Speciation of Cu(II) with a flow-through permeation liquid membrane: discrimination between free copper, labile and inert Cu(II) complexes, under natural water conditions

Metal toxicity is not related to the total metal ion concentration, but to those of some specific Cu(II) species. The Permeation Liquid Membrane technique is based on the carrier-mediated transport of the test metal across a hydrophobic membrane and enables discrimination between various trace metal species in solution. The present work shows how the labile and inert Cu(II) complexes can be determined selectively, by varying the flow-rate of the test solution, in a flow-through cell. A mathematical model of metal flux through the PLM, based on diffusion-limited transport under steady-state conditions, is described. The model and the performance of the technique were studied in well-defined synthetic solutions containing simple organic hydrophilic ligands forming either inert (nitrilotriacetic acid), or labile complexes with Cu(II) (tartaric acid, malonic acid). The results were compared with theoretical predictions of thermodynamic species distribution in solution. Uncertainties on stability constants for copper speciation calculation were taken into account. The detection limits of the device are discussed. This work demonstrates that the flow-through cell is a reliable tool for copper speciation measurements in natural waters.     

Minimal number of chromatographic test parameters for the characterisation of reversed-phase liquid chromatographic stationary phases

This paper focuses on the classification or differentiation of RP-HPLC columns based on measured chromatographic properties. A chemometric study has been conducted on a published data set consisting of 85 RP-HPLC columns and on a data set consisting of 47 self-tested columns. Principal component analysis enables determination of the number of parameters necessary for a rational differentiation. The results show that reducing the number of parameters for such differentiation still allows classification of the columns just as a higher number did. It is shown that three test parameters produce a classification similar to that obtained with five parameters.     

Thermal properties and structure of electrospun blends of PVDF with a fluorinated copolymer

We report the structure and thermal properties of blends comprising poly(vinylidene fluoride) (PVDF) and a random fluorinated copolymer (FCP) of poly(methyl methacrylate)‐random‐1H,1H,2H,2H‐perfluorodecyl methacrylate, promising membrane materials for oil–water separation. The roles of processing method and copolymer content on structure and properties were studied for fibrous membranes and films with varying compositions. Bead‐free, nonwoven fibrous membranes were obtained by electrospinning. Fiber diameters ranged from 0.4 to 1.9 μm, and thinner fibers were obtained for PVDF content >80%. As copolymer content increased, degree of crystallinity and onset of degradation for each blend decreased. Processing conditions have a greater impact on the crystallographic phase of PVDF than copolymer content. Fibers have polar beta phase; solution‐cast films contain gamma and beta phase; and melt crystallized films form alpha phase. Kwei's model was used to model the glass transition temperatures of the blends. Addition of FCP increases hydrophobicity of the electrospun membranes. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 312–322     

Crystallization and melting of cold-crystallized poly(phenylene sulfide)

In this study, we report the melting behavior of poly(phenylene sulfide), PPS, which has been cold-crystallized from the rubbery amorphous state. We find that the crystallization kinetics are faster for cold-crystallized PPS than for melt-crystallized material, due to formation during quenching of a short-range ordered, but noncrystalline, structure. We observe that the endothermic response of cold-crystallized PPS at a large undercooling consists of a low temperature endotherm, followed by an exothermic region, and by the main higher melting endotherm. The lower melting peak temperature of cold-crystallized PPS increases as the crystallization temperature increases, but the main upper melting peak temperature remains almost the same. The size of the exothermic region is strongly related to the degree of undercooling, and must be taken into account in order properly to determine the degree of crystallinity of the material prior to the scan. When the crystallization time is varied, we see a systematic decrease in the size of the main endotherm, and an increase in size of the lower melting endotherm. This suggests that a portion of the main endothermic response is due to reorganization during the scan. Annealing will not only increase the degree of crystallinity but also improve the crystal perfection; therefore the ability of an annealed sample to reorganize decreases as the annealing time increases. However, an additional third melting peak is seen when a cold-crystallized sample is annealed at high temperature for a sufficiently long residence time. The existence of the third melting peak suggests that more than one kind of distribution of crystal perfection may occur when PPS has been cold-crystallized and subsequently annealed.     

Distance distributions recovered from steady-state fluorescence measurements on thirteen donor-acceptor pairs with different Förster distances

The end-to-end distance distribution of a flexible molecule was recovered from steady-state fluorescence energy transfer measurements using the method suggested by Cantor and Pechukas (Proc. Natl. Acad. Sci. USA 68, 2099–2101, 1971). In this method, the Förster distance (R ₀) is varied by attaching different donor-acceptor (D-A) pairs to the flexible linker of interest. Distance distributions are then recovered from energy transfer efficiency measurements on the set of D-A pairs with differentR ₀ values. Thirteen D-A pair compounds were synthesized withR ₀ values ranging from 6 to 32 Å. Each compound contained a tryptamine donor linked by an alkyl chain (10 carbons) to 1 of 13 acceptors. Using these compounds, we have experimentally confirmed the Cantor and Pechukas method for recovering distance distributions. The measured transfer efficiencies, as a function ofR ₀, were fit to the transfer efficiencies predicted for both Gaussian and skewed Gaussian distance distributions. The data support the existence of a skewed Gaussian distribution, and we believe that this is the first experimental observation of an asymmetric distribution for a flexible molecule using fluorescence resonance energy transfer measurements. Finally, the experimentally recovered distance distribution was found to be in good agreement with the distribution predicted from the rotational isomeric state model of Flory (Statistical Mechanics of Chain Molecules, John Wiley & Sons, New York, 1969, Chaps. 1, 3, and 5) but not with the predicted distribution for a freely rotating or freely jointed chain.     

A Convenient and Reproducible Procedure for the Transfer Hydrogenation of 2-Benzyloxy-Tetronic Acids Based on 〈Preactivation〉 of the Catalyst

Access to 2-hydroxy tetronic acids 3 via selective heterogeneous transfer hydrogenation of benzyl ether 2 based on preactivation of the catalyst.     

高光谱最优波长选择及Fisher判别分析法判别玉米颗粒表面黄曲霉毒素

黄曲霉毒素是广泛存在于玉米中且具有剧毒的一种代谢产物,以美国农业部农业研究署(USDA-ARS) Toxicology and Mycotoxin Research Unit提供的2010年先锋玉米为研究对象,验证了高光谱成像技术对玉米中黄曲霉毒素检测的可行性。以甲醇为溶剂制备四种不同浓度的黄曲霉毒素溶液,并将其逐一滴在等量的4组共120粒玉米颗粒表面,以未处理的30粒洁净玉米作为一组对照样本,将大小、形状相似的150个样品随机分为训练集103个,验证集47个;对获取的400～1 000 nm波段范围内的高光谱图像,先进行标准正态变量变换(standard normal variate transformation, SNV)预处理,然后引入基于Fisher判别最小误判率的方法选择最优波长,并以所选波长作为Fisher判别分析法的输入建立判别模型,对玉米颗粒表面不同浓度的黄曲霉毒素进行识别,最后对模型判别正确率进行了验证。结果表明,选取四个最优波长(812.42, 873.00, 900.36和965.00 nm)时Fisher判别分析模型对训练集与验证集的准确率分别为87.4%和80.9%。该方法为含黄曲霉毒素玉米颗粒便携式检测仪器的开发,以及对田间霉变玉米自然代谢产生毒素的检测奠定了技术基础。     

The interlaboratory comparison "IMEP-19 trace elements in rice"—a new approach for measurement performance evaluation

The aim of IMEP is to present objectively the quality of chemical measurements. Participants in IMEP compare their reported measurement results with independent external certified reference values with demonstrated traceability and uncertainty, as evaluated according to international guidelines. IMEP-19 focused on measurements of trace elements in rice aiming to support the Commission Regulation (EC) No. 466/2001 on maximum levels for certain contaminants in foodstuff. Measurement results for the elements Cd, Cu, Pb and Zn were reported by 267 field laboratories involved in food analysis from 43 countries. Performance criteria for the evaluation of the reported measurement results in IMEP-19 are suggested. The chosen performance indicators not only take into account the deviation of the reported measurement value from the certified reference value, but also set criteria for maximum and minimum acceptable uncertainty. The IMEP-19 participants' performance is reviewed by means of using new simple graphical tools, called "Naji plots".