Phosphine-catalyzed [4+2] cycloaddition of sulfamate-derived cyclic imines with allenoates: synthesis of sulfamate-fused tetrahydropyridines

Using n-PrPPh₂ as the nucleophilic catalyst, the [4+2] cycloaddition reaction of the sulfamate-derived cyclic imines with allenoates works efficiently to yield various sulfamate-fused tetrahydropyridines in high yields with excellent diastereoselectivities. Using amino acid-based bifunctional phosphine as chiral catalyst, an asymmetric [4+2] cycloaddition reaction was achieved, giving chiral sulfamate-fused tetrahydropyridines in high yields with good enantiomeric excesses.     

Lewis acid-catalyzed tandem acylation–Nazarov cyclization for the syntheses of fused cyclopentenones

Treatment of N-tosylpyrroles or N-tosylindoles with α-unsubstituted α,β-unsaturated carboxylic acids or unsaturated carboxylic acids having an α electron-withdrawing substituent in the presence of TFAA and a Lewis acid catalyst resulted in the formation of fused cyclopentenones via a tandem acylation–Nazarov cyclization sequence, while either the acylation product obtained or no reaction occurred in the absence of the Lewis acid catalyst.     

Surface modification to improve the sorption property of U(VI) on mesoporous silica

Polyoxometalates K₇[α-PW₁₁O₃₉]·14H₂O (PW11) modified mesoporous silica (MCM-48) with cubic structure, was prepared by impregnation and calcination methods. The modified mesoporous silica sorbent (PW11/MCM-48) was studied as a potential adsorbent for U(VI) from aqueous solutions. MCM-48 and PW11/MCM-48 were confirmed by X-ray diffraction and nitrogen physisorption techniques. The results indicate the original keggin structure of PW11 and mesoporous structure of MCM-48 are maintained after supporting PW11 on mesoporous silica MCM-48. The effects of contact time, solid-to-liquid ratio (m/V), solution pH and ionic strength on U(VI) sorption behaviors of the pure and modified mesoporous silicas were also studied. Typical sorption isotherms such as Langmuir and Freundlich isotherms were determined for sorption process. The results suggest that the sorption of U(VI) on MCM-48 or PW11/MCM-48 are strongly dependent on pH values but independent of ionic strength. The sorption capacity of PW11/MCM-48 for U(VI) is about ten times more than that of MCM-48.     

Evaluation of Se(IV) removal from aqueous solution by GMZ Na-bentonite: batch experiment and modeling studies

Bentonite has been studied extensively because of its strong sorption and complexation ability. In this work, the sorption of Se(IV) on purified GMZ bentonite was investigated under ambient temperature as functions of contact time, pH, Se(IV) concentration and co-existing ion Eu(III) using batch techniques. Sorption kinetics of Se(IV) was successfully described by the pseudo-second-order rate equation. The sorption amount of Se(IV) was strongly dependent on the solution pH, and a positive effect was observed on Se(IV) and Eu(III) co-sorption when these two elements existed in the same system under high surface coverage of sorbent. Double layer model was set up and used to quantitatively interpret the sorption experimental data collected in binary and ternary sorption systems. From the experimental results, one can conclude that GMZ bentonite may have good potentialities for immobilizing selenium in nuclear wastes.     

爆炸条件下溶菌酶反应产物的基质辅助激光解吸-飞行时间质谱分析

以爆炸条件下溶菌酶的反应产物为研究对象,运用基质辅助激光解吸-飞行时间质谱的方法研究其反应产物与不同炸药的反应特征性.结果显示,雷管的使用不会对溶菌酶有影响,而在有爆炸物爆炸的条件下,除了正常溶菌酶酶解多肽信号外,一些[MH+17]+,[MH+18]+,[MH+28]+,[MH+32]+和[MH+44]+的加合峰信号也能被检测到.这可能是在炸药爆炸过程中产生的一些活性小分子(如NH3,H2O,CO/N2,O2,CO2)与溶菌酶发生反应得到的反应产物.不同炸药生成的活性小分子能够分别与溶菌酶的某些反应位点反应生成特征性的反应产物,有利于这些炸药的分析与检测.     

Construction of a portable sample preparation device with a magnetic poly(methacrylic acid‐co‐ethylene dimethacrylate) monolith as the extraction medium and its application in the enrichment of UV filters in water samples

A portable sample preparation device with a magnetic polymer monolith as the extraction medium was constructed. The monolith was synthesized by polymerizing methacrylic acid and ethylene dimethacrylate around a cylindrical magnet. In this way, the monolith with a magnetic core could be readily attached to the extraction device by magnetism. The constructed device was evaluated for the enrichment of UV filters in water samples, followed by high‐performance liquid chromatographic analysis. The extraction efficiency for the targets was satisfactory with no matrix interference. Good linearities were obtained for the UV filters with the correlation coefficients >0.9986. The limits of detection and quantification for the UV filters were 0.3–0.8 and 1.0–2.4 ng/mL, respectively. The recoveries of the UV filters from the spiked water samples at the concentration of 100 ng/mL were 95.3–101.7%, with relative standard deviations <10%. Accordingly, the proposed portable device was demonstrated to be suitable for on‐site simultaneous sampling, purification, and preconcentration within a single step.     

Negative‐pressure‐induced collector for a self‐balance free‐flow electrophoresis device

Uneven flow in free‐flow electrophoresis (FFE) with a gravity‐induced fraction collector caused by air bubbles in outlets and/or imbalance of the surface tension of collecting tubes would result in a poor separation. To solve these issues, this work describes a novel collector for FFE. The collector is composed of a self‐balance unit, multisoft pipe flow controller, fraction collector, and vacuum pump. A negative pressure induced continuous air flow rapidly flowed through the self‐balance unit, taking the background electrolyte and samples into the fraction collector. The developed collector has the following advantages: (i) supplying a stable and harmonious hydrodynamic environment in the separation chamber for FFE separation, (ii) effectively preventing background electrolyte and sample flow‐back at the outlet of the chamber and improving the resolution, (iii) increasing the preparative scale of the separation, and (iv) simplifying the operation. In addition, the cost of the FFE device was reduced without using a multichannel peristaltic pump for sample collection. Finally, comparative FFE experiments on dyes, proteins, and cells were carried out. It is evident that the new developed collector could overcome the problems inherent in the previous gravity‐induced self‐balance collector.     

Tissue imaging and serum lipidomic profiling for screening potential biomarkers of thyroid tumors by matrix-assisted laser desorption/ionization-Fourier transform ion cyclotron resonance mass spectrometry

Changes in serum lipidome and in tissue lipidome are associated with cancer. In this study, tissue mass spectrometry imaging (MSI) and serum lipid profiling by matrix-assisted laser desorption/ionization-Fourier transform ion cyclotron resonance mass spectrometry (MALDI-FTICR MS) were performed to investigate significantly changed lipids in both tumor (malignant thyroid cancer (MTC) and benign thyroid tumor (BTT)) tissues and sera. Y-scatterplots of variable importance in the projection (VIP) values vs. fold change values indicate that change trends in the levels of ten lipids (i.e., phosphatidylcholine (PC)(34:1), PC(36:1), PC(38:6), phosphatidic acid (PA) (36:2), PA(36:3), PA(38:3), PA(38:4), PA(38:5), PA(40:5), and sphingomyelin (SM)(34:1)) in both tissues and sera from MTC patients, BTT patients, and normal individuals are significantly associated with these three types of pathophysiological status. In order to examine their diagnostic ability, 289 serum samples from 124 MTC patients, 43 BTT patients, and 122 normal controls were randomly divided into the training set and validation set. A biomarker of PC(34:1) exhibited excellent diagnostic ability to differentiate both MTC and BTT patients from normal individuals, with an area under the receiver operating characteristic (ROC) curve value of 0.984, a sensitivity of 96.4 %, and a specificity of 92.7 %. A panel which included PA(36:3) and SM(34:1) could distinguish between MTC and BTT, with an area under receiver operating characteristic curve (AUC) of 0.961, a sensitivity of 87.8 %, and a specificity of 92.9 %. It is worth noting that a panel consisting of PC(34:1), PA(36:3), and SM(34:1) could differentiate MTC patients from both BTT patients and normal individuals, with an AUC of 0.841, a sensitivity of 86.6 %, and a specificity of 75.5 %.

Determination of phthalate esters in edible oils by use of QuEChERS coupled with ionic-liquid-based dispersive liquid–liquid microextraction before high-performance liquid chromatography

A selective and low organic-solvent-consuming method of sample preparation combined with high-performance liquid chromatography with diode-array detection is introduced for analysis of phthalic acid esters in edible oils. Sample treatment involves initial liquid–liquid partitioning with acetonitrile, then QuEChERS cleanup by dispersive solid-phase extraction with primary secondary amine as sorbent. Preconcentration of the analytes is performed by ionic-liquid-based dispersive liquid–liquid microextraction, with the cleaned-up extract as disperser solvent and 1-hexyl-3-methylimidazolium hexafluorophosphate as extraction solvent. Under the optimized conditions, correlation coefficients (r) were 0.998–0.999 and standard errors (S _y/x ) were 2.67–3.37?×?10³ for calibration curves in the range 50–1000 ng g^?1. Detection limits, at a signal-to-noise ratio of 3, ranged from 6 to 9 ng g^?1. Intra-day and inter-day repeatability, expressed as relative standard deviation, were in the ranges 1.0–6.9 % and 2.4–9.4 %, respectively. Recovery varied between 84 % and 106 %. The developed method was successfully used for analysis of the analytes in 28 edible oils. The dibutyl phthalate content of four of the 28 samples (14 %) exceeded the specific migration limit established by domestic and international regulations.

Validation of an LC-MS/MS method for the quantitative determination of a novel fungicide: pyraoxystrobin in rat plasma and its application to a toxicokinetics study

A simple, sensitive, and reliable liquid chromatography tandem mass spectrometry (LC-MS/MS) method has been developed for determination of pyraoxystrobin in rat plasma and applied to a toxicokinetics study. The separation was performed by gradient elution on a Luna 5 μ C18 (2) 100 Å column (50?×?4.6 mm I.D., 5 μm) with mobile phase: water (0.1 % formic acid, v/v)/acetonitrile (0.1 % formic acid, v/v), followed by quantification with a mass detector in multiple reaction monitoring (MRM) mode using ESI as an interface. The calibration curve was linear over a concentration range of 1.00–200 ng/mL. The recovery for pyraoxystrobin ranged from 101.4 to 108.2 %. The intraday bias and precision ranged from ?9.3 to 8.1 % and from 0.7 to 8.4 %, respectively, and the interday bias and precision ranged from ?0.3 to 4.0 % and from 4.4 to 7.2 %, respectively. The toxicokinetics of pyraoxystrobin after single 100 and 1,000 mg/kg oral doses were studied in rats. Figure

The chromatogram of pyraoxystrobin highest calibration standard (ULOQ) extract.