A groove-ploughing theory for the production of mega-scale glacial lineations, and implications for ice-stream mechanics

Mega-scale glacial lineations (MSGLs) are longitudinally aligned corrugations (ridge-groove structures 6-100 km long) in sediment produced subglacially. They are indicators of fast flow and a common signature of ice-stream beds. We develop a qualitative theory that accounts for their formation, and use numerical modelling, and observations of ice-stream beds to provide supporting evidence. Ice in contact with a rough (scale of 10-10(3) m) bedrock surface will mimic the form of the bed. Because of flow acceleration and convergence in ice-stream onset zones, the ice-base roughness elements experience transverse strain, transforming them from irregular bumps into longitudinally aligned keels of ice protruding downwards. Where such keels slide across a soft sedimentary bed, they plough through the sediments, carving elongate grooves, and deforming material up into intervening ridges. This explains MSGLs and has important implications for ice-stream mechanics. Groove ploughing provides the means to acquire new lubricating sediment and to transport large volumes of it downstream. Keels may provide basal drag in the force budget of ice streams, thereby playing a role in flow regulation and stability We speculate that groove ploughing permits significant ice-stream widening, thus facilitating high-magnitude ice discharge.

Goal sketching: towards agile requirements engineering

This paper describes a technique that can be used as part of a simple and practical agile method for requirements engineering. The technique can be used together with Agile Programming to develop software in internet time. We illustrate the technique and introduce lazy refinement, responsibility composition and context sketching. Goal sketching has been used in a number of real-world development projects, one of which is described here.

Selectivity of bis(calix[4]diquinone) ionophores towards metal ions in solvent dimethylsulfoxide: a molecular mechanics and molecular dynamics study

Molecular modelling studies have been carried out on two bis(calix[4]diqu(inone) ionophores, each created from two (calix[4]diquinone)arenes bridged at their bottom rims via alkyl chains (CH2)(n), 1: n = 3, 2; n = 4, in order to understand the reported selectivity of these ligands towards different sized metal ions such as Na+, K+, Rb+, and Cs+ in dmso solution. Conformational. analyses have been carried out which show that in the lowest energy conformations of the two macrocycles, the individual calix[4]diquinones exhibit a combination of partial cone, 1,3-alternate and cone conformations. The interactions of these alkali metals with the macrocycles have been studied in the gas phase and in a periodic box of solvent dmso by molecular mechanics and molecular dynamics calculations. Molecular mechanics calculations have been carried out on the mode of entry of the ions into the macrocycles and suggest that this is likely to occur from the side of the central cavity, rather than through the main axis of the calix[4]diquinones. There are energy barriers of ca. 19 kcal mol(-1) for this entry path in the gas phase, but in solution no energy barrier is found. Molecular dynamics simulations show that in both 1 and 2, though particularly in the latter macrocycle, one or two solvent molecules are bonded to the metal throughout the course of the simulation, often to the exclusion, of one or more of the ether oxygen atoms. By contrast the carbonyl oxygen atoms remain bonded to the metal atoms throughout with bond lengths that remain significantly less than those to the ether oxygen atoms. Free energy perturbation studies have been carried out in dmso and indicate that for 1, the selectivity follows the order Rb+ approximate to K+ > Cs+ >> Na+, which is partially in agreement with the experimental results. The energy differences are small and indeed the ratio between stability constants found for Cs+ and K+ complexes is only 0.60, showing that 1 has only a slight preference for K+. For the larger receptor 2, which is better suited to metal complexation, the binding affinity follows the pattern Cs+ >> Rb+ >> K+ >> Na+, with energy differences of 5.75, 2.61, 2.78 kcal mol(-1) which is perfectly consistent with experimental results.

Quantum mechanics studies of the tautomers of dlhydrodiacetylformoin, an important Maillard intermediate and the synthesis of furaneol

Conformational analyses have been carried out on the acyclic and cyclic forms of dihydrodiacetylformoin, an important Maillard intermediate and precursor for furaneol. For the acyclic forms, the 2,5-dicarbonyl isomers have the lowest energy, while for the cyclic forms, the 3-carbonyl are favoured over the 4-carbonyl isomers. The likely path for cyclisation is investigated and it is shown that the favoured path is dependent upon the relative chiralities of the carbon atoms and in particular that the reaction proceeds more readily if C2 and C3 have different chiralities. After cyclisation, the reaction path to produce furaneol proceeds via the loss of a water molecule. This reaction has been studied with a model including two water molecules and a hydroxide anion and shows relatively low-energy barriers. (C) 2008 Published by Elsevier B.V.