A general synthesis of macrocyclic pi-electron-acceptor systems

Cyclocondensations of aromatic diamines with 1,1'-bis(2,4-dinitrophenyl)-4,4'-bipyridinium salts afford doubly or quadruply charged, macrocyclic, N,N'-diarylbipyridinium cations. These are tolerant of a wide range of acids, bases, and nucleophiles, although they appear to undergo reversible, one-electron reduction by tertiary amines. Single-crystal X-ray analysis demonstrates the presence of a macrocycle conformation in which the 4,4'-bipyridinium and 4,4'-biphenylenedisulfonyl residues are suitably spaced and aligned for complexation with pi-donor arenes, and NMR studies in solution indeed confirm binding to 1,5-bis[hydroxy(ethoxy)ethoxy]naphthalene.

Disentangling multi-level systems: averaging, correlations and memory

We consider two weakly coupled systems and adopt a perturbative approach based on the Ruelle response theory to study their interaction. We propose a systematic way of parameterizing the effect of the coupling as a function of only the variables of a system of interest. Our focus is on describing the impacts of the coupling on the long term statistics rather than on the finite-time behavior. By direct calculation, we find that, at first order, the coupling can be surrogated by adding a deterministic perturbation to the autonomous dynamics of the system of interest. At second order, there are additionally two separate and very different contributions. One is a term taking into account the second-order contributions of the fluctuations in the coupling, which can be parameterized as a stochastic forcing with given spectral properties. The other one is a memory term, coupling the system of interest to its previous history, through the correlations of the second system. If these correlations are known, this effect can be implemented as a perturbation with memory on the single system. In order to treat this case, we present an extension to Ruelle's response theory able to deal with integral operators. We discuss our results in the context of other methods previously proposed for disentangling the dynamics of two coupled systems. We emphasize that our results do not rely on assuming a time scale separation, and, if such a separation exists, can be used equally well to study the statistics of the slow variables and that of the fast variables. By recursively applying the technique proposed here, we can treat the general case of multi-level systems.

Regularization of time-varying descriptor systems by the asvd

We study linear variable coefficient control problems in descriptor form. Based on a behaviour approach and the general theory for linear differential algebraic systems we give the theoretical analysis and describe numerically stable methods to determine the structural properties of the system.

The economic theory of international supply chains: a systems view

This paper offers an integrated analysis of out-sourcing, off-shoring and foreign direct investment within a systems view of international business. This view takes the supply chain rather than the firm as the basic unit of analysis. It argues that competition in the global economy selects supply chains that maximise the joint profit of all the firms in the chain. The systems view is compared with the firm-centred view commonly used in strategy literature. The paper shows that a firm’s strategy must be embedded within an efficient supply chain strategy, and that this strategy must be negotiated with, rather than imposed upon, other firms. The paper analyses the conditions under which various supply chain strategies - and by implication various firm-level strategies - are efficient. Only by adopting a systems view of supply chains is it possible to determine which firm-level strategies will succeed in a volatile global economy.

A unified theory of balance in the extratropics

Many physical systems exhibit dynamics with vastly different time scales. Often the different motions interact only weakly and the slow dynamics is naturally constrained to a subspace of phase space, in the vicinity of a slow manifold. In geophysical fluid dynamics this reduction in phase space is called balance. Classically, balance is understood by way of the Rossby number R or the Froude number F; either R ≪ 1 or F ≪ 1. We examined the shallow-water equations and Boussinesq equations on an f -plane and determined a dimensionless parameter _, small values of which imply a time-scale separation. In terms of R and F, ∈= RF/√(R^2+R^2 ) We then developed a unified theory of (extratropical) balance based on _ that includes all cases of small R and/or small F. The leading-order systems are ensured to be Hamiltonian and turn out to be governed by the quasi-geostrophic potential-vorticity equation. However, the height field is not necessarily in geostrophic balance, so the leading-order dynamics are more general than in quasi-geostrophy. Thus the quasi-geostrophic potential-vorticity equation (as distinct from the quasi-geostrophic dynamics) is valid more generally than its traditional derivation would suggest. In the case of the Boussinesq equations, we have found that balanced dynamics generally implies hydrostatic balance without any assumption on the aspect ratio; only when the Froude number is not small and it is the Rossby number that guarantees a timescale separation must we impose the requirement of a small aspect ratio to ensure hydrostatic balance.

A general method for finding extremal states of Hamiltonian dynamical systems, with applications to perfect fluids

In addition to the Hamiltonian functional itself, non-canonical Hamiltonian dynamical systems generally possess integral invariants known as ‘Casimir functionals’. In the case of the Euler equations for a perfect fluid, the Casimir functionals correspond to the vortex topology, whose invariance derives from the particle-relabelling symmetry of the underlying Lagrangian equations of motion. In a recent paper, Vallis, Carnevale & Young (1989) have presented algorithms for finding steady states of the Euler equations that represent extrema of energy subject to given vortex topology, and are therefore stable. The purpose of this note is to point out a very general method for modifying any Hamiltonian dynamical system into an algorithm that is analogous to those of Vallis etal. in that it will systematically increase or decrease the energy of the system while preserving all of the Casimir invariants. By incorporating momentum into the extremization procedure, the algorithm is able to find steadily-translating as well as steady stable states. The method is applied to a variety of perfect-fluid systems, including Euler flow as well as compressible and incompressible stratified flow.

Low and middle altitude cusp particle signatures for general magnetopause reconnection rate variations: 1. Theory

We present predictions of the signatures of magnetosheath particle precipitation (in the regions classified as open low-latitude boundary layer, cusp, mantle and polar cap) for periods when the interplanetary magnetic field has a southward component. These are made using the “pulsating cusp” model of the effects of time-varying magnetic reconnection at the dayside magnetopause. Predictions are made for both low-altitude satellites in the topside ionosphere and for midaltitude spacecraft in the magnetosphere. Low-altitude cusp signatures, which show a continuous ion dispersion signature, reveal "quasi-steady reconnection" (one limit of the pulsating cusp model), which persists for a period of at least 10 min. We estimate that “quasi-steady” in this context corresponds to fluctuations in the reconnection rate of a factor of 2 or less. The other limit of the pulsating cusp model explains the instantaneous jumps in the precipitating ion spectrum that have been observed at low altitudes. Such jumps are produced by isolated pulses of reconnection: that is, they are separated by intervals when the reconnection rate is zero. These also generate convecting patches on the magnetopause in which the field lines thread the boundary via a rotational discontinuity separated by more extensive regions of tangential discontinuity. Predictions of the corresponding ion precipitation signatures seen by midaltitude spacecraft are presented. We resolve the apparent contradiction between estimates of the width of the injection region from midaltitude data and the concept of continuous entry of solar wind plasma along open field lines. In addition, we reevaluate the use of pitch angle-energy dispersion to estimate the injection distance.

Health care rights and NHS rationing: turning theory into practice

How should we understand the nature of patients’ right in public health care systems? Are health care rights different to rights under a private contract for car insurance? This article distinguishes between public and private rights and the relevance of community interests and notions of social solidarity. It discusses the distinction between political and civil rights, and social and economic rights and the inherently political and redistributive nature of the latter. Nevertheless, social and economic rights certainly give rise to “rights” enforceable by the courts. In the UK (as in many other jurisdictions), the courts have favoured a “procedural” approach to the question, in which the courts closely scrutinise decisions and demand high standards of rationality from decision-makers. However, although this is the general rule, the article also discusses a number of exceptional cases where “substantive” remedies are available which guarantee patients access to the care they need.