•Pentafluorophenyl stationary phase showed superior selectivity for ginsenosides.•The influence of LC–MS parameters on the relative response factors was investigated.•The implementation of group ...reference standards enhances reproducibility.•The LC–MS analysis of multi-component system was tested using 3 different instruments.
The lack of standard substances is a bottleneck for quality control in traditional and alternative medicine. Development of the HPLC-UV approaches combined with single standard for quantitative analysis of multi-component system (QAMS) allowed determination of several plant biomarkers by implementation of the relative response factors (RRFs). Robustness and ruggedness of such methods are commonly demonstrated by performing the analysis in changing analytical conditions on the different HPLC equipment and columns. The nature of MS detection is much more complicated and dependent on the instrumentation. Therefore, this study was conducted to justify the use of RRFs for HPLC–MS determination of bioactive compounds from plants. Protopanaxatriol (PPT), protopanaxadiol (PPD) and ocotillol (OT) ginseng saponins (ginsenosides) were successfully separated on a reversed-phase PFP-column with high group selectivity. Fragmentation patterns for these groups of compounds were established on different HPLC-ESI-MS systems and at varied declustering potentials (DPs). The use of sapogenin fragmentation ions in positive detection mode along with group reference standards was shown to be an optimal way to perform quantification. The performance of the developed group targeted HPLC-MS-QAMS approach was tested in the course of measurements conducted on the different instrumentation. The differences between QAMS and external standard method (ESM) quantification results were below 15% for all determined saponins.
•A sensitive method based on HPLC-MS/MS was developed to determine carbohydrates in atmosphere.•This may be the first time to attach CH3COO− to 2-Methylbutane-1,2,3,4-tretraol using HPLC-MS/MS.•There ...is no need to separate carbohydrates completely in SRM scan mode.•The LODs of carbohydrates may be the lowest in HPLC-MS/MS methods.
Carbohydrates (such as levoglucosan) are a class of important water-soluble organic compounds in atmosphere. In this study, a high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) was applied to characterize carbohydrates in aerosol particles. Since carbohydrate was a kind of compound with low response in mass spectrometry, the conventional HPLC-MS/MS method was not sensitive enough to determine it. When acetate acid was added into mobile phase as buffer, the transition of M+CH3COO−→M-H− could be selected as the quantification ions. In the range from 1.0 μg L−1 to 20 μg mL−1, the coefficients of regression (r2) were more than 0.990, and relative standard deviations (RSD) for replicated injections were lower than 2%. The limit of detection (LOD) and quantification (LOQ) were lower than 2.5 ng L−1 and 10 ng L−1, respectively. The precision and accuracy were examined by spiked samples at three different concentration levels (10 μg L−1, 100 μg L−1, and 500 μg L−1) in five replicates. Recovery ratios ranged from 85% to 115% with RSD lower than 16%. Matrix effects of different carbohydrates ranged from 62% to 120%. The most sensitive HPLC-MS/MS method was developed and validated to analyze 40 aerosol samples successfully. The carbohydrates including three sugar alcohols (threitol, arabitol and sorbitol), one monosaccharide sugar (inositol), two disaccharides (sucrose, trehalose), one anhydrosugar (levoglucosan) and one 2-methyltetrols (2-Methylbutane-1,2,3,4-tretraol) were successfully quantified.
•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.
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.
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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.
•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.
