Leveraging Material Properties in Fluorescence Anion Sensor Arrays: A General Approach

As the demand for probes suitable for sensor development increases, investigation of approaches that utilize known successful receptors gains in general importance. This study describes a two‐prong approach that can be used as a guide to developing sensors from known receptors. First, the conversion of a simple receptor, calix[4]pyrrole, into a fluorescent probe to establish a ratiometric signal is described. Secondly, the sensors that employ an output from a single ratiometric calix[4]pyrrole probe are fabricated by using poly(ether‐urethane) hydrogel copolymers. These hydrogels are designed to absorb, internalize and transport aqueous electrolytes. A sensor array of ten different poly(ether‐urethane) matrices with varying comonomer proportions were doped with a single probe and were exposed to eight different anions: acetate, benzoate, fluoride, chloride, phosphate, pyrophosphate, hydrogen sulfide, and cyanide, eight urine samples and anti‐inflammatory drugs (NSAIDs). The poly(ether‐urethane) matrices comprise different proportions of anion‐binding urethane moieties and different hydrophilicity given by the ratio between ethylene glycol ether and butylene glycol ether. This diversity in the hydration behavior provides different environment polarity, in which the recognition and self‐assembly processes display enough diverse behavior to allow for unique response of the probe to the analytes. Furthermore, a single probe is shown to recognize eight different aqueous anions and eight urine samples when embedded in ten different polyurethanes in an array that displays 100 % classification accuracy. To demonstrate the potential of the concept for quantitative studies, an estimation of non‐steroidal anti‐inflammatory drugs ibuprofen and diclofenac in water and in saliva was performed. A limit of detection of 0.1 ppm and a dynamic range of 0.1–0.6 and 0.05–60 ppm was observed, respectively. Given the general difficulty of chemosensors to recognize aqueous anions, the fact that one probe recognizes eight different analytes attests to an enormous effect of the polymer environment on the recognition process. This method could be used to generate a variety of sensor arrays for various analyses including species that are difficult to recognize, such as small‐molecule‐ and inorganic anions.     

Accurate integration over atomic regions bounded by zero‐flux surfaces

The approach for the integration over a region covered by zero‐flux surface is described. This approach based on the surface triangulation technique is efficiently realized in a newly developed program TWOE . The elaborated method is tested on several atomic properties including the source function. TWOE results are compared with those produced by using well‐known existing programs. Absolute errors in computed atomic properties are shown to range usually from 10^?6 to 10^?5 au. The demonstrative examples prove that present realization has perfect convergence of atomic properties with increasing size of angular grid and allows to obtain highly accurate data even in the most difficult cases. It is believed that the developed program can be bridgehead that allows to implement atomic partitioning of any desired molecular property with high accuracy. © 2012 Wiley Periodicals, Inc.     

Experimental shift allowance in the deconvolution of SIMS depth profiles

We study the deconvolution of the secondary ion mass spectrometry (SIMS) depth profiles of silicon and gallium arsenide structures with doped thin layers. Special attention is paid to allowance for the instrumental shift of experimental SIMS depth profiles. This effect is taken into account by using Hofmann's mixing‐roughness‐information depth model to determine the depth resolution function. The ill‐posed inverse problem is solved in the Fourier space using the Tikhonov regularization method. The proposed deconvolution algorithm has been tested on various simulated and real structures. It is shown that the algorithm can improve the SIMS depth profiling relevancy and depth resolution. The implemented shift allowance method avoids significant systematic errors of determination of the near‐surface delta‐doped layer position. Copyright © 2013 John Wiley & Sons, Ltd.     

Effect of AlF3 production waste on the processes of hydration and hardening of the alkali-activated Portland cement with sodium silicate hydrate

Journal of Thermal Analysis and Calorimetry - Generally, the early strength of hardened Portland cement paste is controlled, by changing the mineral composition of clinker and grinding fineness. By...     

Tetrathiomolybdates of nickel

Summary The complexes [Ni(en)₃]MoS₄, [Ni(dien)₂]MoS₄ and [Ni(phen)₂(MoS₄)]·2H₂O (en = ethylenediamine, dien = diethylenetriamine, phen = 1,10-phenanthroline) were prepared. On the basis of their magnetochemical and spectral properties the compounds can be characterized as octahedral nickel(II) complexes. The complexes were also studied by c.v. Chemical oxidation of [Ni(en)₃]MoS₄ affords [Ni(en)MoS₄]₂SO₄; this complex has been characterized by i.r. and e.p.r. spectroscopy and by magnetic measurements.     

Decomposition of molybdate–hexamethylenetetramine complex: One single source route for different catalytic materials

Decomposition of ammonium heptamolybdate–hexamethylentetramine (HMTA) complex (HMTA)₂(NH₄)₄Mo₇O₂₄·2H₂O was studied as a function of treatment conditions in the range 300–1173 K. The evolution of solid products during decomposition was studied by thermal analysis and in situ EXAFS. Depending on the nature of the gas used for treatment, single phases of highly dispersed nitrides Mo₂N, carbide Mo₂C, or oxide MoO₂ can be obtained. The nature of the products obtained was explained by qualitative thermodynamical considerations. Morphology of the solids considerably depends on such preparation parameters as temperature and mass velocity of the gas flow. For the nitride-based materials, catalytic activity was evaluated in the model thiophene HDS reaction. It was demonstrated that NH₃-treated samples showed better catalytic activity than N₂-treated ones due to cleaner surface and better morphology. Transmission microscopy, XRD and XPS studies showed that MoS₂ is formed on the surface during HDS reaction or sulfidation with H₂S. Optimized nitride-derived catalysts showed mass activity several times higher than unsupported MoS₂ or MoS₂/Al₂O₃ reference catalyst.     

The orientation and charge of water at the hydrophobic oil droplet-water interface

We established the charge and structure of the oil/water interface by combining ζ-potential measurements, sum frequency scattering (SFS) and molecular dynamics simulations. The SFS experiments show that the orientation of water molecules can be followed on the oil droplet/water interface. The average water orientation on a neat oil droplet/water interface is the same as the water orientation on a negatively charged interface. pH dependent experiments show, however, that there is no sign of selective adsorption of hydroxide ions. Molecular dynamics simulations, both with and without intermolecular charge transfer, show that the balance of accepting and donating hydrogen bonds is broken in the interfacial layer, leading to surface charging. This can account for the negative surface charge that is found in experiments.     

Synthesis and Thermal Transformations of 1-Polyfluoro-Alkyl-2-Trialkylsilylethyl Esters of Phosphorus Acids

Abstract

We have studied the phosphorylation of 1-polyfluorólkyl-2-trialkylsilylethanols (I) with phosphorus acids chlorides.     

Ion-chromatographic determination of chromium (VI)

Summary A simple ion-chromatographic method has been developed for the selective determination of chromium (VI) using UV-photometric detection. The anion exchanger was based on a matrix of a 2-hydroxyethyl-methacrylate copolymer; the mobile phase consisted of phosphate buffer and sodium perchlorate. The relative standard deviation was 2.26%. Application was made to waste waters of the metallurgical industry.