Aqueous solution and solid state interactions of lanthanide ions with a methacrylic ester polymer bearing pendant 15‐crown‐5 moieties

The interaction between trivalent lanthanide ions and poly(1,4,7,10,13‐pentaoxacyclopentadecan‐2‐yl‐methyl methacrylate), PCR5, in aqueous solution and in the solid state have been studied. In aqueous solution, evidence of a weak interaction between the lanthanides and PCR5 comes from the small red shift of the Ce(III) emission spectra and the slight broadening of the Gd(III) EPR spectra. From the Tb(III) lifetimes in the presence of H₂O and D₂O the loss of one or two water coordinated molecules is confirmed when Tb(III) is bound to PCR5. An association constant of the order of 200 M^?1 was obtained for a 1:1 (lanthanide:15‐crown‐5) complex from the shift of the polymer NMR signals induced by Tb(III). A similar association constant is obtained from the differences of the molar conductivity of Ce(III) solution at various concentrations in presence and absence of PCR5. When Tb(III) is adsorbed on PCR5 membranes, lifetime experiments in H₂O and D₂O confirm the loss of 5 or 6 water coordinated molecules indicating that in solid state the lanthanide(III)‐PCR5 interaction is stronger than in solution. The adsorption of Ce(III) in PCR5 membranes shows a Langmuir type isotherm, from which an equilibrium constant of 39 M^?1 has been calculated. SEM shows that the membrane morphology is not much affected by lanthanide adsorption. Support for lanthanide ion–crown interactions comes from ab initio calculations on 15‐crown‐5/La(III) complex. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1788–1799, 2007     

Diblock copolymers based on allyl methacrylate: Synthesis,characterization, and chemical modification

Different diblock copolymers constituted by one segment of a monomer supporting a reactive functional group, like allyl methacrylate (AMA), were synthesized by atom transfer radical polymerization (ATRP). Bromo‐terminated polymers, like polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(butyl acrylate) (PBA) were employed as macroinitiators to form the other blocks. Copolymerizations were carried out using copper chloride with N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as the catalyst system in benzonitrile solution at 70 °C. At the early stage, the ATRP copolymerizations yielded well‐defined linear block copolymers. However, with the polymerization progress a change in the macromolecular architecture takes place due to the secondary reactions caused by the allylic groups, passing to a branched and/or star‐shaped structure until finally yielding gel at monomer conversion around 40% or higher. The block copolymers were characterized by means of size exclusion chromatography (SEC), ¹H NMR spectroscopy, and differential scanning calorimetry (DSC). In addition, one of these copolymers, specifically P(BA‐b‐AMA), was satisfactorily modified through osmylation reaction to obtain the subsequent amphiphilic diblock copolymer of P(BA‐b‐DHPMA), where DHPMA is 2,3‐dihydroxypropyl methacrylate; demonstrating the feasibility of side‐chain modification of the functional obtained copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3538–3549, 2007     

Quantification of trace elements in human serum fractions by liquid chromatography and inductively coupled plasma mass spectrometry

On‐line coupling of LC and ICP‐MS has been used for fractionation and detection of species of Cu, Fe, I, Se and Zn in human serum. It has been shown that anion exchange chromatography provided better separation capability (both intra‐ and inter‐element) than size‐exclusion chromatography. The mobile phases for ion exchange chromatography consisted of Tris–HNO₃ buffer and ammonium salt (nitrate, acetate or formate). Formate was found to be the best mobile phase counter ion, enabling good chromatographic separation, and is acceptable for mass spectrometry too. The quantitative evaluation of element concentrations adhering to individual fractions was performed by the peak area normalization method. The repeatability of results ranged from 3 to 15% (depending on the element concentration level) and represented the main part of the result uncertainty. The accuracy of Cu and Zn fraction determinations was confirmed by comparison with the isotope dilution technique. Copyright © 2006 John Wiley & Sons, Ltd.     

On Critical Stability of Three Quantum Charges Interacting Through Delta Potentials

We consider three one-dimensional quantum, charged and spinless particles interacting through delta potentials. We derive sufficient conditions which guarantee the existence of at least one bound state.     

Butyltins in california river and lake marina waters

Butyltins were analyzed in waters from California river and lake marinas and were detected at the part per trillion (ppt) level in most locations. The tributyltin:dibutyltin (TBT/DBT) ratios in the fresh waters were similar to those in their saline counterparts indicating like rates of degradation in the two salinity regimes.     

Reductions in overshoot following intense sound exposures

Overshoot refers to the poorer detectability of brief signals presented soon after the onset of a masking noise compared to those presented after longer delays. In the present experiment, brief tonal signals were presented 2 or 190 ms following the onset of a broadband masker that was 200 ms in duration. These two conditions of signal delay were tested before and after a series of exposures to a tone intense enough to induce temporary threshold shift (TTS). The magnitude of the overshoot was reduced after the exposure when a TTS of at least 10 dB was induced, but not when smaller amounts of TTS were induced. The reduction in overshoot was due to a decrease in the masked thresholds with the 2-ms delay; masked thresholds with the 190-ms delay were not different pre- and post-exposure. The implication is that the mechanisms responsible for the normal overshoot effect are temporarily inactivated by the same stimulus manipulations that produce a mild exposure-induced hearing loss. Thus the result is the paradox that exposure to intense sounds can produce a loss of signal detectability in certain stimulus conditions and a simultaneous improvement in detectability in other stimulus conditions.     

Chemical analysis and distribution investigation of trace elements in indium matrix by spark source mass spectrometry

Summary High-purity indium was analysed by spark source mass spectrometry, using electrical and photoplate detection. For the calibration of the differences in elemental sensitivity, a standard sample was prepared in which 10 impurities were determined by graphite furnace atomic absorption spectrometry. In this way accuracies of less than 40% were obtained for relatively homogeneous elements at ppm and sub-ppm level. About 40 elements could be determined with detection limits of 10 to 30 ppb. Two pattern recognition methods, principal component analysis and clustering analysis, were applied to obtain information on trace element distribution, which indicated that a number of elements were strongly spatially correlated in the analysed sample.

---

Chemische Analyse und Verteilungsbestimmung von Spurenelementen in Indium-Matrix durch Funkenquellen-Massenspektrometrie

---

On leave from: Department of Chemistry, Nanjing Normal University, Nanjing, People's Republic of China