A novel magnetically and efficiently multifunctional boronic acid (BA) -functionalized core-shell nanohybrid (Fe3O4@SiO2@BA) was prepared for capture and separation of cis-diol-flavonoids. The ...morphology and physicochemical properties of resultant nanoparticles were systematically characterized via several techniques, and the results confirmed that the target nanohybrids were successfully functionalized and modified. Meanwhile, two flavonoids (quercetin and luteolin) were selected to investigate the selective capture of the Fe3O4@SiO2@BA in procedure of magnetic solid phase extraction (MSPE). The main parameters influencing the adsorption and elution conditions were systematically investigated and optimized. Furthermore, the adsorption kinetic models were adopted to elucidate the adsorption process, indicating that the pseudo-second-order model was suitable to explain the adsorption kinetics. Under the optimum conditions, the MSPE-HPLC-MS/MS approach was established with a wide linear dynamic range and good linearity (R2 > 0.999), low limits of detection (0.0096–0.033 μg L−1) and satisfactory recoveries (91–107.6%). The proposed analytical method was successfully applicated by determining the content of target flavonoids in food samples (apple and onion). Accordingly, the prepared nanohybrid could serve as an efficient, rapid and economical potential adsorbent for extracting cis-diol-flavonoids in complex food samples.
Novel magnetic Fe3O4@SiO2@BA nanohybrids were fabricated and indicates the prepared nanoparticles could be a promising selective adsorbent for the preconcentration and determination of cis-diol-flavonoids in food samples. Display omitted
•Fe3O4@SiO2@BA was synthesized via a facile and efficient strategy for cis-diol-flavonoids capture.•Fe3O4@SiO2@BA exhibited uniform morphology and excellent magnetic responsiveness.•The adsorption and kinetic parameters of nanoparticles were systematically investigated and optimized.•A novel MSPE-HPLC-MS/MS method was established for the determination of target flavonoids from food samples.
•A HPLC–MS/MS method was developed for determination of four alkaloids in chick.•The developed method was validated as per USFDA bioanalytical guideline.•First paper on drug residue determination of ...sanguinarine in chick.
A specific and reliable HPLC–MS/MS method was developed and validated for simultaneously determination of sanguinarine, chelerythrine and their metabolites (dihydrosanguinarine and dihydrochelerythrine) in chicken tissue for the first time. This is important because these compounds are related to the use of a naturally occurring and novel feed additive with many benefits, but the levels of these compounds must be strictly controlled. The compounds were extracted by acetonitrile and 1% HCl–methanol solution successively and then separated on a C18 column. A triple-quadrupole mass spectrometer equipped with an electrospray ionization (ESI) source was used for detection. Quantification was performed using multiple reaction monitoring with positive mode. The method was validated in terms of specificity, linearity, precision, accuracy and stability. The calibration curves were linear over the concentration range of 0.5–100.0ng/g for sanguinarine, 0.5–100.0ng/g for chelerythrine, 0.2–100.0ng/g for dihydrosanguinarine and 0.1–100ng/g for dihydrochelerythrine, respectively. All of the recovery rates of the four analytes were over 85%. The RSD of intra-day and inter-day precision was less than 5.0%, and the relative error was all within 12.0%. This validated method has been successfully applied to assess the drug residue and metabolite residue characteristics of sanguinarine and chelerythrine in chicken tissue after oral administration of the extracts of Macleaya cordata (Willd.) R. Br, and to investigate the pharmacokinetic parameters of sanguinarine and dihydrosanguinarine in chicken plasma.
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•A fast and more eco-friendly methodology to control opium alkaloids in food products.•First validated methodology for opium alkaloid analysis in biscuits and sponge cakes.•SBA-15 was ...used for the solid-phase extraction to avoid matrix interferences.•Ultrasound-assisted extraction allowed solvent volume and extraction time reduction.•Morphine was detected in all samples studied below the legislated maximum limits.
Food products containing poppy seeds are increasingly consumed. These seeds may be contaminated with opium alkaloids (OAs) from the latex of the plant (Papaver somniferum L.), which may present a health hazard to the consumer. Therefore, the aim of this work was to develop an efficient, fast and environmentally friendly methodology to control OAs in biscuits and sponge cake products by analysis with liquid chromatography coupled to a triple quadrupole tandem mass detector (HPLC-MS/MS). For this purpose, the ultrasound-assisted extraction (UAE) step was optimised using a 5-variable full factorial design at two levels, obtaining lower solvent volume and time than with other classical methods. Then, a solid phase extraction (SPE) was used to remove matrix effects. A commercial material (HLB) and two silica synthesised materials (HMS and SBA-15) were evaluated and optimised, selecting SBA-15 (50 mg). Finally, the method was validated and applied to real samples, showing morphine concentrations in 5 of 7 products but below the maximum permitted limit.
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•Chemical profiling and network pharmacology-based analysis of JWQFY were performed.•A total of 135 constituents were identified, 70 of them were further quantified.•Multi-target ...mechanisms of JWQFY against Alzheimer's disease were predicted.•The modification rationality of the formula JWQFY was elucidated.
Jia-Wei-Qi-Fu-Yin (JWQFY) is a newly developed anti-Alzheimer's disease (AD) prescription modified from a classical traditional Chinese medicine formula, Qi-Fu-Yin (QFY). However, a systematic understanding of its chemical constituents and molecular mechanisms is still elusive. To address this problem, comprehensive chemical profiling followed by network pharmacology-based analysis of JWQFY was performed. Firstly, a total of 136 compounds were characterized by high performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry (HPLC-QTOF MS), 17 of them were specifically identified in JWQFY comparing with QFY. Seventy compounds were further quantified via a validated HPLC coupled with triple quadrupole tandem mass spectrometry (QQQ MS) method. Then the protein targets of the seventy compounds were gathered from public databases for network construction. As a result, fifty-seven compounds were filtered, which interacted with 655 targets. Thirty-four of them were mapped into the KEGG pathway of AD, indicating JWQFY might exert anti-AD effects by anti-inflammation, neuronal apoptosis intervening, Aβ production inhibition and phosphorylating tau protein moderating. Furthermore, in the compound-target-AD network, a list of hub compounds and hub targets was identified based on their topological features, including the degree, node betweenness and closeness. Four of the hub compounds were specifically originated from JWQFY, supporting the modification rationality of this formula. This study provided a scientific basis for understanding the bioactive compounds and the multi-target mechanism of JWQFY.
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•The in-depth phytochemical comparison of A. eupatoria and A. procera is presented.•The variability of chemical composition of both plant materials is presented.•The possibility of ...introduction of A. procera as source for pharmacopoeial herb.•The problem of lack of proper standardization of agrimony herb is highlighted.
The agrimony herb is a traditional plant drug, which is commonly used as a mildly astringent agent. According to European Pharmacopoeia, the only source of this plant drug is Agrimonia eupatoria. By contrast the German Commission E pharmacopoeial monograph used to allow Agrimonia procera to be used as a second valid source of Agrimoniae herba. Several studies have been conducted on the phytochemical composition of common agrimony. The data on the phytochemistry of A. procera are scarce. The aim of the present study was an in-depth phytochemical comparison of A. eupatoria and A. procera in the context of the pharmacopoeial monograph of A. herba.
The comparison of two agrimony species showed that there are no significant qualitative differences. The quantitative HPLC analysis revealed that fragrant agrimony is a much better source of agrimoniin than common agrimony. This difference could not be detected using the pharmacopoeial method of quantification for the total tannin content.
The present study has shown for the first time the possible use of apigenin-C-glycosides (vitexin and isovitexin) as chemotaxonomic markers for distinguishing both agrimony species. The potential chemical markers such as apigenin-7-O-glucoside and high agrimoniin content were also suggested for fragrant agrimony. Based on the data obtained, A. procera should be considered as a valid source of pharmacopoeial plant material.
•A simple, robust and reliable method was developed for measuring phthalates in wine.•HPLC–MS/MS was practically used for wine phthalate analysis.•No effect of HPLC phthalate contamination on ...analysis was confirmed.•Extraction and enrichment were not required for sample preparation.
This paper describes the development and application of a novel method for the analysis of phthalates in wine using HPLC–MS/MS combined with a hold-back column. Phthalates are ubiquitous contaminants in the environment and can be widely found in laboratory materials and equipment. A HPLC system is no exception and can be the source of contamination affecting the accuracy and precision of analytical results. The new method successfully separates phthalates from the different sources, a wine sample and HPLC system by a simple technique using an additional HPLC column (a hold-back column) placed upstream of the injection valve. The hold-back column effectively retains the HPLC-derived contaminants during column equilibrium time and delays their elution times from an analytical column. Consequently, a phthalate from a wine sample can be baseline separated as it elutes sufficiently earlier than the same phthalate from the HPLC system. HPLC–MS/MS analysis combined with the hold-back column demonstrated virtually no influence of the HPLC contaminants on the quantification of phthalates present in wine. Together with a simple and rapid sample preparation and the use of labeled internal standards, the method was confirmed to be robust and reliable to determine concentrations of phthalates in wine. Quantification limits were within the range of 1.6–9.8μgL−1 for dimethyl, diethyl, dibutyl, benzylbutyl, bis(2-ethylhexyl) and dioctyl phthalates, and 7.5–26.6μgL−1 for multiple isomeric phthalates, di-iso-nonyl and di-iso-dodecyl phthalates.
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•This is the first assay quantifying dabrafenib and trametinib simultaneously.•This assay was validated according to the latest US FDA guidance and EMA guidelines.•Dabrafenib is ...degradated by light.•Dabrafenib and trametinib can now simultaneously be quantified in human plasma.
Dabrafenib (Tafinlar®) and trametinib (Mekinist®) are registered for the treatment of patients with BRAF V600 mutation positive unresectable or metastatic melanoma. To support therapeutic drug monitoring (TDM) and clinical pharmacological trials, an assay to simultaneously quantify dabrafenib and trametinib in human plasma using liquid chromatography tandem mass spectrometry was developed and validated.
Human plasma samples were collected on an outpatient base and stored at nominally −20°C.
Analytes and internal standards (stable isotope labeled compounds) were extracted with TBME. After snap freezing the samples in a dry ice-ethanol bath, the organic layer was transferred to a clean tube and evaporated under a gentle stream of nitrogen gas. The dry extract was then reconstituted with 100μL acetonitrile and 5μL of the final extract was injected and separated on a C18 column with gradient elution, and analyzed with triple quadrupole mass spectrometry in positive-ion mode.
The validated assay ranges from 50 to 5000ng/mL for dabrafenib and 0.5–50ng/mL for trametinib were linear, and correlation coefficient (r2) of 0.996 or better. At all concentrations of both analytes the biases were within ±15% of the nominal concentrations and precisions were ≤15%. All results were within the acceptance criteria of the latest US FDA guidance and EMA guidelines on method validation. Dabrafenib was found to degrade under the influence of light in different organic solvents and at least seven degradation products were detected.
In conclusion, the described method to simultaneously quantify dabrafenib and trametinib in human plasma was successfully validated and applied for therapeutic drug monitoring in cancer patients treated with dabrafenib and trametinib.
•A new online μ-MCE method with soil-packed cartridge was developed for fipronil extraction in soil.•Online μ-MCE exhibited ultrahigh desorption efficiency compared with traditional extraction ...methods.•Its universality was validated in different interactions, compounds and soils.•The method is mild, fast, efficient, cost-effective, and automatic.
Nowadays, environment fate and behavior of pesticides in soil is still not fully understood due to the lack of standardized soil extraction method. In this work, a soil-filled micro-matrix cartridge was online combined with high performance liquid chromatography-mass spectrometry (HPLC-MS) through a six-way valve for the simultaneous extraction and determination of residual fipronil in soil. Compared with conventional extraction methods, such as hydroxypropyl-β-cyclodextrin (HPCD) extraction, shaking extraction, ultrasonic-assisted extraction (UAE), three-step extraction and matrix solid phase dispersion (MSPD), the novel, miniaturized, and integrated online micro-matrix cartridge extraction (online μ-MCE) method exhibited better performance in terms of desorption efficiency (99.4%), analysis time, solvent consumption, sensitivity, and automation. In sequential extraction, online μ-MCE could further desorb fipronil from the extracted soil with the percentage of 1.05%-58.55%. High recovery of 92.69% obtained for the ISO certificated test-soil verified the satisfactory accuracy of the method. Besides, its wide universality was also validated in three variables: 1) various pesticides-soil interactions, 2) four types of compounds (aromatic hydrocarbons, carboxylic acids, alcohols and aldehydes), and 3) three types of soils (sandy soil, silty loam and silty clay). The superior desorption capacity might be attributed to the instantaneously increased high-pressure, continuous flow dynamic desorption and short residence time. The present encouraging findings might shed light on new ways to develop a mild, highly efficient, reliable and one-fit-all extraction method toward pesticide contaminated soil.
It is commonly accepted that brain phospholipids are highly enriched with long-chain polyunsaturated fatty acids (PUFAs). However, the evidence for this remains unclear. We used HPLC–MS to analyze ...the content and composition of phospholipids in rat brain and compared it to the heart, kidney, and liver. Phospholipids typically contain one PUFA, such as 18:2, 20:4, or 22:6, and one saturated fatty acid, such as 16:0 or 18:0. However, we found that brain phospholipids containing monounsaturated fatty acids in the place of PUFAs are highly elevated compared to phospholipids in the heart, kidney, and liver. The relative content of phospholipid containing PUFAs is ~ 60% in the brain, whereas it is over 90% in other tissues. The most abundant species of phosphatidylcholine (PC) is PC(16:0/18:1) in the brain, whereas PC(18:0/20:4) and PC(16:0/20:4) are predominated in other tissues. Moreover, several major species of plasmanyl and plasmenyl phosphatidylethanolamine are found to contain monounsaturated fatty acid in the brain only. Overall, our data clearly show that brain phospholipids are the least enriched with PUFAs of the four major organs, challenging the common belief that the brain is highly enriched with PUFAs.