Evidences of phase separation in moisture‐cured poly(urethane urea)s by means of temperature modulated differential scanning calorimetry

The degree of phase separation in several moisture‐cured poly(urethane urea)s (PUUs) was studied by FTIR spectroscopy, wide angle X‐ray diffraction (WAXD), and temperature‐modulated differential scanning calorimetry (TMDSC). This latter technique was shown to be particularly useful in analysing the degree of phase separation in PUU polymers. Both phase mixing and phase segregation coexisted in the PUUs and the degree of phase separation increased as the urea hard segment (HS) content in the PUU increased. The maximum solubility of urea HSs into the polyol soft segments (SSs) was achieved for 50 wt % urea HS content in diol‐based PUUs, whereas for triol‐based PUUs the highest solubility between HS and SS was reached for lower urea HS amount. Finally, the higher the urea HS content the higher the extent of phase separation in the PUU. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3034–3045, 2007     

Mechanisms of n‐butanol formation in butyl acrylate latexes

The mechanisms involved in the formation of n‐butanol during the synthesis of butyl acrylate containing latices were investigated. The experimental results showed that neither the hydrolysis of butyl acrylate nor of the ester bond in the butyl acrylate segments of the polymer played a major role in the formation of n‐butanol, which was mainly generated from the polymer backbone, by transfer reactions to polymer chain followed by cyclization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5838–5846, 2007     

Magnetic poly(N‐isopropylacrylamide) microspheres by dispersion and inverse emulsion polymerization

The aim of this study was to develop novel thermally responsive polymer microspheres with magnetic properties. Dispersion and inverse emulsion copolymerization of N‐isopropylacrylamide (NIPAAm) and N,N′‐methylenebisacrylamide (MBAAm) was investigated in the presence of γ‐Fe₂O₃ nanoparticles. The resulting microspheres were characterized in terms of morphology, size, polydispersity, iron content, and temperature‐dependent swelling using optical microscopy, transmission electron microscopy, scanning electron microscopy, QELS, and AAS. The effects of several variables, such as the concentration of γ‐Fe₂O₃, MBAAm crosslinking agent, Span 80 surfactant, 2,2′‐azobis(2‐methyloctanenitrile) (AMON) initiator, and polymerization temperature on the properties of the microspheres were studied. Swelling and thermoresponsive behavior of the microspheres containing γ‐Fe₂O₃ nanoparticles were also investigated. The microspheres contained about 8 wt % of iron. The presence of magnetic nanoparticles and their concentration changes did not have any significant effect on the temperature sensitivity of the composites. The particles gradually shrink into an increasingly collapsed state when the temperature is raised to 40 °C since the increase in temperature weakens the hydration and PNIPAAm chains gradually become more hydrophobic, which leads to the collapse of the particles. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5884–5898, 2007     

Arsenic determination in marine sediment using ultrasound for sample preparation.

This work deals with As determination in marine sediment using ultrasound for sample preparation. It is shown that As can be quantitatively extracted from marine sediment using 20% (v/v) HCl and sonication. The slurry is centrifuged and the analyte is determined in the supernatant by hydride generation atomic absorption spectrometry (HG AAS). A flow injection (FI) system is employed for hydride generation, with 0.5% (m/v) NaBH(4) used as reducdant and a 20% (v/v) HCl used as sample carrier. The limit of quantification is 1.6 microg g(-1) of As, which is based on 800 microl of sample solution and 0.200 g of sample mass in a volume of 50 mL. Certified and non certified marine sediment samples were analyzed; the results were in accordance with the certified or reference values. Speciation analysis by HPLC-ICP-MS showed that As(V) is the only detectable As species present in the supernatant of the centrifuged sample.     

Extension of the chain‐end,free‐volume theory for predicting glass temperature as a function of conversion in hyperbranched polymers obtained through one‐pot approaches

Compared with linear polymers, more factors may affect the glass‐transition temperature (T_g) of a hyperbranched structure, for instance, the contents of end groups, the chemical properties of end groups, branching junctions, and the compactness of a hyperbranched structure. T_g's decrease with increasing content of end‐group free volumes, whereas they increase with increasing polarity of end groups, junction density, or compactness of a hyperbranched structure. However, end‐group free volumes are often a prevailing factor according to the literature. In this work, chain‐end, free‐volume theory was extended for predicting the relations of T_g to conversion (X) and molecular weight (M) in hyperbranched polymers obtained through one‐pot approaches of either polycondensation or self‐condensing vinyl polymerization. The theoretical relations of polymerization degrees to monomer conversions in developing processes of hyperbranched structures reported in the literature were applied in the extended model, and some interesting results were obtained. T_g's of hyperbranched polymers showed a nonlinear relation to reciprocal molecular weight, which differed from the linear relation observed in linear polymers. T_g values decreased with increasing molecular weight in the low‐molecular‐weight range; however, they increased with increasing molecular weight in the high‐molecular‐weight range. T_g values decreased with increasing log M and then turned to a constant value in the high‐molecular‐weight range. The plot of T_g versus 1/M or log M for hyperbranched polymers may exhibit intersecting straight‐line behaviors. The intersection or transition does not result from entanglements that account for such intersections in linear polymers but from a nonlinear feature in hyperbranched polymers according to chain‐end, free‐volume theory. However, the conclusions obtained in this work cannot be extended to dendrimers because after the third generation, the end‐group extents of a dendrimer decrease with molecular weight. Thus, it is very possible for a dendrimer that T_g increases with 1/M before the third generation; however, it decreases with 1/M after the third generation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1235–1242, 2004     

Recent advances in the analysis of steroid hormones and related drugs.

The development during the last 15 years and the state-of-the-art in the analysis of bulk steroid hormone drugs and hormone-like structures and pharmaceutical formulations made thereof are summarized. Other steroids (sterols, bile acids, cardiac glycosides, vitamins D) as well as biological-clinical aspects and pharmacokinetic and metabolic studies are excluded from this review. The state-of-the-art is summarized based on comparisons of monographs in the latest editions of the European Pharmacopoeia, United States Pharmacopoeia and the Japanese Pharmacopoeia. This is followed by sections dealing with new developments in the methodology for the fields of spectroscopic and spectrophotometric, chromatographic, electrophoretic and hyphenated techniques as well electroanalytical methods. The review is terminated by two problem-oriented sections: examples on impurity and degradation profiling as well as enantiomeric analysis.     

A sequential injection system for the spectrophotometric determination of calcium, magnesium and alkalinity in water samples.

A sequential injection methodology for the spectrophotometric determination of calcium, magnesium and alkalinity in water samples is proposed. A single manifold is used for the determination of the three analytes, and the same protocol sequence allows the sequential determination of calcium and magnesium (the sum corresponds to the water hardness). The determination of both metals is based on their reaction with cresolphtalein complexone; mutual interference is minimized by using 8-hydroxyquinoline for the determination of calcium and ethylene glycol-bis(beta-aminoethyl ether)-N,N,N',N'-tetraacetic acid (EGTA) for the determination of magnesium. Alkalinity determination is based on a reaction with acetic acid, and corresponding color change of Bromcresol Green. Working ranges of 0.5 - 5 mg dm(-3) for Ca, 0.5 - 10 mg dm(-3) for Mg, and 10 - 100 mg HCO3- dm(-3), for alkalinity have been achieved. The results for water samples were comparable to those of the reference methods and to a certified reference water sample. RSDs lower than 5% were obtained, a low reagent consumption and a reduced volume of effluent have been accomplished. The determination rate for calcium and magnesium is 80 h(-1), corresponding to 40 h(-1) per element, while 65 determinations of alkalinity per hour could be carried out.     

Singular terms of helicity amplitudes at one loop in QCD and the soft limit of the cross sections of multi-parton processes

We describe a general method that enables us to obtain all the singular terms of helicity amplitudes of n-parton processes at one loop. The algorithm uses helicity amplitudes at tree level and simple color algebra. We illustrate the method by calculating the singular part of the one-loop helicity amplitudes of all 2 → 3 parton subprocesses. The results are used to derive the soft gluon limit of the cross sections of all 2 → 4 parton scattering subprocesses which provide a useful initial condition for the angular ordering approximation to coherent multiple soft gluon emission, incorporated in existing Monte Carlo simulation programs.     

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