ABSTRACT
The use of pesticides has increased with the development of agriculture. However, due to the trace content and the matrix's inherent complexity in environmental water, development of rapid and sensitive detection method present significant challenges in the analysis of pesticide residues. The study synthesized magnetic graphene oxide (MGO) by combining superparamagnetic nanoparticles with the easy modification of graphene oxide (GO). Covalent organic frameworks (COFs) were then modified to have a large specific surface area. Finally, magnetic graphene oxide-based covalent organic frameworks, namely MGO-COFs, were obtained with a spherical structure and used as magnetic solid-phase extraction materials, which was successfully used to determine the seven pesticide residues in environmental samples in conjunction with high performance liquid chromatography. The method has a wide linear range for the tested pesticides, with satisfactory correlation coefficients (R ≥ 0.099) and low detection limits (0.3-1.21 µg L-1). The correlation coefficients for all seven pesticides were high (R2 ≥ 0.9996). The spiked recoveries, exhibiting a range of 91.3 to 109 %, demonstrated that the developed MGO-COF-MSPE-HPLC-UV method is simple, efficient, and suitable for the analysis and detection of seven pesticide residues in environmental water.
ABSTRACT
This study examined the suppressive effects of 16 selected plant-based foods on α-glucosidase and pancreatic lipase and their antioxidant properties. Among these, the bark of Cinnamomum cassia (Cinnamon, WLN-FM 15) showed the highest inhibitory activity against α-glucosidase and the highest antioxidant activity. Additionally, WLN-FM 15 showed promising results in the other tests. To further identify the bioactive constituents of WLN-FM 15, a multi-bioactivity-labeled molecular networking approach was used through a combination of GNPS-based molecular networking, DPPH-HPLC, and affinity-based ultrafiltration-HPLC. A total of nine procyanidins were identified as antioxidants and inhibitors of α-glucosidase and pancreatic lipase in WLN-FM 15. Subsequently, procyanidins A1, A2, B1, and C1 were isolated, and their efficacy was confirmed through functional assays. In summary, WLN-FM 15 has the potential to serve as a functional food ingredient with the procyanidins as its bioactive constituents. These results also suggest that the multi-bioactivity-labeled molecular networking approach is reliable for identifying bioactive constituents in plant-based foods.
Subject(s)
Antioxidants , Biflavonoids , Catechin , Cinnamomum aromaticum , Glycoside Hydrolase Inhibitors , Lipase , Plant Bark , Proanthocyanidins , Proanthocyanidins/pharmacology , Proanthocyanidins/chemistry , Proanthocyanidins/analysis , Lipase/antagonists & inhibitors , Lipase/metabolism , Antioxidants/pharmacology , Antioxidants/chemistry , Antioxidants/analysis , Glycoside Hydrolase Inhibitors/pharmacology , Glycoside Hydrolase Inhibitors/chemistry , Plant Bark/chemistry , Cinnamomum aromaticum/chemistry , Biflavonoids/pharmacology , Biflavonoids/analysis , Biflavonoids/chemistry , Catechin/analysis , Catechin/chemistry , Catechin/pharmacology , Plant Extracts/chemistry , Plant Extracts/pharmacology , Chromatography, High Pressure Liquid , Pancreas/enzymology , alpha-Glucosidases/metabolism , Network Pharmacology , Enzyme Inhibitors/pharmacology , Enzyme Inhibitors/chemistryABSTRACT
Molecularly imprinted polymer with water-compatibility for effective separation and enrichment of targeted trace pollutants from complicated matrix has captured extensive attention in terms of their high selectivity and matrix compatibility. This study focuses on modified ß-cyclodextrin is used as a hydrophilic functional monomer to develop magnetic molecularly imprinted polymers (MMIPs). MMIPs were prepared using Fe3O4 nanoparticles as carriers and bisphenol A (BPA) as templates using a two-step fixation strategy and surface imprinting technology. The structural characteristic and binding properties of the prepared MMIPs were thoroughly studied. The MMIPs exhibited high crystallinity, high adsorption capacity, fast rebinding rate, remarkable selectivity and distinguish reusability. In addition, through magnetic solid-phase extraction separation technology and high-performance liquid chromatography ultraviolet quantitative detection technology, MMIPs are used for selective enrichment and detection of BPA in complex media such as environmental water and milk. This work provides a new route to construct the hydrophilic molecularly imprinted materials and a new sight on developing more effective sample pretreatment strategies for monitoring targeted pollution in complicated aqueous media.
Subject(s)
Benzhydryl Compounds , Hydrophobic and Hydrophilic Interactions , Molecularly Imprinted Polymers , Phenols , Solid Phase Extraction , Water Pollutants, Chemical , Benzhydryl Compounds/analysis , Benzhydryl Compounds/chemistry , Phenols/analysis , Phenols/chemistry , Molecularly Imprinted Polymers/chemistry , Solid Phase Extraction/methods , Adsorption , Chromatography, High Pressure Liquid/methods , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/chemistry , Molecular Imprinting , Milk/chemistry , Magnetite Nanoparticles/chemistry , Animals , beta-Cyclodextrins/chemistry , Limit of DetectionABSTRACT
The identification of dietary exposure biomarkers is crucial for advancing our understanding of the health benefits of specific foods. Broccoli, a vegetable with well-known anticancer properties, contains active ingredients, such as isothiocyanates with indole side chains. Hence, indole metabolites related to broccoli consumption have the potential to serve as biomarkers of dietary exposure. In this work, we developed a new analytical method for indole metabolites in urine using a poly(deep eutectic solvents)-molecularly imprinted polymer/vinyl-functionalized graphene oxide (PDESs-MIP/VGO) in miniaturized centrifugal pipet-tip solid-phase extraction (CPT-SPE) coupled with liquid chromatography. This method integrates the strengths of PDESs-MIP/VGO, including rich adsorption interactions, high adsorption capacity, and excellent selectivity, with the simplicity and cost-effectiveness of CPT-SPE. The proposed method demonstrated low limits of quantification (1.2-2.5 ng mL-1), high accuracy (91.7-104.8%), and good precision (relative standard deviation ≤4.4%). By applying this method to analyze indole metabolites in urine, our results suggested that indole-3-carbinol and indole-3-acetonitrile have the potential to emerge as reliable dietary exposure biomarkers for broccoli intake. Furthermore, highly selective analytical methods based on molecular imprinting technology are advantageous for precise screening and analysis of dietary exposure biomarkers associated with food consumption.
Subject(s)
Biomarkers , Brassica , Indoles , Solid Phase Extraction , Humans , Indoles/urine , Indoles/metabolism , Biomarkers/urine , Brassica/chemistry , Brassica/metabolism , Solid Phase Extraction/methods , Dietary Exposure , Chromatography, High Pressure Liquid/methods , Molecularly Imprinted Polymers/chemistry , Molecularly Imprinted Polymers/metabolism , GraphiteABSTRACT
Perfluoroalkyl acids (PFAAs) are emerging pollutants that endangers food safety. Developing methods for the selective determination of trace PFAAs in complex samples remains challenging. Herein, an ionic liquid modified porous imprinted phenolic resin-dispersive filter extraction-liquid chromatography-tandem mass spectrometry (IL-PIPR-DFE-LC-MS/MS) method was developed for the determination of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in eggs. The new IL-PIPR adsorbent was prepared at room temperature, which avoids the disorder and instability of the template at high temperatures. The imprinting factor of IL-PIPR for PFOA and PFOS exceeded 7.3. DFE, combined with IL-PIPR (15 mg), was used to extract PFOA and PFOS from eggs within 15 min. The established method exhibits low limits of detection (0.01-0.02 ng/g) and high recoveries (84.7%-104.7%), which surpass those of previously reported methods. This work offers a new approach to explore advanced imprinted adsorbents for PFAAs, efficient sample pretreatment technique, and analytical method for pollutants in foods.
Subject(s)
Eggs , Fluorocarbons , Food Contamination , Ionic Liquids , Molecular Imprinting , Tandem Mass Spectrometry , Fluorocarbons/isolation & purification , Fluorocarbons/analysis , Fluorocarbons/chemistry , Eggs/analysis , Food Contamination/analysis , Ionic Liquids/chemistry , Alkanesulfonic Acids/analysis , Alkanesulfonic Acids/isolation & purification , Alkanesulfonic Acids/chemistry , Caprylates/chemistry , Caprylates/analysis , Caprylates/isolation & purification , Adsorption , Animals , Solid Phase Extraction/methods , Solid Phase Extraction/instrumentation , ChickensABSTRACT
This study presents novel methodologies and materials for selectively and sensitively determining gibberellin traces in licorice to address food safety concerns. A novel hydrophilic imprinted resin-graphene oxide composite (HMIR-GO) was developed with fast mass transfer, high adsorption capacity, and exceptional aqueous recognition performance for gibberellin. Leveraging the advantages of molecular imprinting, hydrophilic resin synthesis, and rapid mass transfer characteristics of GO, HMIR-GO was employed as an adsorbent, showing resistance to matrix interference. Coupled with HPLC, a rapid and selective method for determining gibberellin was established. Under optimal conditions, the method exhibited a wide linear range (0.02-5.00 µg g-1, r = 0.9999), low detection limits (3.3 ng g-1), and satisfactory recoveries (92.0-98.4%), enabling the accurate and rapid detection of gibberellin in licorice. This study introduces a pioneering strategy for the selective extraction and determination of trace gibberellin levels, offering insights for similar applications in functional foods.
Subject(s)
Gibberellins , Glycyrrhiza , Graphite , Hydrophobic and Hydrophilic Interactions , Molecular Imprinting , Graphite/chemistry , Glycyrrhiza/chemistry , Gibberellins/chemistry , Gibberellins/analysis , Gibberellins/isolation & purification , Adsorption , Solid Phase Extraction/methods , Solid Phase Extraction/instrumentation , Chromatography, High Pressure Liquid , Limit of DetectionABSTRACT
The escalating use of pesticides on fruits and vegetables has raised concerns about potential health risks. Therefore, we developed a superhydrophilic resin/graphene oxide (SR/GO) with rich adsorption interactions using an eco-friendly synthetic approach. SR/GO demonstrated excellent hydrophilicity, ensuring optimal contact with aqueous sample matrices. The multiple adsorption interactions, including π-π conjugation, hydrogen bonding, and electrostatic adsorption, facilitated multi-pesticide residue co-extraction. The synthesized SR/GO was applied to a miniaturized centrifugation-accelerated pipette-tip extraction method, coupled with high-performance liquid chromatography. The optimized method exhibited low consumption (15.0 mg adsorbent), and high efficiency, with low detection limits (1.4-2.9 ng g-1) and high recoveries (75.3-113.0%). Water-compatible SR/GO, along with a miniaturized extraction process, showcases a potent analytical approach for pesticide residue analysis in fruits and vegetables. The significance of this method lies in its ability to ensure agricultural and food safety by using a low-cost and efficient multi-pesticide residue analytical strategy.
Subject(s)
Fruit , Vegetables , Hydrophobic and Hydrophilic Interactions , Graphite/chemistry , Pesticide Residues/chemistry , Fruit/chemistry , Vegetables/chemistry , Pyrus/chemistry , Citrullus/chemistry , Solanum lycopersicum/chemistry , Malus/chemistry , Cucurbita/chemistry , Chromatography, High Pressure LiquidABSTRACT
Nanozymes have gained much attention as a replacement for natural enzymes duo to their unique advantages. Two-dimensional layered double hydroxide (LDH) nanomaterials with high physicochemical plasticity are emerging as the main forces for the construction of nanozymes. Unfortunately, high-performance LDH nanozymes are still scarce. Recently, defects in nanomaterials have been verified to play a significant role in modulating the catalytic microenvironment, thereby improving catalytic performances of nanozymes. Therefore, the marriage between defect engineering and LDH nanozymes is expected to spark new possibilities. In this work, twenty kinds of natural amino acids were separately inserted into the interlayer of CoFe-LDH to obtain defect-rich CoFe-LDH nanozymes. The peroxidase (POD)-like activity and catalytic mechanism of the as-prepared LDH nanozymes were systematically studied. The results showed that the intercalation of amino acids can effectively enhance the POD-like activity of LDH nanozymes owing to the increasing oxygen/metal vacancies. And l-cysteine intercalated LDH exhibited the highest catalytic activity ascribed to its thiol group. As a proof of concept, LDH nanozymes with superb POD-like activity were used in biosensing and antibacterial applications. This work suggests that modulating the catalytic microenvironment through defect engineering is an effective way to obtain high-efficiency POD mimics.
ABSTRACT
It is extremely significant while challenging to accurately detect low-levels of perfluoroalkyl carboxylic acid compounds (PFCAs) in environmental water. Herein, adopting perfluorotetradecanoic acid as the dummy template, selective molecularly imprinted composites (CNTs@ILs@MIPs) grafted carbon nanotubes integrating hydrophilic ionic liquids were successfully prepared via surface imprinting and dummy-template imprinting techniques. The obtained CNTs@ILs@MIPs were applied as selective extraction adsorbent for specifically extract PFCAs in environmental water coupled with gas chromatography-mass spectrometry quantification. Detailed studies were conducted on the main preparation parameters and extraction conditions. The CNTs@ILs@MIPs displayed excellent adsorptivity, and the established method exhibited low LODs (0.60-1.64 ng L-1), wide linearity with R2 above 0.9994, and satisfactory adsorption recoveries (80.5-112.5%) for seven PFCAs. This proposed method provides a new applicable approach for the detection of targeted pollutants in environmental water by utilizing the high affinity and recognition ability of molecularly imprinted carbon nanotube functional materials modified with ionic liquids.
ABSTRACT
In this study, a novel three-dimensional hierarchical porous deep eutectic solvents-modified graphene aerogel (3D DES-GA) was synthesized for use as a solid-phase microextraction (SPME) fiber coating. The SPME fiber was characterized by its fluffy and hierarchical porous structure, uniform thickness, and rapid mass transfer capabilities. This fiber demonstrated a lifetime (≥160 uses) and excellent precision (with relative standard deviations of 2.4-6.6% for single fiber and 6.0-9.8% for fiber-to-fiber repeatability). The SPME fiber also exhibited remarkable extraction performance for polycyclic aromatic hydrocarbons and polychlorinated biphenyls, which are common persistent organic pollutants in environmental samples. When combined with gas chromatography-tandem mass spectrometry, the method allowed for high-efficiency extraction (enrichment factors ranging from 1225 to 4652 folds) and sensitive determination (limit of detection ranging from 0.010 to 0.056 pg g-1) of polychlorinated naphthalenes (PCNs) in complex samples. To validate this method, we applied it to the determination of four PCNs in five types of fish tissues. The results revealed the presence of 1-chloronaphthalene at concentrations of 7.0 ± 2.9-34.8 ± 2.1 pg g-1 and 1,4-dichloronaphthalene at concentrations of 6.0 ± 0.3-10.9 ± 1.4 pg g-1 in three fish species. Compared with reported sample pretreatment methods reported in the literature, this proposed headspace SPME method offers additional advantages, including simplicity of operation and reduced sample and organic solvent consumption.
ABSTRACT
The residues of polychlorinated naphthalenes (PCNs) produced in multiple industrial production and life processes are continuously entering environmental waters through atmospheric deposition and land drainage, and the water pollution caused by PCNs is continuing public concern due to their potential threat to aquatic ecosystems and public health. Herein, a new chlorine-functionalized covalent organic framework anchored graphene aerogel (COF-GA) was synthesized by covalent modification technology and used as fiber coating of solid-phase microextraction for synergically enhanced extraction of PCNs in environmental water. The extraction efficiency of COF-GA coated fiber was superior to commercial fiber due to the multiple interactions (π-π, hydrophobic interaction, and halogen bonding interaction). The COF-GA coated fiber has good stability, can avoid water vapor interference at 80 °C for a long time (30 -50 min) to maintain adsorption equilibrium, and can be reused at least 96 times. Combined with gas chromatography-tandem mass spectrometry, a sensitive method for the high-efficient enrichment (enrichment factors were 501 -7453 folds) and ultra-sensitive detection (LODs were 0.001 -0.428 pg/mL) of PCNs in environmental water was established. The enrichment factor for PCNs is significantly higher than in previous studies. This proposed method provides new technical support for the daily monitoring and risk assessment of trace PCNs in environmental water.
ABSTRACT
The defatted seeds of evening primrose (DE), a by-product of evening primrose oil extraction, are currently underutilized. This study aimed to valorize DE by examining its effects on melanogenesis and tyrosinase activity in zebrafish embryos and in vitro, and an innovative affinity-labeled molecular networking workflow was proposed for the rapid identification of tyrosinase inhibitors in DE. Our results indicated DE significantly reduced melanin content (53.3 % at 100 µg/mL) and tyrosinse activity (80.05 % for monophenolase and 70.40 % for diphenolase at 100 µg/mL). Furthermore, through the affinity-labeled molecular networking approach, 20 compounds were identified as potential tyrosinase inhibitors within DE, predominantly flavonoids and tannins characterized by catechin and galloyl substructures. Seven of these compounds were isolated and their inhibitory effects on tyrosinase were validated using functional assays. This study not only underscores the potential of DE as a rich source of natural tyrosinase inhibitors but also establishes the effectiveness of affinity-labeled molecular networking in pinpointing bioactive compounds in complex biological matrices.
Subject(s)
Oenothera biennis , Animals , Oenothera biennis/chemistry , Monophenol Monooxygenase , Zebrafish , Plant Extracts/pharmacology , Flavonoids/pharmacologyABSTRACT
BACKGROUND: The detection of disease biomarkers in biological samples plays an important role in early diagnosis and treatment of carcinoid tumor. However, due to the complexity of biological samples and the extremely low concentration of disease biomarkers, sample pretreatment is still the bottleneck of achieving accurate quantitative determination. In this work, new hydrophilic molecularly imprinted resin-hexagonal boron nitride (HMIR-h-BN) composites were developed and used as a new solid phase extraction (SPE) adsorbent for selective detection of 5-hydroxyindoleacetic acid (5-HIAA), a biomarker of carcinoid tumor, in urine. RESULTS: Twenty-two types of HMIR-h-BN were successfully synthesized through growing hydrophilic molecularly imprinted resin on surface of activated two-dimensional h-BN nanosheets, and preparation parameters affecting the adsorption performance of HMIR-h-BN were investigated and optimized through adsorption experiments. HMIR-h-BN #19 (the ratio of resorcinol to hexamethylenetetramine: 6:3; the dosage of h-BN: 300 mg; the dosage of dummy template: 0.12 mmol; the imprinting time: 4 h) has demonstrated to be the optimal material for efficient separation and extraction of 5-HIAA. Combined with HPLC-UV, the limit of detection and the limit of quantification of 5-HIAA in real urine samples were 9.4 ng mL-1 and 31.3 ng mL-1, respectively, the coefficient of determination (R2) was 0.9996 in the linear range of 0.1-300 µg mL-1 and the relative recoveries ranged from 86.9 % to 97.7 % with RSD ≤5.1 %. Moreover, after being processed by HMIR-h-BN-SPE, there are no interferences from other peaks at the peak position of 5-HIAA. SIGNIFICANCE: The HMIR-h-BN composite has been demonstrated to be capable of selective extraction of 5-HIAA from urine samples and have a significant purification effect. Based on the established HMIR-h-BN-SPE-HPLC-UV method, accurate quantitative determination of 5-HIAA in urine samples was achieved, which is expected to be applied in the early diagnostic of carcinoid tumor.
Subject(s)
Boron Compounds , Carcinoid Tumor , Molecular Imprinting , Humans , Biomarkers, Tumor , Hydroxyindoleacetic Acid , Solid Phase Extraction/methods , Molecular Imprinting/methods , Chromatography, High Pressure Liquid , AdsorptionABSTRACT
Efficiently detecting diamide insecticides in environmental water is challenging due to their low concentrations and complex matrix interferences. In this study, we developed ionic liquids (ILs)-incorporated magnetic molecularly imprinted polymers (IL-MMIPs) for the detection of diamide insecticides, capitalizing on the advantages of ILs and quick magnetic separation through surface imprinting. Tetrachlorantraniliprole was used as the template, and a specific IL, 1-vinyl-3-ethylimidazolium hexafluorophosphate ([VEIm][PF6]), was employed as the functional monomer. Various synthesis conditions were investigated to optimize adsorption efficiency. The prepared IL-MMIPs were successfully employed as adsorbents in magnetic solid-phase extraction (MSPE) to selectively extract, separate, and quantify three types of diamide insecticides from water samples using HPLC-UV detection. Under optimal conditions, the analytical method achieved low limits of detection (0.69 ng mL-1, 0.64 ng mL-1, 0.59 ng mL-1 for cyantraniliprole, chlorantraniliprole and tetrachlorantraniliprole, respectively). The method also displayed a wide linear range (0.003-10 µg mL-1 for cyantraniliprole and chlorantraniliprole, and 0.004-10 µg mL-1 for tetrachlorantraniliprole, respectively) with satisfactory coefficients (R2≥0.9996), and low relative standard deviation (RSD≤2.55%). Additionally, extraction recoveries fell within the range of 79.4%-109%. The results clearly demonstrate that IL-MMIPs exhibit exceptional recognition and rebinding capabilities. The developed IL-MMIPs-MSPE-HPLC-UV method is straightforward and rapid, making it suitable for the detection and analysis of three kinds of diamide insecticides in environmental water.
Subject(s)
Insecticides , Ionic Liquids , Molecular Imprinting , Pyrazoles , ortho-Aminobenzoates , Water , Molecularly Imprinted Polymers , Diamide , Molecular Imprinting/methods , Chromatography, High Pressure Liquid , Polymers , Adsorption , Magnetic Phenomena , Solid Phase Extraction/methodsABSTRACT
The three-dimensional porous ionic liquid-chitosan-graphene oxide aerogel (IL-CS-GOA) monolithic adsorbent with a through-hole structure was prepared using natural chitosan (CS) as the skeletal framework, graphene oxide (GO) as the support to provide mechanical strength, and ionic liquid (IL) as the porogen and modifier. The resulting IL-CS-GOA demonstrated a fluffy and porous structure with various pore sizes and excellent regeneration capability (over six cycles). Its specific surface area exceeded that of CS-GOA and IL-GOA by more than 7 times, enhancing its polyhalogenated carbazoles (PHCZs) adsorption capacity. Within 5 min, IL-CS-GOA (1.0 mg) exhibited adsorption amounts of 539 ng mg-1 for 3-bromocarbazole (3-BCZ), 716 ng mg-1 for 2,7-dibromocarbazole (2,7-BCZ), and 798 ng mg-1 for 1,3,6,8-tetrabromocarbazole (1,3,6,8-BCZ), showcasing its rapid mass transfer and high adsorption capabilities. IL-CS-GOA was utilized as the adsorbent for glass dropper extraction (GDE) in conjunction with gas chromatography-mass spectrometry (GC-MS/MS), to develop a highly efficient and accurate method for determining PHCZs in sediments. Under optimal conditions, the established method exhibited a wide linear range (0.4-250 ng g-1, r ≥ 0.9990), low detection limits (0.04-0.24 ng g-1), and satisfactory recoveries (80.5 %-93.8 %), enabling the accurate and rapid detection of PHCZs in sediment samples. This study presents a novel approach for creating three-dimensional porous aerogels, introduces a new form of sample pretreatment using GDE with a monolithic adsorbent, and offers a new method for the determination of PHCZs in environmental matrices.
ABSTRACT
Alectinib is known as an effective targeted drug, which has excellent therapeutic effect on non-small cell lung cancer and can significantly prolong the survival of patients. Therapeutic drug monitoring is necessary due to the photo-instability of alectinib and the individual differences in patients. In this work, a porous polydopamine graphene oxide composite (PDAG) was prepared by a simple surface modification method. A PDAG-based pipette-tip solid-phase extraction (PT-SPE) coupled with HPLC-UV detection was proposed for the separation and detection of alectinib and its active metabolite M4 in plasma. The method was methodologically validated and showed good linearity in the range of 50-5000 ng mL-1 (R2 > 0.9995). The limit of detection (LOD) was 4.8 ng mL-1 and 3.9 ng mL-1 for alectinib and M4, respectively, and the limit of quantitation (LOQ) was 16.1 ng mL-1 and 13.1 ng mL-1, respectively. The intra-day and inter-day precision expressed by coefficient of variation was less than 4.8 %. The recovery of this method ranged from 84.9 % to 103.5 % with a standard deviation of less than 4.3 %. In conclusion, the established method is accurate, stable and inexpensive, and can be used to monitor the levels of alectinib and M4 in plasma, which provide technical and data support for exploring optimal individualized remedial dosing regimens.
Subject(s)
Carcinoma, Non-Small-Cell Lung , Lung Neoplasms , Humans , Chromatography, High Pressure Liquid/methods , Porosity , Carcinoma, Non-Small-Cell Lung/drug therapy , Solid Phase Extraction/methodsABSTRACT
Overweight and obesity are the causes of many diseases and have become global "epidemics". Research on natural active components with anti-adipogenesis effects in plants has aroused the interest of researchers. One of the most critical problems is establishing sample preparation and analytical techniques for quickly and selectively extracting and determining the active anti-adipogenesis components in complex plant matrices for developing new anti-adipogenic drugs. In this study, a new poly(deep eutectic solvents) surface imprinted graphene oxide composite (PDESs-MIP/GO) with high selectivity for phenolic acids was prepared using deep eutectic solvents as monomers and crosslinkers. A miniaturized centrifugation-accelerated pipette-tip matrix solid-phase dispersion method (CPT-MSPD) with PDESs-MIP/GO as adsorbent, coupled with high-performance liquid chromatography, was further developed for the rapid determination of anti-adipogenesis markers in Solidago decurrens Lour. (SDL). The established method was successfully used to determination anti-adipogenesis markers in SDL from different regions, with the advantages of accuracy (recoveries: 94.4 - 115.9 %, RSDs ≤ 9.8 %), speed (CPT-MSPD time: 11 min), selectivity (imprinting factor: â¼2.0), and economy (2 mg of adsorbent and 1 mL of solvents), which is in line with the current advanced principle of "3S+2A" in analytical chemistry.
Subject(s)
Deep Eutectic Solvents , Graphite , Solidago , Solid Phase Extraction/methods , Solvents/chemistry , Chromatography, High Pressure LiquidABSTRACT
Simultaneous determination of multiple biomarkers can improve the effectiveness and accuracy of cancer diagnosis. Cortisol, cortisone, and 4-methoxyphenylacetic acid (4-Me) are metabolic biomarker group with high specificity and sensitivity for the diagnosis of non-small cells lung cancer (NSCLC), and the development of their simultaneous determination method is desired. Herein, a simple, sensitive, and low-cost method involving pipette-tip solid-phase extraction (PT-SPE) using anion exchange adsorbent (MAX) coupled with liquid chromatography tandem mass spectrometry (LC-MS/MS) was developed for the simultaneous determination of three biomarkers (cortisol, cortisone, and 4-Me) in human urine. The sample (0.1 mL), adsorbent (1.5 mg) and organic reagent (3.5 mL) of MAX-PT-SPE are less consumed, and have the advantages of easy access to raw materials, simple assembly, convenient on-site instant extraction, low pollution, and low cost. The limits of detection of the three biomarkers were 0.006-0.024 ng mL-1, the recoveries of three spiked levels (2, 50, and 500 ng mL-1) were 91.0%-99.3%, with the relative standard deviations (RSDs) ≤ 5.9%. Finally, the MAX-PT-SPE-LC-MS/MS method achieved the quantitative analysis of cortisol, cortisone, and 4-Me in urine of different patients of NSCLC. This method is expected to be used in the non-invasive auxiliary diagnosis of NSCLC, and it provides a new strategy for multi-molecular diagnosis and multi-omics combined diagnosis.
Subject(s)
Cortisone , Lung Neoplasms , Humans , Chromatography, Liquid , Tandem Mass Spectrometry , Hydrocortisone , Lung Neoplasms/diagnosis , Solid Phase Extraction/methods , Chromatography, High Pressure Liquid/methodsABSTRACT
Osimertinib (OSIM) is widely used as a mainstream drug for the treatment of non-small cell lung cancer (NSCLC). However, the lack of a rapid extraction and detection method for OSIM and its metabolite, AZ-5104, has limited clinical drug metabolism and drug resistance research because the drug is unstable. In this study, a new ionic liquid hybrid hierarchical porous material (IL-HHPM) was synthesized with hierarchical porous structures, including micropores (1.6-2.0 nm), mesopores (2.0-50.0 nm), macropores (50.0-148.7 nm), and multiple functional groups via a one-step hydrothermal method using silanized ionic liquids (IL) as functionalized hybrid monomer. The IL-HHPM has the advantages of a high specific surface area (437.4 ± 4.6 m2 g-1), sizable pore volume (0.74 cm3 g-1), and fast mass transfer, additionally, the IL-HHPM adsorbed OSIM and AZ-5104 via π-π interactions and hydrogen bonding. OSIM and AZ-5104 were rapidly extracted and measured in human urine using rapid and miniaturized centrifugal spin-column extraction (MCSCE), which was based on the IL-HHPM. The optimized factors for the extraction recoveries of OSIM and AZ-5104 were adsorbent dosage (8.0 mg), sample volume (0.5 mL), and operation time (9.0 min), and markedly reduced the adsorbent dosage and operation time. The IL-HHPM-MCSCE-HPLC method displayed good linearity (0.02-5.00 µg mL-1, r ≥ 0.9997), satisfying accuracy (spiked recoveries of 87.7%-100.0%), and good precision (RSDs ≤ 7.0%). The developed method is rapid, sensitive, and reproducible for the simultaneous determination of trace level of OSIM and AZ-5104 in human urine.
Subject(s)
Carcinoma, Non-Small-Cell Lung , Ionic Liquids , Lung Neoplasms , Humans , Ionic Liquids/chemistry , Porosity , Chromatography, High Pressure Liquid/methods , Solid Phase Extraction/methodsABSTRACT
Natural glycosides widely distributed in medicinal plants are valuable sources of therapeutic agents, showing various pharmacological effects. The separation and purification of natural glycosides are meaningful for their pharmacological research, which face with great challenges due to the complex of medicinal plants samples. In this work, two kinds of functional monolithic separation mediums A and S were fabricated and fully applied in the online extraction, separation and purification of active glycoside components from medicinal plants with a simple-procedure closed-loop mode. Chrysophanol glucoside and physcion glucoside were detected and separated from Rhei Radix et Rhizoma using separation medium A as a solid-phase extraction adsorbent. Rhapontin was isolated and purified from Rheum hotaoense C. Y. Cheng et Kao using separation medium S as the stationary phase of high-performance liquid chromatography. Compared to the reported literatures, high yield of 5.68, 1.20 and 4.76 mg g-1 of these three products were obtained with high purity. These two online closed-loop mode methods were carried out using high-performance liquid chromatography system, in which the sample injection, isolation and purification procedures are all online mode, and reduced loss compared to offline extraction and purification procedures, thus achieving high recovery and high purity.