962 resultados para metallosupramolecular architectures
Resumo:
The effect of hyperbranched macromolecular architectures (dendrimers) upon chirality has received significant attention in recent years in the light of the proposal of amplification of chirality. In particular, several studies have been carried out on the chiroptical properties of dendrimers that contain a chiral core and achiral branches in order to determine if the chirality of the central core can be transmitted to the distal. region of the macromolecule. In addition to interest of a pure academic nature, the presence of such chiral conformational order would be extremely useful in the development of asymmetric catalysts. In this paper, a novel class of chiral dendrimers is described - these perfect hyperbranched macromolecules have been prepared by a convergent route by the coupling of a chiral central core based upon tris(2-aminoethyl)amine and poly(aromatic amide ester) dendritic branches. The chiral properties of these dendrimers have been investigated by detailed optical rotation studies and circular dichroism analysis; the results of these studies are described herein. (C) Wiley-VCH Verlag GmbH Co.
Resumo:
Syntactic theory provides a rich array of representational assumptions about linguistic knowledge and processes. Such detailed and independently motivated constraints on grammatical knowledge ought to play a role in sentence comprehension. However most grammar-based explanations of processing difficulty in the literature have attempted to use grammatical representations and processes per se to explain processing difficulty. They did not take into account that the description of higher cognition in mind and brain encompasses two levels: on the one hand, at the macrolevel, symbolic computation is performed, and on the other hand, at the microlevel, computation is achieved through processes within a dynamical system. One critical question is therefore how linguistic theory and dynamical systems can be unified to provide an explanation for processing effects. Here, we present such a unification for a particular account to syntactic theory: namely a parser for Stabler's Minimalist Grammars, in the framework of Smolensky's Integrated Connectionist/Symbolic architectures. In simulations we demonstrate that the connectionist minimalist parser produces predictions which mirror global empirical findings from psycholinguistic research.