Quantum mechanics studies of the tautomers of diacetylformoin, an important maillard product and odorant

Diacetylformoin (3,4-dihydroxy-3-hexene-2,5-dione) has 16 tautomers, many with several possible conformations and all have been geometry optimised using quantum mechanics at the HF/6-31+G* level. Eleven structures have been identified with energies within 10 kcal mol(-1) of the minimum energy structure. Of these eight are acyclic and three cyclic. Calculations of NMR spectra have clarified the identity of the acyclic and cyclic structures found experimentally. The mechanism for cyclisation has been investigated and transition states obtained. The lowest energy reaction path requires the loss and gain of a proton during cyclisation. (c) 2006 Elsevier B.V. All rights reserved.

Generation of inertia-gravity waves in the rotating thermal annulus by a localised boundary layer instability

Waves with periods shorter than the inertial period exist in the atmosphere (as inertia-gravity waves) and in the oceans (as Poincaré and internal gravity waves). Such waves owe their origin to various mechanisms, but of particular interest are those arising either from local secondary instabilities or spontaneous emission due to loss of balance. These phenomena have been studied in the laboratory, both in the mechanically-forced and the thermally-forced rotating annulus. Their generation mechanisms, especially in the latter system, have not yet been fully understood, however. Here we examine short period waves in a numerical model of the rotating thermal annulus, and show how the results are consistent with those from earlier laboratory experiments. We then show how these waves are consistent with being inertia-gravity waves generated by a localised instability within the thermal boundary layer, the location of which is determined by regions of strong shear and downwelling at certain points within a large-scale baroclinic wave flow. The resulting instability launches small-scale inertia-gravity waves into the geostrophic interior of the flow. Their behaviour is captured in fully nonlinear numerical simulations in a finite-difference, 3D Boussinesq Navier-Stokes model. Such a mechanism has many similarities with those responsible for launching small- and meso-scale inertia-gravity waves in the atmosphere from fronts and local convection.

Inertia in Japanese organizations: knowledge management routines and failure to innovate

This paper argues that features of Japanese organizations, previously held to be the foundations of innovation, change and flexibility, can equally be significant barriers to change, innovation and adaptation in turbulent economic environments. This paper draws on two in-depth case studies of Japanese organizations. It shows how, in both cases, these firms displayed specific weaknesses in the ways in which they integrate and bundle knowledge, in particular around their research and development (R&D) functions. Despite the adoption of strategies of technological innovation and internationalization, the data suggest that the pursuit of both strategies is beset by barriers of inertia. Embedded internal network connections and knowledge-sharing routines between central R&D and other divisions are inappropriate for the revised strategy. Existing external connections, with preferred suppliers and customers within keiretsu structures, and close relationships with existing R&D partners retard these firms' strategic flexibility. With a limited variety of latent routines, knowledge, capabilities and agency to draw on when needed, these firms have limited organizational responsiveness and high levels of path-dependency.

Response theory for equilibrium and non-equilibrium statistical mechanics: causality and generalized Kramers-Kronig relations

We consider the general response theory recently proposed by Ruelle for describing the impact of small perturbations to the non-equilibrium steady states resulting from Axiom A dynamical systems. We show that the causality of the response functions entails the possibility of writing a set of Kramers-Kronig (K-K) relations for the corresponding susceptibilities at all orders of nonlinearity. Nonetheless, only a special class of directly observable susceptibilities obey K-K relations. Specific results are provided for the case of arbitrary order harmonic response, which allows for a very comprehensive K-K analysis and the establishment of sum rules connecting the asymptotic behavior of the harmonic generation susceptibility to the short-time response of the perturbed system. These results set in a more general theoretical framework previous findings obtained for optical systems and simple mechanical models, and shed light on the very general impact of considering the principle of causality for testing self-consistency: the described dispersion relations constitute unavoidable benchmarks that any experimental and model generated dataset must obey. The theory exposed in the present paper is dual to the time-dependent theory of perturbations to equilibrium states and to non-equilibrium steady states, and has in principle similar range of applicability and limitations. In order to connect the equilibrium and the non equilibrium steady state case, we show how to rewrite the classical response theory by Kubo so that response functions formally identical to those proposed by Ruelle, apart from the measure involved in the phase space integration, are obtained. These results, taking into account the chaotic hypothesis by Gallavotti and Cohen, might be relevant in several fields, including climate research. In particular, whereas the fluctuation-dissipation theorem does not work for non-equilibrium systems, because of the non-equivalence between internal and external fluctuations, K-K relations might be robust tools for the definition of a self-consistent theory of climate change.

Friction and inertia: business change, corporate real estate portfolios and the UK office market

It has been asserted that business reorganisation and new working practices are transforming the nature of demand for business space. Downsizing, delayering, business process reengineering and associated initiatives alter the amount, type and location of space required by firms. The literature has neglected the impact of real estate market structures on the ability of organisations to successfully implement these new organisational forms or contemporary working practices. Drawing from UK research, the paper demonstrates that, while new working practices are widespread, their impact on the corporate real estate portfolio is less dramatic than often supposed. In part, this is attributed to inflexibility in market structures which constrains the supply of appropriate space.

Models, moulds and mass production: the mechanics of stylistic influence form the Mediterranean to Bactria

Classical Greek and Roman influence on the material culture of Central Asia and northwestern India is often considered in the abstract. This article attempts to examine the mechanisms of craft production and movement of artisans and objects which made such influence possible, through four case studies: (1) Mould-made ceramics in Hellenistic eastern Bactria; (2) Plaster casts used in the production of metalware from Begram; (3) Terracotta figurines and the moulds used to produce them, from various archaeological sites; and (4) Mass production of identical gold adornments in the nomadic tombs from Tillya Tepe. The implications of such techniques for our understanding of the development of Gandhāran art are also discussed.

The physical pendulum in an advanced undergraduate course in mechanics

The physical pendulum treated with a Hamiltonian formulation is a natural topic for study in a course in advanced classical mechanics. For the past three years, we have been offering a series of problem sets studying this system numerically in our third-year undergraduate courses in mechanics. The problem sets investigate the physics of the pendulum in ways not easily accessible without computer technology and explore various algorithms for solving mechanics problems. Our computational physics is based on Mathematica with some C communicating with Mathematica, although nothing in this paper is dependent on that choice. We have nonetheless found this system, and particularly its graphics, to be a good one for use with undergraduates.

Continuum sea ice rheology determined from subcontinuum mechanics

[1] A method is presented to calculate the continuum-scale sea ice stress as an imposed, continuum-scale strain-rate is varied. The continuum-scale stress is calculated as the area-average of the stresses within the floes and leads in a region (the continuum element). The continuum-scale stress depends upon: the imposed strain rate; the subcontinuum scale, material rheology of sea ice; the chosen configuration of sea ice floes and leads; and a prescribed rule for determining the motion of the floes in response to the continuum-scale strain-rate. We calculated plastic yield curves and flow rules associated with subcontinuum scale, material sea ice rheologies with elliptic, linear and modified Coulombic elliptic plastic yield curves, and with square, diamond and irregular, convex polygon-shaped floes. For the case of a tiling of square floes, only for particular orientations of the leads have the principal axes of strain rate and calculated continuum-scale sea ice stress aligned, and these have been investigated analytically. The ensemble average of calculated sea ice stress for square floes with uniform orientation with respect to the principal axes of strain rate yielded alignment of average stress and strain-rate principal axes and an isotropic, continuum-scale sea ice rheology. We present a lemon-shaped yield curve with normal flow rule, derived from ensemble averages of sea ice stress, suitable for direct inclusion into the current generation of sea ice models. This continuum-scale sea ice rheology directly relates the size (strength) of the continuum-scale yield curve to the material compressive strength.