Entropic effect implication for change in polymer coils swelling state in the demixing enthalpy recovery of aqueous poly(vinyl methyl ether) solutions

Time‐dependent demixing enthalpy recovery behavior of aqueous poly(vinyl methyl ether) (PVME) solutions exhibits distinct recovery characteristics in three concentration regions. The absence of recovery behavior below a water concentration of 38.3 wt % indicates that the PVME coil is in a globular state. The typically sigmoidal recovery behavior of demixing enthalpy above 38.3 wt % is ascribed to the reswelling of the collapsed polymer coils induced by the entropic effect. The increase in difference between the upper and lower limits indicates the continued swelling of the PVME coils. Above 65 wt %, a dominant diluting effect can be observed, and a much longer phase separation time is needed to reach the expected lower limit. In contrast, the recovery of demixing enthalpy in a wide range of water concentration (from 38.3 to 90 wt %) exhibits the same feature. The infrared spectroscopy results are in agreement with the above macroscopic differential scanning calorimetry results. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 142–151     

Rapid and easy quantification of elemental sulphur in aqueous samples from biological reactors: the turbidimetric method revisited

Recent developments in wastewater treatment have led to a renewed interest to obtain elemental sulphur (S°) as a by-product from bioreactors. However, practical studies are limited by the gap of adequate analytical techniques for its determination. This paper provides a statistical study and matrix effect evaluation of an adapted spectrophotometric method for routine S° analyses in aqueous samples, based on a methodology previously described by Hart (1961). Four complex matrices were tested: domestic sewage and effluent samples from three different bioreactors. Tested performance criteria included linearity, matrix effect, limit of detection and quantification and S° recovery. Results were linear (R² = 0.99994) in the studied range (5 to 100 mg S° L^?1) and no matrix effect was observed. The accuracy was based on recovery values that varied from 100% to 106%. The colloidal S° separation and extraction protocol was also considered suitable for aqueous samples, reaching more than 99.0% of S° recovery.     

Liquid chromatographic determination of trace levels of nitrophenols in water samples after dispersive magnetic solid phase extraction

An efficient and fast dispersive magnetic solid phase extraction method was developed using MIL‐101(Cr)/poly (mercaptobenzothiazole)@magnetite nanoparticles for the preconcentration and determination of nitrophenols in river and rain water samples. High‐performance liquid chromatography‐Ultraviolet instrument was applied for the analysis of target nitrophenols. The effect of several variables on the extraction performance was explored via design of experiment approach. Limits of detection and linear dynamic ranges were attained in the range of 0.05–0.10 µg/L and 0.2–250 µg/L, respectively. The enrichment factors were in the range of 317–363. The precision (n = 3) of dispersive magnetic solid phase extraction method was in the range of 5.3–6.8%. Eventually, the method was utilized for the analysis of target nitrophenols in river and rain water samples.     

Validation of a HPLC/MS method for simultaneous quantification of clonidine,morphine and its metabolites in human plasma

A high‐performance liquid chromatography–tandem mass spectrometry method was developed and validated for the simultaneous quantification of morphine, morphine's major metabolites morphine‐3‐glucuronide and morphine‐6‐glucuronide, and clonidine, to support the pharmacokinetic analysis of an ongoing double‐blinded randomized clinical trial that compares the use of morphine and clonidine in infants diagnosed with neonatal abstinence syndrome. Plasma samples were processed by solid‐phase extraction and separated on an Inertsil ODS‐3 (4 μm) column using an 0.1% formic acid in water–0.1% formic acid in methanol gradient. Detection of the analytes was conducted in the positive multiple reaction monitoring mode. The range of quantitation was 1–1000 ng/mL for morphine, morphine‐3‐glucuronide and morphine‐6‐glucuronide, and 0.25–100 ng/mL for clonidine. Intra‐day and inter‐day accuracy and precision were ≤15% for all analytes across the quantitation range. Extraction recovery rates were ≥94% for morphine, ≥90% for M3G, ≥87% for M6G and ≥ 79% for clonidine. Matrix effect ranged from 85–94% for clonidine to 101–106% for M3G. The method fulfilled all predetermined acceptance criteria and required only 100 μL of starting plasma volume. Furthermore, it was successfully applied to 30 clinical trial plasma samples.     

Er3+单掺、Er3+/Yb3+共掺杂Ca12Al14O32F2的 制备及上转换发光性质

利用高温固相法成功制备了Er~(3+)单掺、Er~(3+)/Yb~(3+)共掺杂Ca_(12)Al_(14)O_(32)F_2上转换发光样品。在980 nm激光激发下,Er~(3+)单掺和Er~(3+)/Yb~(3+)共掺杂样品均呈现出较强的绿光(528,549 nm)和较弱的红光(655 nm)发射,分别归因于Er~(3+)离子的~2H_(11/2),~4S_(3/2)→~4I_(15/2)和~4F_(9/2)→~4I_(15/2)能级跃迁。随着Er离子浓度的增加,单掺杂样品上转换发光强度先增大后减小,最佳掺杂浓度为0.8%。共掺杂Yb~(3+)后,Er~(3+)的发光强度明显增大。还原气氛下合成的样品上转换发光强度增大约两倍,可能和笼中阴离子基团变化有关。发光强度和激发光功率的关系表明所得上转换发射为双光子吸收过程,借助Er~(3+)-Yb~(3+)体系能级结构详细讨论了上转换发射的跃迁机制。     

Novel thionin-functionalised core shell magnetic nanoparticles for dispersive solid-phase extraction of Hg(II) in food and water samples

To develop an accurate and precise method for separation and pre-concentration of Hg(II), a novel thionin functionalised core shell structure magnetic material has been prepared and characterised. The extraction ability of the material was evaluated by magnetic solid-phase extraction coupled with inductively coupled plasma mass spectrometry determination of Hg(II) in food and water samples. Combining the advantages of magnetic separation with selective extraction of thionin towards Hg(II), the material exhibits enhanced enrich selectivity and efficiency for Hg(II). The experimental parameters influencing Hg(II) extraction efficiency, including pH of the aqueous solution, the dosage of the adsorbent, extraction time and sample volume, were systematically investigated. Under the optimised conditions, concentration of Hg(II) at 1.0 μg L^?1 can be successfully enriched by the material without the interference of the common co-existing ions. The enrichment factor and adsorption capacity were 250 and 75.2 mg g^?1, and precise of the method was confirmed by analysing the spiked food, water samples and standard water reference samples with the recoveries of 92.5–101.8%.     

SIMS of organic layers with unknown matrix parameters: Locating the interface in dual beam argon gas cluster depth profiles

Four simple methods are evaluated to determine their accuracies for establishing the interface location in secondary ion mass spectrometry intensity depth profiles of organic layers where matrix effects have not been measured. Accurate location requires the separate measurement of each ion's matrix factor. This is often not possible, and so estimates using matrix-less methods are required. Six pure organic material interfaces are measured using many secondary ions to compare their locations from the four methods with those from full evaluation with matrix terms. For different secondary ions, matrix effects cause the apparent interface positions to vary over 20 nm. The shifts in the intensity profiles on going from a layer of P into a layer of Q are in the opposite direction to that for going from Q into P, so doubling layer thickness errors. The four methods are as follows: M1, use of the median interface position in the intensity profiles for the five lightest ions for 15 ≤ m/z ≤ 150; M2, extrapolation of the position for each ion to m/z = 0 for ions with m/z ≤ 150; M3, as M2 but for m/z ≤ 300; and M4, the extreme positions for all m/z ≤ 100. Comparison with the location using matrix terms shows their ranking, from best to worst, to be M4, M3, M1, and M2 with average errors of 10%, 12%, 14%, and 17%, respectively, of the profile interface full widths at half maximum. Use of pseudo-molecular ions is very much poorer, exceeding 50%, and should be avoided.     

Critical Assessment of the DFT + U Approach for the Prediction of Vanadium Dioxide Properties

In a previous study (Stahl and Bredow, Chem. Phys. Lett. 2018, 695, 28–33), we have studied structural, energetic, and electronic properties of two vanadium dioxide VO₂ polymorphs with modified global and range-separated hybrid functionals. Since hybrid methods are computationally demanding, we evaluate the computationally more efficient DFT + U method in the present study. We assessed the widely used Dudarev PBE + U approach with a literature value of the effective Hubbard parameter U_eff = 3.4 eV. We compared the PBE + U results for the two VO₂ polymorphs with our previous results, a self-consistent hybrid functional sc-PBE0, and the meta-GGA functional SCAN. It was found that the PBE + U method yields a strongly distorted monoclinic phase and does not reproduce the metal-to-insulator transition of VO₂ correctly, even with modified values of U_eff. On the other hand, sc-PBE0 and SCAN describe the relative stability and the electronic structure of both polymorphs correctly and also provide reasonable lattice parameters. The functional SCAN yields the optimal balance between computational efficiency and accuracy. © 2019 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc.     

Extremal generalized centralizers in matrix algebras

We describe matrices with extremal generalized centralizers over algebraically closed fields.     

Determination of sugars and cyclitols isolated from various morphological parts of Medicago sativa L

Plant research interest has increased all over the world, and a large body of evidence has been collected to show the huge potential of medicinal plants in various disease treatments. Medicago sativa L., known as alfalfa, is a rich source of biologically active components and secondary metabolites and was frequently used from the ancient times both as fodder crop and as a traditional medicine in the treatment of various diseases. Cyclitols, naturally occurring in this plant, have a particular interest for us due to their significant anti‐diabetic, antioxidant, anti‐inflammatory, and anti‐cancer properties. In the present study we revealed the isolation, the identification, and the quantification of some cyclitols and sugars extracted from different morphological parts of alfalfa plant. Soxhlet extraction and solid phase extraction were used as extraction and purification methods, while for the analyses derivatization followed by gas chromatography with mass spectrometry was involved. The obtained results showed significant differences in the quantities of cyclitols and sugars found in the investigated morphological parts, ranging between 0.02 and 13.86 mg/g of plant in case of cyclitols, and in the range of 0.09 and 40.09 mg/g of plant for sugars. However, roots have the richest part of cyclitols and sugars in contrast to the leaves.