Ion-selective Membranes Prepared Upon Layer-by-Layer Assembly of Azamacrocycles and Polyelectrolytes

Summary : Recent studies on ion transport across multilayered membranes of azamacrocycles and polyelectrolytes are reviewed. Membranes were built up on porous PAN/PET supports using electrostatic layer-by-layer assembly. Two types of separation membranes were prepared, type I consisting of protonated hexaazacyclooctadecane and polyvinylsulfate, and type II of hexaazacyclo-octadecane hexaacetic acid and protonated polyvinylamine. Ion transport was studied under dialysis, nanofiltration and reverse osmosis conditions. Type I membranes were suitable for efficient separation of mono- and divalent anions, whereas type II membranes were suited for separation of mono- from di- and trivalent cations.     

On the hyperbolic unitary geometry

Hans Cuypers (Preprint) describes a characterisation of the geometry on singular points and hyperbolic lines of a finite unitary space—the hyperbolic unitary geometry—using information about the planes. In the present article we describe an alternative local characterisation based on Cuypers’ work and on a local recognition of the graph of hyperbolic lines with perpendicularity as adjacency. This paper can be viewed as the unitary analogue of the second author’s article (J. Comb. Theory Ser. A 105:97–110, 2004) on the hyperbolic symplectic geometry.     

Bringing brain imaging to the school to assess arithmetic problem solving: chances and limitations in combining educational and neuroscientific research

Scientific collaboration between neuroscience and mathematics education has mostly focused on brain imaging trying to inform education. This study aims at meeting expectations of both research fields, thus enhancing the ecological validity. We investigated the influence of age, mathematical competency, and task characteristics (format, complexity) on students’ arithmetic performance. Based on behavioral data from a pilot study (n = 73), arithmetic tasks were chosen for a subsequent investigation (n = 90), in which parietal brain activation was measured with near-infrared spectroscopy. Substantial group differences in calculation time were observed. While task characteristics influenced arithmetic performance in both age groups, this influence was much smaller for grade 8 students. However, parietal brain activation during calculation was not affected by age, mathematical competency, or task characteristics. Limitations of the experimental design and general problems of applying imaging methods to the school context are discussed.     

New application of a subcellular fractionation method to kidney and testis for the determination of conjugated linoleic acid in selected cell organelles of healthy and cancerous human tissues

To clarify the mechanism of the anticarcinogenic effect of conjugated linoleic acid (CLA), its intracellular distribution needs to be determined. Subcellular fractionation using centrifugation techniques is a method that is frequently used for isolation of cell organelles from different tissues. But as the size and density of the organelles differ, the method needs to be optimised for every type of tissue. The novelty of this study is the application of a subcellular fractionation method to human healthy and cancerous renal and testicular tissue. Separation of total tissue homogenate into nuclei, cytosol, and a mixture of mitochondria and plasma membranes was achieved by differential centrifugation. As mitochondria and plasma membranes seemed to be too similar in size and weight to be separated by differential centrifugation, discontinuous density-gradient centrifugation was carried out successfully. The purity of the subcellular fractions was checked by measuring the activity of marker enzymes. All fractions were highly enriched in their corresponding marker enzyme. However, the nuclear fractions of kidney and renal cell carcinoma were slightly contaminated with mitochondria and plasma membrane fractions of all tissues with lysosomes. The fraction designated the cytosolic fraction contained not only cytosol, but also microsomes and lysosomes. The CLA contents of the subcellular fractions were in the range 0.13–0.37% of total fatty acids and were lowest in the plasma membrane fractions of all types of tissue studied. C16:0, C18:0, C18:1 c9, C18:2 n-6, and C20:4 n-6 were found to be the major fatty acids in all the subcellular fractions studied. However, marked variations in fatty acid content between subcellular fractions and between types of tissue were detectable. Because of these differences between tissues, no general statement on characteristic fatty acid profiles of single subcellular fractions is possible.     

Small-angle neutron scattering study of poly(methyl methacrylate-block-sodium acrylate-block-methyl methacrylate) and poly(sodium acrylate-block-methyl methacrylate-block-sodium acrylate) triblock copolymers in aqueous solutions

 Small-angle neutron scattering experiments were made on poly(methyl methacrylate-block-sodium acrylate-block-methyl methacrylate) [p(MMA-b-NaA-b-MMA)] and p(NaA-b-MMA-b-NaA) solutions by varying the composition and the concentration of the polymer with and without 1 M NaCl added. Scattering curves could be evaluated by assuming that the polymers aggregate into polydisperse micelles. The experiments support the expectation that in the case of the p(MMA-b-NaA-b-MMA) block sequence the hydrophilic blocks form closed loops connected by both ends to the micellar cores; in the case of the p(NaA-b-MMA-b-NaA) block sequence they float freely in the solvent. The micellar cores exert considerable stability against dilution and added electrolyte. The interaction of charged micelles could be formally described in terms of volume exclusion and the Derjaguin–Landau–Verwey–Overbeek potential. Received: 20 December 2000 Accepted: 18 August 2001     

Syntheses, Spectra, and Structures of (Diphosphine)platinum(II) Carbonate Complexes

A variety of (diphosphine)platinum(II) carbonate complexes, (LL)Pt(CO(3)), are readily prepared from the corresponding (diphosphine)platinum dichlorides by treatment with silver carbonate in dichoromethane solution provided that water is present. This reaction also permits facile preparation of analogous (13)C-labeled complexes. The carbonate ligands in these complexes have been characterized by IR and (13)C NMR spectroscopy. Alternative preparative routes involve conversion of the precursor dichlorides to the corresponding dialkoxides or diphenoxides, followed by treatment with water and carbon dioxide. Various reaction intermediates have been spectroscopically observed in the latter syntheses. Two crystalline modifications of (Ph(2)PCH(2)CH(2)CH(2)PPh(2))Pt(CO(3)), one with and one without a dichloromethane of solvation, have been studied by single-crystal X-ray diffraction. Crystal data for PtP(2)O(3)C(28)H(26): P2(1)/c, Z = 4, T = 200 K, a = 10.362(8) ?, b = 14.743(6) ?, c = 19.183(10) ?, beta = 122.69(6) degrees. Crystal data for PtP(2)O(3)C(28)H(26).CH(2)Cl(2): P2(1)/c, Z = 4, T approximately 298 K, a = 11.744(2) ?, b = 15.526(3) ?, c = 15.866(3) ?, beta = 101.58(1) degrees.     

Loss of selenium from selenoproteins: conversion of selenocysteine to dehydroalanine in vitro

Characterization of reduced and alkylated rat selenoprotein P by mass spectrometry yielded selenopeptides from which one or more selenium atoms were missing. Predicted selenopeptide mass peaks were accompanied by peaks corresponding to the conversion of one or more selenocysteine residues to dehydroalanine(s). Experiments were carried out to determine whether this loss of selenium occurred in vitro. A selenopeptide was isolated that contained two selenocysteine residues that were both in selenide-sulfide linkages with cysteine residues. After the peptide had been reduced and alkylated, in addition to the predicted mass peak with both selenocysteine residues present, two mass peaks were detected at positions expected for conversion of one and two selenocysteine residues of this selenopeptide to dehydroalanine residues, which was confirmed by tandem mass spectrometry. Similar findings were obtained from a study of another selenoprotein, rat plasma glutathione peroxidase. These results indicate that selenium atoms are lost from selenoproteins during purification and characterization. The loss of selenium from selenoproteins is probably through the mechanism of oxidation of selenocysteine residue to selenoxide followed by syn-beta-elimination of selenenic acid during sample processing.