The synthesis of a [2.2]paracyclophane-derived secondary phosphine oxide and a study of its reactivity

A planar chiral secondary phosphine oxide based on [2.2]paracyclophane was synthesized and its chemistry investigated; it was shown to be a competent pre-ligand in palladium(0)-mediated reactions, and displayed promising activity in gold(I)-catalysed cyclisations. The secondary phosphine oxide could be transformed into a collection of P-stereogenic tertiary phosphine oxides. These are rare examples of the planar chirality of [2.2]paracyclophane being combined with a P-stereogenic centre. Unfortunately, epimerisation of the phosphorus stereocentre during reduction limits the use of this chemistry.     

Carboxyl groups in pre-treated regenerated cellulose fibres

The influence of peroxide bleaching and slack-mercerization on the amount of acidic groups in regenerated fibres (viscose, modal and lyocell) were studied. Conductometric titration was used to determine the total content of acidic carboxylic groups. Polyelectrolyte titration was used for surface and total charge determination, and to obtain information about the charge distribution and accessibilities of charged groups. Changes in fibre crystallinity to pre-treatment processes were characterized using iodine sorption (Schwertassek method) and correlated to treatments and the amount of carboxylic groups. For all three types of fibres the amount of accessible carboxyl groups was lowered by an increase in the degree of crystallinity. Bleaching with hydrogen peroxide causes some oxidative cellulose damage and, therefore, a larger amount of carboxyl groups (presumably formed at the end of cellulose chains). Slack-mercerization did not significantly change the total amount of acidic groups in the fibres, but their accessibility to cationic polyelectrolytes, in particular to polymers with high molecular weight was substantially lowered. Lidija Fras Zemljič, Zdenka Peršin, and Karin Stana Kleinschek are the members of the European Polysaccharide Network of Excellence (EPNOE).     

Polymerization effects on molecular dynamics of n-ethylene glycol dimethacrylates followed by dielectric relaxation spectroscopy

A detailed dielectric characterization of n-ethylene glycol dimethacrylate monomers with n = 2 and 4 is provided. Besides the α relaxation associated to the glass transition, two secondary relaxation processes were detected: the γ process assigned to the twisting motions within the ethylene glycol moiety, and the β process related with hindered rotations of carboxylic groups. While the relaxation time of the γ process is independent of the size of the ethylene glycol group, the β process deviates to higher times with increasing n. Upon polymerization the α process goes to extinction, faster in the 4-ethylene monomer, with a concomitant depletion of the β process that remains at higher polymerization degrees relatively to the α process, thus acting as a more sensitive probe to evaluate conversion. The height decrease of α and β processes of monomers with the polymerization progress, occurs without significant changes of position. At intermediate states of polymerization, a new relaxation process evolves being only detectable in a narrow temperature range. In the end, the polymer networks show, in addition to the γ_pol relaxation identical to the γ relaxation of the monomer, a β_pol relaxation with similar features to the β relaxation found in poly n-alkyl methacrylates originated by a π flip of the ester unit accompanied by a restricted main chain rearrangement. The main dielectric relaxation corresponding to the swollen polymer network should appear at quite high temperatures already in early stages of the polymerization process because phase segregation occurs and only a limited amount of liquid monomer plasticizes the newly formed material.     

A functional model for polynomially posinormal operators

In this paper we introduce a class of operators naturally extending the classes of hyponormal and posinormal operators. For this class we construct a generating family of eigendistributions, unitary invariants and a functional model.     

Extension and lifting of polynomials

We characterize the Banach spaces enjoying polynomial lifting properties, and the spaces that admit compact extensions of polynomials.Received: 20 June 2002     

The central kernel of the Peirce-one space

Further investigation into the properties of the Peirce-one space J₁ corresponding to a weak^*-closed inner ideal J in a JBW^*-triple A is carried out, and, in particular, it is shown that J₁ contains no non-trivial weak^*-closed ideals.Received: 12 June 2002     

Operators of Fourier type <Emphasis Type="Italic">p</Emphasis> with respect to some subgroups of a locally compact Abelian group

It is shown that all Banach space operators which have Fourier type p(1 < p 2) with respect to a second countable locally compact abelian group G also have Fourier type p with respect to every closed discrete subgroup H of G. The same statement holds for any closed subgroup H of G when p = 2. Also shown as a corollary is that Fourier type 2 operators have Walsh type 2. Received: 10 June 2002     

Approximation of regularized evolution operators

This paper is devoted to the approximation of a regularized evolution operator by a sequence of regularized discrete parameter evolution operators, and the results obtained here are applied to some degenerate partial differential equation.Received: 4 December 2001     

A non-trivial Fréchet quotient of the space of real analytic functions

We prove that the space of real analytic functions ${\cal A}(\Omega)$ on an arbitrary open set $\Omega \subseteq \mathbb{R}^d$ has a Fréchet infinite dimensional quotient space with a continuous norm. Received: 4 February 2002     

Some remarks on half-factorial orders

In questo articolo, si dimostra il legame fra la semi-fattorialità e la fattorialità debole nel contesto degli ordini algebrici. In particolare, si ottiene che un ordine semi-fattoriale ha il stesso numero di classi che su chiusura integrale.