Syringe cleanup with UHPLC-MS/MS for nitroimidazoles and steroids detection in manure-based fertilizers.

A syringe-dispersive solid-phase extraction method was developed for the determination of seven nitroimidazoles and nine steroids in manure-based fertilizers by ultra-high performance liquid chromatography with tandem mass spectrometry. Methanol and acetonitrile were used to extract the sample, and mixed dispersive sorbents dispersed in the syringe were used for purification. The extract was separated with an HSS-T3 column and detected in positive or negative multiple reaction monitoring mode. Under the optimal conditions, the recoveries of the 16 compounds ranged from 70.3 to 112.3% at the four spiked levels (3, 10, 20, and 50 µg/kg) and the relative standard deviations ranged from 1.0 to 12.4%. The limits of detection and quantification were 0.22-0.86 and 0.73-2.87 µg/kg, respectively. This method is simple, fast, and reliable, and can be used to simultaneously screen and determine nitroimidazoles and steroids in manure-based fertilizers.

In-syringe dispersive solid phase filter extraction cleanup followed by liquid chromatography-triple quadrupole mass spectrometry for fast determination of colchicine in plasma/urine.

As an effective treatment for acute gouty arthritis and cardiovascular disease, colchicine is also a toxic alkaloid and may cause poisoning or even death in overdose. The study of colchicine elimination and the diagnosis of poisoning etiology need the rapid and accurate quantitative analysis method in biological matrix. An analytical method was developed for colchicine in plasma and urine by in-syringe dispersive solid phase extraction (DSPE) followed by liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS). Sample extraction and protein precipitation were proceeded with acetonitrile. The extract was cleaned by in-syringe DSPE. An XBridge™ BEH C18 column（100 mm × 2.1 mm, 2.5 µm）was used to separate colchicine by gradient elution with mobile phase of 0.01% (v/v) ammonia-methanol. The amount and filling sequence of magnesium sulfate (MgSO4) and primary secondary amine (PSA) suitable for in-syringe DSPE were studied. Scopolamine was screened as the quantitative internal standard (IS) for colchicine analysis according to the consistency of recovery rate, chromatographic retention time and matrix effects. The limits of detection for colchicine in plasma and urine were both 0.06 ng mL-1 and the limits of quantitation were both 0.2 ng mL-1. The linear range was 0.04 - 20 ng mL-1 (Equivalent to 0.2-100 ng mL-1 in plasma or urine) with a correlation coefficient r > 0.999. By IS calibration, the average recoveries at three spiking levels in plasma and urine were 95.3-102.68% and 93.9-94.8% with the relative standard deviations (RSDs) of 2.9-5.7% and 2.3-3.4%, respectively. The matrix effects, stability, dilution effects and carryover for determination of colchicine in plasma and urine were also evaluated. The elimination of colchicine within 72-384 h post-ingestion was studied for a poisoning patient with the doses of 1 mg d-1 for 39 days and then 3 mg d-1 for 15 days).

Carbon fibers as green and sustainable sorbent for the extraction of isoflavones from environmental waters.

Isoflavones are a group of phytoestrogens of important environmental concern due to their endocrine disrupting effects. This article presents a rapid, green, and sustainable method for determining four isoflavones (daidzein, genistein, formononetin, and biochanin A) in environmental waters complying with current trends in Analytical Chemistry. The method consists of in-syringe dispersive solid-phase extraction (DSPE) as the extraction approach, using carbon fibers as extraction material. The synthesis of carbon fibers is simple and sustainable, since it only requires a natural product such as raw cotton as precursor, which is thermally treated (600 °C for 30 min) in an inert (Ar) atmosphere to convert it into carbon fibers. After extraction, the final eluate is analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The proposed methodology allows the determination of the four isoflavones in water samples at the ng L-1 range, with limits of detection in the range from 17 to 25 ng L-1, relative standard deviations (RSD) from 2.8 to 10.1%, and good batch-to-batch repeatability (RSD < 13%). The method was finally applied to six environmental water samples from different sources and two swimming pool waters, and concentrations of all analytes up to 490 ng L-1 were found. The highest concentrations were found in those samples close to crop fields. Relative recovery values (80-121%) showed that the aqueous matrices considered in this work did not significantly affect the extraction process. This method overcomes the drawbacks of the previous works with the same purpose, such as consuming large volumes of organic solvents or prolonged extraction times. Moreover, this procedure would allow the extraction stage to be carried out in situ, since only the sorbent material (previously synthesized in the laboratory) and disposable syringes are required.

Effervescence-assisted ß-cyclodextrin/attapulgite composite for the in-syringe dispersive solid-phase extraction of pyrethroids in environmental water samples.

In this research, an effervescence-assisted ß-cyclodextrin/attapulgite composite (ß-CD/ATP) for the in-syringe dispersive solid-phase extraction (EAIS-DSPE) of pyrethroids in environmental samples was developed for the first time. A syringe was used to conduct the extraction procedure and a small amount of ß-CD/ATP was dispersed into the solution with the release of carbon dioxide when the effervescent tablet components dissolved in water. Then, the sorbent was recovered using a filter membrane, and the analytes were directly eluted using acetonitrile. In the process, the ß-CD/ATP sorbent resulted in an excellent extraction efficiency compared to commercially available sorbents such as C18 and HLB. Moreover, in the extraction procedure, both the ß-cyclodextrin inclusion interactions (especially the hydrophobic effects) and the special structure of the ATP contributed to the efficient enrichment of pyrethroids in aqueous media. The amount of ß-CD/ATP sorbent, the volume of desorption, the ratio of NaH2PO4/Na2CO3, the volume of the sample, and the pH were screened using a Plackett-Burman design. All factors affecting the procedure were optimized by applying a central composite design. Under the optimized conditions, a good repeatability (RSDs) ranging from 1.7 to 2.3, linearity (2.5-500µgL(-1)), limits of detection (LODs) (0.15-1.03µgL(-1)), and an acceptable recoveries (76.8-86.5%) were achieved. Finally, the proposed method was successfully applied for the determination of pyrethroids in environmental samples including river water, reservoir water and lake water.

Facile synthesis of polyaniline-coated SiO2 nanofiber and its application in enrichment of fluoroquinolones from honey samples.

In this study, polyaniline coated SiO2 nanofibers (PANI/SiO2) was prepared by combining electrospinning technique with in-situ polymerization. The proposed strategy for the preparation of PANI/SiO2 can eliminate the aggregation of PANI and the yield of PANI/SiO2 was high. Scanning electron microscopy (SEM) images showed that PANI nanoparticles were uniformly coated on the surface of SiO2 nanofibers. The as-prepared PANI/SiO2 nanofibers were then applied as the sorbent for in-syringe dispersive solid-phase extraction (dSPE) for the extraction of fluoroquinolones (FQs) from honey samples. The influence of SiO2 amount on the formation of PANI/SiO2 and several parameters that affect the extraction efficiency were investigated. Under optimized conditions, a rapid, simple and effective method for the determination of FQs in honey sample was developed by coupling with liquid chromatography-fluorescence detector (LC-FLD) analysis. Due to the fast extraction equilibrium, the whole sample pretreatment process could be accomplished within 4 min. The limits of detection (LODs) for the target FQs were found to be 0.1-1.3 ng/g. The recoveries in honey sample were in the range of 81.4-118.1% with the RSDs of 0.8-14.4% (intra-day) and 1.4-14.9% (inter-day). This study offers a new strategy for the preparation of functional SiO2 nanofibers using post-electrospinning modification by in-situ polymerization, which could be generally applied in the preparation of various separation materials with electrospun nanofibers.