Novel dinitroxide mediating agent for stable free‐radical polymerization

A novel dinitroxide mediating agent that was suitable for stable free‐radical polymerization was synthesized and used in the block copolymerization of styrene and t‐butyl styrene. Quantitative yields of a novel dinitroxide based on 1,6‐hexamethylene diisocyanate and 4‐hydroxy‐2,2,6,6‐tetramethyl‐1‐piperidinyloxy were obtained. Various experimental parameters, including the nitroxide‐to‐initiator molar ratio, were examined, and it was determined that the polymerization was most controlled under conditions similar to those of conventional 2,2,6,6‐tetramethyl‐1‐piperidinyloxy‐mediated stable free‐radical polymerization. Moreover, the dinitroxide mediator proved to be a viable route for the facile two‐step synthesis of triblock copolymers of styrene and t‐butyl styrene. However, the dinitroxide mediation process resulted in a higher than expected level of nitroxide decomposition, which resulted in polymers possessing a terminal alkoxyamine and an adjacent hydroxylamine rather than a preferred internal bisalkoxyamine. This decomposition resulted in the formation of diblock copolymer species during the triblock copolymer synthesis. Gel permeation chromatography was used to monitor the chain‐end decomposition kinetics, and the determined observed rate constant (5.89 × 10^?5 s^?1) for decomposition agreed well with previous studies for other dinitroxide mediating agents. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1547–1556, 2004     

Simplicial trees are sequentially Cohen–Macaulay

This paper uses dualities between facet ideal theory and Stanley–Reisner theory to show that the facet ideal of a simplicial tree is sequentially Cohen–Macaulay. The proof involves showing that the Alexander dual (or the cover dual, as we call it here) of a simplicial tree is a componentwise linear ideal. We conclude with additional combinatorial properties of simplicial trees.     

Spin-trapped hydroxyl free radicals studied at low field by Field-Cycled Dynamic Nuclear Polarization

The technique of Field-Cycled Dynamic Nuclear Polarization (FC-DNP) involves the EPR irradiation of a free radical solution and the subsequent observation of the NMR signal, the experiment being carried out at a range of magnetic field strengths in order to measure the free radical’s EPR spectrum. In this work FC-DNP has been used to study the EPR spectrum of DMPO spin-trapped hydroxyl free radicals at magnetic field strengths between 0.5 mT and 13.0 mT (5–130 Gauss). The low-field EPR spectrum contains six separate EPR lines, in contrast to the well-known X-band spectrum where only four are seen. Knowledge of the spin-adduct’s EPR spectrum will be of use to workers involved in low-field EPR, especially those conducting biological or in-vivo spin-trapping experiments.     

Bargaining over the division of a shrinking pie: An axiomatic approach

The Bargaining Problem paradigm is extended to time-consuming conflict situations. Such a situation can be represented by a chain of bargaining domains, each representing the conflict at a different point in time. The solution function selects a point in the union of all these domains. We characterize a solution function which satisfies several requirements and explore its properties. One of the results is that an extension of the Adding requirement (Thomson-Myerson 1980) is enough, under some conditions, to yield a solution point, so there is no need to extend the stronger requirements of Independence of Irrelevant Alternatives (Nash 1950) or Monotonicity (Kalai-Smorodinsky 1975).     

Investigating and ordering Quadrilaterals and their analogies in space—problem fields with various aspects

Problem fields with one or two generating problems and possibilities of varying existing problems give a good chance for self-activities of students and can be used for reaching different general aims. In this paper some topics concerning quadrilaterals will be presented. I hope they will animate teachers for more problem orientation in mathematics education. First we will reflect about different types of convex and non-convex quadrilaterals and possibilities of ordering them. Then we focus on middle-quadrilaterals and types of quadrilaterals with special middle-quadrilaterals as well as their logical ordering. Finally we investigate the analogies in space to the parallelogram and its sub-types and order them in the “house of parallelepipeds”.     

Einfluß der Dilatation einer ebenen Phasengrenzfläche auf den Stoffdurchgang

The common methods for calculating the mass transfer across liquid-liquid interfaces in technical applications take into account the mass transfer resistances within the bulk phases. The transfer resistance of the interface and a possible coupling between the momentum and the mass transport is not taken into account. In the present paper a survey is given of theoretical approaches which can describe this coupling and the additional mass transfer resistance. A theory is proposed by Hampe which can be used to explain the coupling between momentum and mass transport employing thermodynamics of irreversible processes. On the basis of this work, the influence of the dilatation of a flat interface on the mass transfer is deduced. It is also concluded from this theory that the diffusion coefficients within the bulk phases are coupled near the thermodynamic equilibrium.