Determination of absolute configuration of conformationally flexible cis-dihydrodiol metabolites: Effect of diene substitution pattern on the circular dichroism spectra and optical rotations

Absolute configurations of a number of cis-dihydrodiols (cis-1,2-dihydroxy-3,5-cyclohexadienes), synthetically useful products of TDO-catalyzed dihydroxylations of 1,2- and 1,3-disubstituted benzene derivatives, have been determined by a comparison of calculated and experimental CD spectra and optical rotations and by methods involving X-ray crystallography, H-1 NMR spectra of diastereoisomeric derivatives, and by stereochemical correlations. The computations disclosed a significant effect of the substituents on conformational equilibria of cis-dihydrodiols and chiroptical properties of individual conformers. The assigned absolute configurations of cis-dihydrodiols have allowed the validity of a simple predictive model for TDO-catalyzed arene dihydroxylations to be extended.

Absolute configuration of conformationally flexible cis-dihydrodiol metabolites by the method of confrontation of experimental and calculated electronic CD spectra and optical rotations

We have determined the absolute configurations of conformationally flexible cis-dihydrodiol metabolites (cis-1,2-dihydroxy-3,5-cyclohexadienes), bearing different substituents (e.g., Br, F, CF3, CN, Me) in 3- and 5-positions, by the method of confrontation of experimental and calculated electronic CD spectra and optical rotations. Convergent results were obtained by both methods in eight out of ten cases. For the difficult cases, where either conformer population and/or chiroptical properties (calculated rotational strengths of the long-wavelength Cotton effect or optical rotations) of contributing conformers remain inconclusive, the absolute configuration could still be correctly assigned based on one of the biased properties (either ECD or optical rotation). This approach appears well-suited for a broad spectrum of conformationally flexible chiral molecules.

Flexible Natural Language Generation in Multiple Contexts

We present a practical approach to Natural Language Generation (NLG) for spoken dialogue systems. The approach is based on small template fragments (mini-templates). The system’s object architecture facilitates generation of phrases across pre-defined business domains and registers, as well as into different languages. The architecture simplifies NLG in well-understood application contexts, while providing the flexibility for a developer and for the system, to vary linguistic output according to dialogue context, including any intended affective impact. Mini-templates are used with a suite of domain term objects, resulting in an NLG system (MINTGEN – MINi-Template GENerator) whose extensibility and ease of maintenance is enhanced by the sparsity of information devoted to individual domains. The system also avoids the need for specialist linguistic competence on the part of the system maintainer.

Development of a Java-based Unified and Flexible Natural Language Discourse System

This paper outlines the design and development of a Java-based, unified and flexible natural language dialogue system that enables users to interact using natural language, e.g. speech. A number of software development issues are considered with the aim of designing an architecture that enables different discourse components to be readily and flexibly combined in a manner that permits information to be easily shared. Use of XML schemas assists this component interaction. The paper describes how a range of Java language features were employed to support the development of the architecture, providing an illustration of how a modern programming language makes tractable the development of a complex dialogue system.

Alkali-metal salts of aromatic carboxylic acids: Liquid crystals without flexible chains

The alkali-metal salts of meta-substituted benzoic acids exhibit a smectic A mesophase at high temperatures. These compounds are examples of liquid crystals without terminal alkyl chains. The influence of the metal ion and of the type of substituents on the transition temperatures is discussed. Compounds with the substituent in the ortho- and para-positions are non-mesomorphic. The crystal structures of the compounds Rb(C7H4ClO2)(C7H4ClO2H), Na(C7H4IO2)(H2O), K(C7H4ClO2)(C7H4ClO2H) and Rb(C7H4BrO2)(C7H4BrO2H) have been determined by X-ray crystallography. These compounds possess a layerlike structure in the solid state. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Assessing the Transaction Costs of Firms in the EU ETS: Lessons form Ireland

Until now, there has been little empirical evidence that EU Emissions Trading Scheme (ETS) transaction costs are incurred at firm level. The transaction costs (internal costs, capital costs, consultancy and trading costs) incurred by Irish firms under the EU ETS during its pilot phase (2005-2007) were measured and analysed. Evidence for the sources of transaction costs, their magnitude and the distribution of costs shows that these were mainly administrative in nature. Considerable variation in costs was found due to economies of scale, as the costs per tonne of CO2 were lower for participants with larger allocations. For the largest firms - accounting for over half the emissions - average transaction costs were €0.05 per tonne. However, for small firms, average transaction costs were €2.02 - over 18% of the current allowance price. This supports the concerns that transaction costs are excessive for smaller participants. The immediate policy implication is that additional attention will be needed to address different sizes of firms, number of installations per firm, and the size of the initial allocations.

A study of Heck cyclization reactions to form phenanthridine ring systems

A survey of conditions for the palladium catalyzed intramol. Heck cyclization of protected amines has shown that the Herrmann-Beller palladacycle can be exploited under 'cationic' conditions to provide a robust and rapid route (