , Tandem Mass Spectrometry , Sulfonamides/analysis , Solid Phase Extraction/methods , Sulfanilamide/analysis , Limit of Detection
20.
Anal Chem ; 95(49): 18149-18157, 2023 12 12.
Article in English | MEDLINE | ID: mdl-38044549

ABSTRACT

Improving the speediness of complex sample analysis has attracted much research interest in analytical science. In this work, an enrichment-sensing all-in-one strategy was presented for rapid surface-enhanced Raman spectroscopy (SERS) analysis of purine components by using the La(OH)3-Au@AgNPs nanocomposite. Two-dimensional (2D) La(OH)3 nanosheets with nanothickness and accessible active sites not only acted as efficient media for the rapid enrichment of analytes but also provided flat planes for the intensive decoration of Au@AgNPs nanoparticles to amplify the SERS signals of adsorbed analytes. The nanocomposite could realize the rapid enrichment-sensing of purine components in 1 min, including mercaptopurine, thioguanine, adenine, and purine. Subsequently, the surface adsorption behaviors were explored by density functional theory and the enhancement mechanisms were simulated by the finite-difference time-domain method. Moreover, the nanocomposite also exhibited good SERS performances with relative standard deviations (RSDs) of uniformity less than 6.5% (n = 23), RSDs of batch-to-batch stability less than 7.3% (n = 9), and long-term stability over 9 weeks with RSDs within 6.6%. Finally, the enrichment-sensing strategy was applied for the rapid SERS analysis of two projects: mercaptopurine in tablets and adenine in beers with detection limits of 6.0 and 0.76 µg/L and spiked recoveries of 90.9-100 and 84.2-101%, respectively. Benefiting from the high-performance enrichment medium and closely packed plasmonic nanoparticles, the enrichment-sensing all-in-one strategy possesses great potential for rapid on-site detection in food safety and pharmaceutical analysis.


Subject(s)
Metal Nanoparticles , Nanocomposites , Spectrum Analysis, Raman/methods , Mercaptopurine , Nanocomposites/chemistry , Adenine , Metal Nanoparticles/chemistry
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