Development and validation of a high‐throughput assay for the quantification of multiple green tea‐derived catechins in human plasma

A rapid, accurate and robust method for the determination of catechin (C), epicatechin (EC), gallocatechin (GC), epigallocatechin (EGC), catechin gallate (Cg), epicatechin gallate (ECg), gallocatechin gallate (GCg) and epigallocatechin gallate (EGCg) concentrations in human plasma has been developed. The method utilizes protein precipitation following enzyme hydrolysis, with chromatographic separation and detection using reversed‐phase liquid chromatography–tandem mass spectrometry (LC–MS/MS). Traditional issues such as lengthy chromatographic runtimes, sample and extract stability, and lack of suitable internal standards have been addressed. The method has been evaluated using a comprehensive validation procedure, confirming linearity over appropriate concentration ranges, and inter/intra‐batch precision and accuracies within suitable thresholds (precisions within 13.8% and accuracies within 12.4%). Recoveries of analytes were found to be consistent between different matrix samples, compensated for using suitable internal markers and within the performance of the instrumentation used. Similarly, chromatographic interferences have been corrected using the internal markers selected. Stability of all analytes in matrix is demonstrated over 32 days and throughout extraction conditions. This method is suitable for high‐throughput sample analysis studies.     

PEEK tube‐based online solid‐phase microextraction–high‐performance liquid chromatography for the determination of yohimbine in rat plasma and its application in pharmacokinetics study

Yohimbine is a novel compound for the treatment of erectile dysfunction derived from natural products, and pharmacokinetic study is important for its further development as a new medicine. In this work, we developed a novel PEEK tube‐based solid‐phase microextraction (SPME)–HPLC method for analysis of yohimbine in plasma and further for pharmacokinetic study. Poly (AA‐EGDMA) was synthesized inside a PEEK tube as the sorbent for microextraction of yohimbine, and parameters that could influence extraction efficiency were systematically investigated. Under optimum conditions, the PEEK tube‐based SPME method exhibits excellent enrichment efficiency towards yohimbine. By using berberine as internal standard, an online SPME‐HPLC method was developed for analysis of yohimbine in human plasma sample. The method has wide linear range (2–1000 ng/mL) with an R ² of 0.9962; the limit of detection was determined and was as low as 0.1 ng/mL using UV detection. Finally, a pharmacokinetic study of yohimbine was carried out by the online SPME‐HPLC method and the results have been compared with those of reported methods.     

Polymeric monolith column composited with multiwalled carbon nanotubes‐β‐cyclodextrin for the selective extraction of psoralen and isopsoralen

A polymeric column that contains multiwalled carbon nanotubes‐β‐cyclodextrin composite was developed. The composite was wrapped into the poly(butyl methacrylate‐ethylene dimethacrylate) monolith column (0.76 mm id and 10 cm in length). The column was then applied for the online solid‐phase microextraction of psoralen and isopsoralen from Fructus Psoraleae. Following microextraction, the coumarins were quantified by high‐performance liquid chromatography with C₁₈ separation column and UV detection. The effects of sample flow rate, sample volume, and pH value were optimized. The method showed low limits of detection (20 pg/mL, S/N = 3) for both psoralen and isopsoralen. Finally the method was successfully applied to the determination of psoralen and isopsoralen in spiked herb extracts and rat plasma where it gave recoveries that ranged between 93.2 and 102.1%. The empty hydrophobic cavities of β‐cyclodextrin and the hydrophobicity of multiwalled carbon nanotubes provided specific extraction capability for psoralen and isopsoralen.     

Magnetic chitosan functionalized with β‐cyclodextrin as ultrasound‐assisted extraction adsorbents for the removal of methyl orange in wastewater coupled with high‐performance liquid chromatography

Three types of choline chloride based deep eutectic solvents were prepared and used to modify magnetic chitosan. The adsorption capacity of the three deep‐eutectic‐solvent‐modified magnetic chitosan/carboxymethyl‐β‐cyclodextrin for removing methyl orange from wastewater was examined. The different deep eutectic solvents were used to strengthen the adsorption capacity of magnetic chitosan. Deep‐eutectic‐solvent‐modified magnetic chitosan/carboxymethyl‐β‐cyclodextrin materials were characterized by Fourier transform infrared spectroscopy and Brunauer–Emmett–Teller surface area measurements. Among the three deep eutectic solvents, choline chloride/glycerol (1:2) modified magnetic chitosan/carboxymethyl‐β‐cyclodextrin showed the highest adsorption capacity to methyl orange. Therefore, choline chloride/glycerol (1:3, 1:4, 1:5, 1:6) deep eutectic solvents were prepared for the assay, and choline chloride/glycerol‐modified magnetic chitosan/carboxymethyl‐β‐cyclodextrin prepared with choline chloride/glycerol (1:3) (volume: 40 μg, contact time: 30 min, and pH: 6) had the best adsorption capacity over the concentration range of 10–200 μg/mL.     

An NMR tool for cyclodextrin selection in enantiomeric resolution by high‐performance liquid chromatography

Complexation‐induced chemical shifts and diffusion coefficients (HR‐DOSY) of enantiomers with native and derivatized cyclodextrins were used for calculations of the apparent binding constants of three cyclohexanone inclusion complexes. Correlations between these data and high‐performance liquid chromatography were established, revealing that this approach can be applied as an alternative method to predict enantiomeric discrimination. Copyright © 2002 John Wiley & Sons, Ltd.     

Mesoporous titanium oxide with high‐specific surface area as a coating for in‐tube solid‐phase microextraction combined with high‐performance liquid chromatography for the analysis of polycyclic aromatic hydrocarbons

Stainless‐steel wires coated with mesoporous titanium oxide were placed into a polyether ether ketone tube for in‐tube solid‐phase microextraction, and the coating sorbent was characterized by X‐ray diffraction and scanning electron microscopy. It was combined with high‐performance liquid chromatography to build an online system. Using eight polycyclic aromatic hydrocarbons as the analytes, some conditions including sample flow rate, sample volume, organic solvent content, and desorption time were investigated. Under optimum conditions, an online analysis method was established and provided good linearity (0.03–30 μg/L), low detection limits (0.01–0.10 μg/L), and high enrichment factors (77.6–678). The method was applied to determine target analytes in river water and water sample of coal ash, and the recoveries are in the range of 80.6–106.6 and 80.9–103.5%, respectively. Compared with estrogens and plasticizers, extraction coating shows better extraction efficiency for polycyclic aromatic hydrocarbons.     

Matrix solid‐phase dispersion coupled with homogeneous ionic liquid microextraction for the determination of sulfonamides in animal tissues using high‐performance liquid chromatography

Matrix solid‐phase dispersion coupled with homogeneous ionic liquid microextraction was developed and applied to the extraction of some sulfonamides, including sulfamerazine, sulfamethazine, sulfathiazole, sulfachloropyridazine, sulfadoxine, sulfisoxazole, and sulfaphenazole, in animal tissues. High‐performance liquid chromatography was applied to the separation and determination of the target analytes. The solid sample was directly treated by matrix solid‐phase dispersion and the eluate obtained was treated by homogeneous ionic liquid microextraction. The ionic liquid was used as the extraction solvent in this method, which may result in the improvement of the recoveries of the target analytes. To avoid using organic solvent and reduce environmental pollution, water was used as the elution solvent of matrix solid‐phase dispersion. The effects of the experimental parameters on recoveries, including the type and volume of ionic liquid, type of dispersant, ratio of sample to dispersant, pH value of elution solvent, volume of elution solvent, amount of salt in eluate, amount of ion‐pairing agent (NH₄PF₆), and centrifuging time, were evaluated. When the present method was applied to the analysis of animal tissues, the recoveries of the analytes ranged from 85.4 to 118.0%, and the relative standard deviations were lower than 9.30%. The detection limits for the analytes were 4.3–13.4 μg/kg.     

On‐line high‐performance liquid chromatography coupled with biochemical detection method for screening of α‐glucosidase inhibitors in green tea

An on‐line high‐performance liquid chromatography–biochemical detection (HPLC‐BCD) method, in which compounds separated by HPLC were on‐line reacted with enzyme and substrate solutions delivered by flow injection and the enzyme inhibition signal was collected by UV detection, was developed to rapidly screen α‐glucosidase inhibitors from green tea extracts in this study. The chromatographic fingerprints and enzyme inhibition profiles of the different brands of green tea could be simultaneously detected by the on‐line HPLC‐BCD method. Enzyme inhibition profiles were detected by the UV detector at 415 nm based on the reaction of α‐glucosidase and p‐nitrophenyl α‐d ‐glucopyranoside (PNPG). PNPG (1.25 mm ), α‐glucosidase (0.4 U/mL) and the flow rate 0.07 mL/min were applied as optimized parameters to detect α‐glucosidase inhibitors in green tea. Four components in green tea showed α‐glucosidase inhibition action and three of them were identified as HHDP‐galloyl glucose, (−)‐epigallocatechin‐3‐gallate and (−)‐epicatechin‐3‐gallate by HPLC–fourier‐transform mass spectrometry (HPLC‐FTMS). Two brands of green tea derived from Mengding and Enshi mountainous areas might be superior to the other samples in the prevention and treatment of diabetes owing to their stronger activities of enzyme inhibitors. The proposed on‐line HPLC‐BCD method could be used to rapidly identify the potential enzyme inhibitors in complex matrixes.     

Evaluation of solid‐phase extraction procedures for the quantitation of venlafaxine in human saliva by high‐performance liquid chromatography

In recent years, the use of human saliva for diagnostic purposes has evoked great interest. Thus, the aim of this study was to choose the optimal solid‐phase extraction cartridges and extraction solvents for the quantitation of venlafaxine in saliva. Blank saliva samples spiked with venlafaxine concentrations between 25 and 750 ng/mL were analyzed using five solid‐phase extraction columns (C18, C8, Strata‐X, Strata‐X‐C, and Strata‐X‐AW), washing solvents (deionized water, phosphate buffer at pH 5.5, and their mixtures with methanol), and elution solvents (methanol, acetonitrile, and their mixtures with 25% ammonia). A high‐performance liquid chromatography system was used to quantify venlafaxine in saliva. The results of this study revealed that nine of 25 procedures enabled quantitation of venlafaxine in the tested concentration range. The procedure that used a C18 cartridge, a mixture of methanol and deionized water as the washing solvent, and methanol as the elution solvent was the most effective and allowed quantitation of all venlafaxine concentrations with an acceptable recovery. In contrast, the Strata‐X‐C cartridge could not detect venlafaxine at the lowest concentration (25 ng/mL). The data acquired from the high‐performance liquid chromatography system were confirmed by a multivariate data analysis.     

Application of micro‐solid‐phase extraction for the on‐site extraction of heterocyclic aromatic amines in seawater

An efficient on‐site extraction technique to determine carcinogenic heterocyclic aromatic amines in seawater has been reported. A micro‐solid‐phase extraction device placed inside a portable battery‐operated pump was used for the on‐site extraction of seawater samples. Before on‐site applications, parameters that influence the extraction efficiency (extraction time, type of sorbent materials, suitable desorption solvent, desorption time, and sample volume) were investigated and optimized in the laboratory. The developed method was then used for the on‐site sampling of heterocyclic aromatic amines determination in seawater samples close to distillation plant. Once the on‐site extraction completed, the small extraction device with the analytes was brought back to the laboratory for analysis using high‐performance liquid chromatography with fluorescence detection. Based on the optimized conditions, the calibration curves were linear over the concentration range of 0.05–20 μg/L with correlation coefficients up to 0.996. The limits of detection were 0.004–0.026 μg/L, and the reproducibility values were between 1.3 and 7.5%. To evaluate the extraction efficiency, a comparison was made with conventional solid‐phase extraction and it was applied to various fortified real seawater samples. The average relative recoveries obtained from the spiked seawater samples varied in the range 79.9–95.2%.     

Multiple monolithic fiber solid‐phase microextraction based on a polymeric ionic liquid with high‐performance liquid chromatography for the determination of steroid sex hormones in water and urine

The development of a simple and sensitive analytical approach that combines multiple monolithic fiber solid‐phase microextraction with liquid desorption followed by high‐performance liquid chromatography with diode array detection is proposed for the determination of trace levels of seven steroid sex hormones (estriol, 17β‐estradiol, testosterone, ethinylestradiol, estrone, progesterone and mestranol) in water and urine matrices. To extract the target analytes effectively, multiple monolithic fiber solid‐phase microextraction based on a polymeric ionic liquid was used to concentrate hormones. Several key extraction parameters including desorption solvent, extraction and desorption time, pH value and ionic strength in sample matrix were investigated in detail. Under the optimal experimental conditions, the limits of detection were found to be in the range of 0.027–0.12 μg/L. The linear range was 0.10–200 μg/L for 17β‐estradiol, 0.25–200 μg/L estriol, ethinylestradiol and estrone, and 0.50–200 μg/L for the other hormones. Satisfactory linearities were achieved for analytes with the correlation coefficients above 0.99. Acceptable method reproducibility was achieved by evaluating the repeatability and intermediate precision with relative standard deviations of both less than 8%. The enrichment factors ranged from 54‐ to 74‐fold. Finally, the proposed method was successfully applied to the analysis of steroid sex hormones in environmental water samples and human urines with spiking recoveries ranged from 75.6 to 116%.     

Nanostructured‐silver‐coated polyetheretherketone tube for online in‐tube solid‐phase microextraction coupled with high‐performance liquid chromatography

Polyetheretherketone tube is a better substrate for in‐tube solid‐phase microextraction than fused‐silica capillary and metal tube because of its resistance to high pressure and good flexibility. It was modified with a nanostructured silver coating, and characterized by scanning electron microscopy and energy dispersive X‐ray spectroscopy. It was connected into high‐performance liquid chromatography equipment to build the online analysis system by replacing the sample loop of a six‐port injection valve. To get the highest extraction capacity, the preparation conditions of the coating was investigated. Important extraction conditions including length of tube, sample volume, and desorption time were optimized using eight polycyclic aromatic hydrocarbons as model analytes. The tube exhibits excellent extraction efficiency toward them, with enrichment factors from 52 to 363. The online analysis method provides good linearity (0.5–100 or 1.0–100 μg/L) and low detection limits (0.15–0.30 μg/L). It has been used to determine polycyclic aromatic hydrocarbons in water samples, with relative recoveries in the range of 92.3–120%. The tube showed highest extraction ability for polycyclic aromatic hydrocarbons, higher extraction ability for hydrophobic phthalates and anilines, and almost no extraction ability for low hydrophobic phenols, due to the possible extraction mechanism including hydrophobic and electron‐rich element‐metal interactions.     

Electrospun titania sol–gel‐based ceramic composite nanofibers for online micro‐ solid‐phase extraction with high‐performance liquid chromatography

Titanium(IV) tetraisopropoxide was employed as a metal oxide sol–gel precursor to prepare ceramic composite nanofibers by the electrospinning system. To facilitate this process and obtain the desired nanofibers with higher aspect ratios and surface area, poly(vinylpyrrolidone) was added to the sol of titania. Four ceramic nanofibers sheets based on titania were prepared while each sheet contained different transition metals such as Fe‐Mn, Fe‐Ni, Fe‐Co, and Fe‐Mn‐Co‐Ni. The scanning electron microscope images showed good homogeneity for all the prepared ceramic composites with a diameter range of 100–250 nm. The sorption efficiency was investigated by a micro‐solid‐phase extraction setup in online combination with high‐performance liquid chromatography for the determination of naproxen and clobetasol. All the prepared composites exhibited comparable efficiencies for the desired analytes and the type of metal showed insignificant effect. For the selected composite with Fe‐Mn, the linearity of the analytes was in the range of 1–1000 μg/L and the limit of detection values were found to be 2 and 0.3 μg/L for naproxen and clobetasol, respectively. The developed method was extended to the analysis of urine and blood plasma samples and acceptable relative standard deviations were obtained at two concentration levels.     

Ultrapreconcentration and determination of organophosphorus pesticides in water by solid‐phase extraction combined with dispersive liquid–liquid microextraction and high‐performance liquid chromatography

Solid‐phase extraction coupled with dispersive liquid–liquid microextraction was developed as an ultra‐preconcentration method for the determination of four organophosphorus pesticides (isocarbophos, parathion‐methyl, triazophos and fenitrothion) in water samples. The analytes considered in this study were rapidly extracted and concentrated from large volumes of aqueous solutions (100 mL) by solid‐phase extraction coupled with dispersive liquid–liquid microextraction and then analyzed using high performance liquid chromatography. Experimental variables including type and volume of elution solvent, volume and flow rate of sample solution, salt concentration, type and volume of extraction solvent and sample solution pH were investigated for the solid‐phase extraction coupled with dispersive liquid–liquid microextraction with these analytes, and the best results were obtained using methanol as eluent and ethylene chloride as extraction solvent. Under the optimal conditions, an exhaustive extraction for four analytes (recoveries >86.9%) and high enrichment factors were attained. The limits of detection were between 0.021 and 0.15 μg/L. The relative standard deviations for 0.5 μg/L of the pesticides in water were in the range of 1.9–6.8% (n = 5). The proposed strategy offered the advantages of simple operation, high enrichment factor and sensitivity and was successfully applied to the determination of four organophosphorus pesticides in water samples.     

Analysis of microcystins using high‐performance liquid chromatography and magnetic solid‐phase extraction with silica‐coated magnetite with cetylpyridinium chloride

Microcystins (MCs), produced by freshwater cyanobacteria, can be serious water pollutants, so it is important to monitor their concentration in drinking water. We have developed a method for rapid and accurate determination of microcystin levels in environmental water, using magnetic solid‐phase extraction and high‐performance liquid chromatography with UV detection. The magnetic composite material, which was combined with cetylpyridinium chloride, was prepared by hydrothermal synthesis. The optimal extraction of microcystins in water sample was achieved by optimizing the amount of adsorbent, time of adsorption, ratio of eluting solvent, and volume of eluent. Under the optimal conditions, the limit of detection of MC‐LR was 0.001 μg/L, and the limit of quantification was 0.0028 μg/L. The limit of detection of MC‐RR was 0.001 μg/L, and the limit of quantification was 0.003 μg/L. These values are far lower than those established by the International Health Organization for the maximum concentration of microcystins in drinking water. The magnetic solid‐phase extraction adsorbent used in this method has the advantages of simple preparation, low price, and easy solid–liquid separation, and it can be used for the rapid and sensitive monitoring of trace microcystins in environmental water samples.     

Application of sunflower stalk‐carbon nitride nanosheets as a green sorbent in the solid‐phase extraction of polycyclic aromatic hydrocarbons followed by high‐performance liquid chromatography

A green biocomposite of sunflower stalks and graphitic carbon nitride nanosheets has been applied as a solid‐phase extraction adsorbent for sample preparation of five polycyclic aromatic hydrocarbons in different solutions using high‐performance liquid chromatography with ultraviolet detection. Before the modification, sunflower stalks exhibited relatively low adsorption to the polycyclic aromatic hydrocarbons extraction. The modified sunflower stalks showed increased adsorption to the analytes extraction due to the increase in surface and existence of a π–π interaction between the analytes and graphitic carbon nitride nanosheets on the surface. Under the optimal conditions, the limits of detection and quantification for five polycyclic aromatic hydrocarbons compounds could reach 0.4–32 and 1.2–95 ng/L, respectively. The method accuracy was evaluated using recovery measurements in spiked real samples and good recoveries from 71 to 115% with relative standard deviations of <10% have been achieved. The developed method was successfully applied for polycyclic aromatic hydrocarbons determination in various samples—well water, tap water, soil, vegetable, and barbequed meat (kebab)—with analytes contents ranging from 0.065 to 13.3 μg/L. The prepared green composite as a new sorbent has some advantages including ease of preparation, low cost, and good reusability.     

Multiwalled‐carbon‐nanotubes‐based matrix solid‐phase dispersion extraction coupled with high‐performance liquid chromatography for the determination of honokiol and magnolol in Magnoliae Cortex

In this paper, multiwalled‐carbon‐nanotube‐based matrix solid‐phase dispersion coupled to HPLC with diode array detection was used to extract and determine honokiol and magnolol from Magnoliae Cortex. The extraction efficiency of the multiwalled‐carbon‐nanotube‐based matrix solid‐phase dispersion was studied and optimized as a function of the amount of dispersing sorbent, volume of elution solvent, and flow rate of elution solvent, with the aid of response surface methodology. An amount of 0.06 g of carboxyl‐modified multiwalled carbon nanotubes and 1.5 mL of methanol at a flow rate of 1.1 mL/min were selected. The method obtained good linearity (r² > 0.9992) and precision (RSD < 4.7%) for honokiol and magnolol, with limits of detection of 0.045 and 0.087 μg/mL, respectively. The recoveries obtained from analyzing in triplicate spiked samples were determined to be from 90.23 to 101.10% and the RSDs from 3.5 to 4.8%. The proposed method that required less samples and reagents was simpler and faster than Soxhlet and maceration extraction methods. The optimized method was applied for analyzing five real samples collected from different cultivated areas.     

Graphene oxide based molecularly imprinted polymers modified with β‐cyclodextrin for selective extraction of di(2‐ethylhexyl) phthalate in environmental waters

Graphene oxide based molecularly imprinted polymers modified with β‐cyclodextrin were prepared as solid‐phase extraction column sorbents for specific recognition and sensitive detection of di(2‐ethylhexyl) phthalate in water samples. The morphology and composition of synthesized sorbents were characterized by scanning electron microscopy, thermo‐gravimetric analysis, Raman spectroscopy, and Fourier‐transform infrared spectroscopy. The conditions affecting the performance of extraction procedures such as desorption solvent types and volume, sample pH and volume were investigated. The loading capacity (8.2 μg/mg) of the prepared sorbents increased eight times after modification with β‐cyclodextrin. The developed extraction procedures coupled to high‐performance liquid chromatography exhibited good linearity (0.2–500 μg/L), low limit of detection (0.052 μg/L), and good precision (relative standard deviation?5.7%) under optimized conditions. The developed solid‐phase extraction technique with prepared sorbents has been successfully applied in extracting trace di(2‐ethylhexyl) phthalate from real natural waters with high efficiency, good selectivity, and desirable recoveries.     

Effervescence‐assisted dispersive solid‐phase extraction using ionic‐liquid‐modified magnetic β‐cyclodextrin/attapulgite coupled with high‐performance liquid chromatography for fungicide detection in honey and juice

In this study, a simple effervescence‐assisted dispersive solid‐phase extraction method was developed to detect fungicides in honey and juice. Most significantly, an innovative ionic‐liquid‐modified magnetic β‐cyclodextrin/attapulgite sorbent was used because its large specific surface area enhanced the extraction capacity and also led to facile separation. A one‐factor‐at‐a‐time approach and orthogonal design were employed to optimize the experimental parameters. Under the optimized conditions, the entire extraction procedure was completed within 3 min. In addition, the calibration curves exhibited good linearity, and high enrichment factors were achieved for pure water and honey samples. For the honey samples, the extraction efficiencies for the target fungicides ranged from 77.0 to 94.3% with relative standard deviations of 2.3–5.44%. The detection and quantitation limits were in the ranges of 0.07–0.38 and 0.23–1.27 μg/L, respectively. Finally, the developed technique was successfully applied to real samples, and satisfactory results were achieved. This analytical technique is cost‐effective, environmentally friendly, and time‐saving.     

Simultaneous extraction and quantification of albendazole and triclabendazole using vortex‐assisted hollow‐fiber liquid‐phase microextraction combined with high‐performance liquid chromatography

A novel, simple, and rapid vortex‐assisted hollow‐fiber liquid‐phase microextraction method was developed for the simultaneous extraction of albendazole and triclabendazole from various matrices before their determination by high‐performance liquid chromatography with fluorescence detection. Several factors influencing the microextraction efficiency including sample pH, nature and volume of extraction solvent, ionic strength, vortex time, and sample volume were investigated and optimized. Under the optimal conditions, the limits of detection were 0.08 and 0.12 μg/L for albendazole and triclabendazole, respectively. The calibration curves were linear in the concentration ranges of 0.3–50.0 and 0.4–50.0 μg/L with the coefficients of determination of 0.9999 and 0.9995 for albendazole and triclabendazole, respectively. The interday and intraday relative standard deviations for albendazole and triclabendazole at three concentration levels (1.0, 10.0, and 30.0 μg/L) were in the range of 6.0–11.0 and 5.0–7.9%, respectively. The developed method was successfully applied to determine albendazole and triclabendazole in water, milk, honey, and urine samples.