Conformational analysis of dipeptide‐derived polyisocyanides

The conformational properties of polymers derived from isocyanodipeptides have been investigated with a combination of model calculations, X‐ray diffraction, and circular dichroism spectroscopy. Depending on the configuration of the side chains, defined arrays of hydrogen bonds along the polymeric backbone are formed. This leads to a well‐defined conformation as, for example, expressed in the formation of lyotropic liquid‐crystalline phases and increased helical stability. Upon the disruption of the hydrogen bonds by a strong acid, a less well‐defined macromolecular conformation is observed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1725–1736, 2003     

On additives, morphological evolution and dielectric breakdown in low density polyethylene

A series of low density polyethylene systems has been studied with respect to structural evolution and short-term dielectric breakdown behaviour. All materials were based upon a single polymer, that is commonly used in high voltage applications, but with different additives. In all three of these systems, multiple melting transitions were observed, as a result of molecular fractionation effects during crystallization. In the virgin polymer, a space-filling banded spherulitic morphology was found to develop at low temperatures (102 °C and below) whereas, at higher temperatures, only a few isolated axialites were observed. Inclusion of the antioxidant resulted in greatly increased nucleation densities, such that, at low temperatures, no evidence of spherulitic organisation remained. At higher temperatures, sheaf-like lamellar aggregates developed, which were much smaller and much more numerous than in the case of the virgin polymer. Further addition of dicumyl peroxide (DCP) resulted in the rapid formation of a crosslinked network at 200 °C. Some crosslinking also occurred at 150 °C, but over a much longer timescale. Where extensive crosslinking occurred prior to crystallization, the resulting gel inhibited structural development, such that only a few small, isolated sheaves were able to form at 102 °C. In view of the principal application area of this material, the breakdown strength of each of the above systems was then measured and the whole data set was analysed statistically. When structural factors were considered alongside the statistics, no clear trends emerged to indicate that either the compositional or morphological variations were reflected in the short-term electrical failure processes.     

Post deposition purification of PTCDA thin films

The decomposition of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecules during evaporation of unpurified raw material in ultra high vacuum was studied. The fragments were identified by mass spectrometry and the influence of these fragments and further contaminations of the raw material on the electronic structure of PTCDA thin films was measured by photoemission spectroscopy. Annealing of contaminated PTCDA films was tested as cheap and easy to perform method for (partial) post deposition purification of the contaminated films.     

Equilibrium Problems with Applications to Eigenvalue Problems

In this paper, we consider equilibrium problems and introduce the concept of (S)₊ condition for bifunctions. Existence results for equilibrium problems with the (S)₊ condition are derived. As special cases, we obtain several existence results for the generalized nonlinear variational inequality studied by Ding and Tarafdar (Ref. 1) and the generalized variational inequality studied by Cubiotti and Yao (Ref. 2). Finally, applications to a class of eigenvalue problems are given.     

Backscattering in the vicinity of a mode cutoff

In a recent paper to this journal (Whitman A M et al 2003 Waves Random Media 13 269-86) we derived a set of coupled equations that describe the intermodal scattering of acoustic radiation in a duct whose speed of sound varies randomly in space and time. In the paper we were mainly interested in modes that were not near cutoff. Here we study the solution of these equations in the vicinity of the cutoff. We find that near cutoff almost all the energy is reflected back independent of the other duct parameters. In addition to presenting these results, we analyse the mathematical structure of the equations in these regions in order to elucidate the reason for this behaviour.     

Positions of convex bodies associated to extremal problems and isotropic measures

We show that there are close relations between extremal problems in dual Brunn-Minkowski theory and isotropic-type properties for some Borel measures on the sphere. The methods we use allow us to obtain similar results in the context of Firey-Brunn-Minkowski theory. We also study reverse inequalities for dual mixed volumes which are related with classical positions, such as ?-position or isotropic position.     

A solvent-free synthesis of coumarins using a Wells-Dawson heteropolyacid as catalyst

Substituted coumarins are synthesized from phenols and β-ketoesters by the Pechmann reaction, using a Wells-Dawson heteropolyacid (H₆P₂W₁₈O₆₂·24H₂O) as catalyst by a solvent-free procedure. This one requires low reaction times, 130 °C temperature and as little as 1 mol % of Wells-Dawson acid, obtaining good to excellent yields of coumarins. The catalyst showed to be reusable with no differences in the yields. The results are compared with those of the reactions performed in toluene solution. The presented synthetic procedure is a convenient, clean and fast alternative for synthesizing 4-substituted coumarins (17 examples).     

Design of an experimental procedure for energy evaluation from biomass

The rational and sustainable exploitation of nature resources is one of the priority objectives of our society. In this article a method is proposed to evaluate and exploit the energetic resources contained in different forest formations. This method is based on the use of a combustion bomb calorimeter to determine the calorific values of the different samples studied. These results were complemented with chemical analysis of the samples and with environmental and geomorphological studies of the zones were samples were taken. The results obtained during the last 3 years for the residual biomass originated from the forest formations existing in Galicia ensure the reliability and usefulness of the method that can be extended to any forest formation all over the world.