Rapid qualitative profiling and quantitative analysis of Juglandis Mandshuricae Cortex and seven flavonoids by ultra-high performance liquid chromatography–quadrupole/orbitrap high-resolution mass spectrometry

Juglandis Mandshuricae Cortex is the bark of Juglans mandshurica Maxim., which has been used as a folk medicine plant in China and India. In this study, an ultra-high performance liquid chromatography–quadrupole/orbitrap high-resolution mass spectrometry method was developed to clarify and quantify the chemical profiling of Juglandis Mandshuricae Cortex rapidly. A total of 113 compounds were characterized. Among them, seven flavonoids were simultaneously quantified in 15 min, including myricetin, myricetrin, taxifolin, kaempferol, quercetin, quercitrin, and naringenin. The method was validated for accuracy, precision, and the limits of detection and quantification. All calibration curves showed a good linear relationship (r > 0.9990) within test ranges. The intra- and inter-day relative standard deviations were less than 2.16%. Accuracy validation showed that the recovery was between 95.6 and 101.3% with relative standard deviation values below 2.85%. The validated method was successfully applied to determine the contents of seven flavones in Juglandis Mandshuricae Cortex from seven sources and the contents of these places were calculated respectively. This method provides a theoretical basis for further developing the medicinal value of Juglandis Mandshuricae Cortex.     

Sample preparation,instrumental analysis,and natural distribution of complex organic pollutants in the wastewater from unconventional gas production

Large amounts of flowback and produced water (FPW) have been generated from hydraulic fracturing process for the production of unconventional gas such as shale gas. Complex organic pollutants are abundantly present in FPW with revealed toxicity to aquatic organisms and these contaminants may transfer into surrounding aquatic environment. Characterization and determination of complicated organic pollutants in FPW remains a challenge due to its complex composition and high salinity matrix. This review article covers the progress of recent 5 years regarding the sample preparation and instrumental analysis methods and thus summarizes the advantages and disadvantages of these methods for critical analysis of organic contaminants in FPW samples. Furthermore, the natural distribution of detected organic compounds and their transformation were reviewed and discussed to enhance the understanding of spatial and temporal behaviors of these organic pollutants in natural environment, paving the way for future development of pollution control policies and strategies. Enlightened by the studies of FPW contamination in the US, the investigations of FPW contamination in China continued to grow due to rapidly growing production of shale gas in China and resulted pollution.     

The behavior of capillary suspensions at diverse length scales: From single capillary bridges to bulk

Liquid-liquid-solid systems are becoming increasingly common in everyday life with many possible applications. Here, we focus on a special case of such liquid-liquid-solid systems, namely, capillary suspensions. These capillary suspensions originate from particles that form a network based on capillary forces and are typically composed of solids in a bulk liquid with an added secondary liquid. The structure of particle networks based on capillary bridges possesses unique properties compared with networks formed via other attractive interactions where these differences are inherently related to the properties of the capillary bridges, such as bridge breaking and coalescence between adjacent bridges. Thus, to tailor the mechanical properties of capillary suspensions to specific requirements, it is important to understand the influences on different length scales ranging from the dynamics of the bridges with varying external stimuli to the often heterogeneous network structure.     

Sensitive CE-MS method for monitoring of riociguat and desmethylriociguat levels in human serum

Riociguat is novel antihypertensive drug for treatment of pulmonary hypertension. As such, it is still being tested in many clinical and pharmacokinetic trials. Existing methods that determine serum riociguat and desmethylriociguat (DMR) are based solely on liquid chromatography with mass spectrometry. Therefore, we present a novel capillary electrophoresis with mass spectrometry method (CE-MS) for their determination in human serum as alternative method for ongoing trials. Complete resolution of both analytes was achieved by means of pH optimization of ammonium formate background electrolytes that are fully compatible with ESI/MS detection. Simple liquid-liquid extraction was used as sample pretreatment. The calibration dependence of the method was linear (in the range of 10–1000 ng/mL), with adequate accuracy (90.1–114.9%) and precision (13.4%). LOD and LOQ were arbitrarily set at 10 ng/mL for both analytes. Clinical applicability was validated using serum samples from patients treated with riociguat in pharmacokinetic study and the results corresponded with reference HPLC-MS/MS values. Capillary electrophoresis proved to be sensitive and selective tool for the analysis of riociguat and DMR.     

Low-cost automated capillary electrophoresis instrument assembled from commercially available parts

A CE instrument that can be assembled from commercially available components with minimal construction effort is described. Except for the electronic control circuitry no specially made parts are required. It is based on a flexible design of microfluidic, electropneumatic, and electronic sections and different configurations can easily be implemented. Automated injection into the capillary is performed hydrodynamically by the application of a pressure for a controlled length of time. The performance of the device was tested with a contactless conductivity detector by separating different metal ions. In addition, nine metal cations related to the quality of honey were separated in 2.3 min and four honey samples were analysed quantitatively to demonstrate the applicability of the method.     

Coupling nanoliter high‐performance liquid chromatography to inductively coupled plasma mass spectrometry for arsenic speciation

Nanoliter high‐performance liquid chromatography shows low consumption of solvents and samples, offering one of the best choices for arsenic speciation in precious samples in combination with inuctively coupled plasma mass spectrometry. A systematic investigation on coupling nanoliter high‐performance liquid chromatography to inductively coupled plasma mass spectrometry from instrument design to injected sample volume and mobile phase was performed in this study. Nanoflow mobile phase was delivered by flow splitting using a conventional high‐pressure pump with reuse of mobile phase waste. Dead volume was minimized to 60 nL for the sheathless interface based on the previously developed nanonebulizer. Capillary columns for nanoliter high‐performance liquid chromatography were found to be sensitive to sample loading volume. An apparent difference was also found between the mobile phases for nanoliter and conventional high‐performance liquid chromatography. Baseline separation of arsenite, arsenate, monomethylarsenic, and dimethylarsenic was achieved within 11 min on a 15 cm C₁₈ capillary column and within 12 min on a 25 cm strong anion exchange column. Detection limits of 0.9–1.8 μg/L were obtained with precisions variable in the range of 1.6–4.2%. A good agreement between determined and certified values of a certified reference material of human urine (GBW 09115) validated its accuracy along with good recoveries (87–102%).     

Recent trends in capillary and micro-chip electrophoretic instrumentation for field-analysis

Technical advances in the development of field-deployable capillary and microchip electrophoretic instruments and reports of their deployment between 2013 and 2017 were reviewed. Strategies and considerations in the design of the injection, separation and detection hardware, chemistry and associated infrastructure were discussed from an in-field perspective, with portability, robustness and automation/“ease of use” featuring as key requirements. Integration of functionality is important for adequate in-field performance. Progress was made towards the use of multiple channel devices for increased throughput and/or resolving power, mixing devices for on-line/in-line sample derivatization, battery operation and temperature control. The strengths and weaknesses of the various approaches described in the literature are discussed from the perspective of in-field operation. An overview of the applications of the field electrophoretic instruments is provided, including environmental science and planetary investigation.     

Enhanced headspace single drop microextraction method using deep eutectic solvent based magnetic bucky gels: Application to the determination of volatile aromatic hydrocarbons in water and urine samples

A facile headspace single drop microextraction method was developed using deep eutectic solvent‐based magnetic bucky gel as the extraction solvent for the first time. The hydrophobic magnetic bucky gel was formed by combining choline chloride/chlorophenol deep eutectic solvent and magnetic multiwalled carbon nanotube nanocomposite. Magnetic susceptibility, high viscosity, high sorbing ability, and tunable extractability of organic analytes are the desirable advantages of the prepared gel. Using a rod magnet as a suspensor in combination with the magnetic susceptibility of the prepared gel resulted in a highly stable droplet. This stable droplet eliminated the possibility of drop dislodgement. The prepared droplet made it possible to complete the extraction process in high temperatures and elevated agitation rates. Furthermore, using larger micro‐droplet volumes without any operational problems became possible. These facts resulted in shorter sample preparation time, higher sensitivity of the method, and lower detection limits. Under the optimized conditions, an enrichment factor of 520–587, limit of detection of 0.05–0.90 ng/mL, and linearity range of 0.2–2000 ng/mL (coefficient of determination = 0.9982–0.9995) were obtained. Relative standard deviations were < 10%. This method was successfully coupled with gas chromatography and used for the determination of benzene, toluene, ethylbenzene, and xylene isomers as harmful volatile organic compounds in water and urine samples.     

Simultaneous quantification of five biogenic amines based on LC–MS/MS and its application in honeybee venom from different subspecies

The use of honeybee venom in traditional medicine is increasing due to its unexpected beneficial effects in the treatment of diseases. In this study, a simple and environmentally friendly sample preparation procedure was developed to quantify five biogenic amines—histamine, 5-hydroxytryptamine, dopamine, adrenaline, and noradrenaline—in honeybee venom using high-performance liquid chromatography tandem mass spectrometry. The instrument and sample preparation method were optimized to achieve stable, sensitive, and accurate quantification of the five biogenic amines. The peak purities of five biogenic amines in bee venom were examined using a diode array detector to ensure that endogenous impurities will not interfere with biogenic amines during the chromatographic separation procedure. The correlation coefficient of each compound was higher than 0.998 in the range of 0.5–1000 ng/mL. The limits of detection and quantification of the developed method ranged between 0.09 and 0.17, and 0.3 and 0.59 μg/g, respectively. The average recoveries of spiked biogenic amines with different concentrations were higher than 70.95%, and the intra- and intermediate-day precisions were lower than 7.51% and 10.17%, respectively. The carry-over between each injection and the stability of the target analytes were also evaluated to ensure the effectiveness of this method. The data obtained are presented in various formats, including boxplot, heat map, and principal component analysis diagram, to visualize the differences in the biogenic amine contents of the honeybee venoms from different subspecies. This method hopes to provide the opportunity to distinguish the bee venom produced by different subspecies.     

A novel LC–MS/MS method for the determination of ziritaxestat in rat plasma and its pharmacokinetic study

Ziritaxestat is a first-in-class autotoxin inhibitor. The purpose of this study was to develop a liquid chromatography/electrospray ionization tandem mass spectrometric (LC–MS/MS) method for the determination of ziritaxestat in rat plasma. The plasma sample was deproteinated using acetonitrile and then separated on an Acquity BEH C₁₈ column with water containing 0.1% formic acid and acetonitrile as mobile phase, which was delivered at 0.4 ml/min. Ziritaxestat and the internal standard (crizotinib) were quantitatively monitored with precursor-to-product transitions of m/z 589.3 > 262.2 and m/z 450.1 > 260.2, respectively. The total running time was 2.5 min. The method showed excellent linearity over the concentration range 0.5–2000 ng/ml, with correlation coefficient >0.9987. The extraction recovery was >82.09% and the matrix effect was not significant. Inter- and intra-day precisions (RSD) were <11.20% and accuracies were in the range of −8.50–7.45%. Ziritaxestat was demonstrated to be stable in rat plasma under the tested conditions. The validated LC–MS/MS method was successfully applied to study the pharmacokinetic profiles of ziritaxestat in rat plasma after intravenous and oral administration. Pharmacokinetic results demonstrated that ziritaxestat displayed a short half-life (~3 h) and low bioavailability (20.52%).