Synthesis, structure, and redox states of homoleptic d-block metal complexes with bis-1,2,4-triazin-3-yl-pyridine and 1,2,4-triazin-3-yl-bipyridine extractants

it has been established that triazinyl bipyridines (hemi-BTPs) and bis-triazinyl pyridines (BTPs), ligands which are currently being investigated as possible ligands for the separation of actinides from lanthanides in nuclear waste, are able to form homoleptic complexes with first row transition metals such as cobalt(IT), copper(II), iron(II), manganese(II), nickel(II) and zinc(II). The metal complexes exhibit six-co-ordinate octahedral structures and redox states largely analogous to those of the related terpyridine complexes. The reactivity of the different redox states of cobalt bis-hemi-BTP complex in aqueous environments has been studied with two-phase electrochemistry by immobilisation of the essentially water-insoluble metal complexes on graphite electrodes and the immersion of this modified electrode in an aqueous electrolyte. It was found that redox potentials for the metal-centred reactions were pH-independent whereas the potentials for the ligand-centred reactions were strongly pH-dependent. The reductive degradation of these complexes has been investigated by computational methods. Solvent extraction experiments have been carried out for a range of metals and these show that cobalt(II) and nickel(II) as well as palladium(II), cadmium(II) and lead(II) were all extracted with the ligands 1e and 2c with higher distribution ratios that was observed for americium(III) under the same conditions. The implications of this result for the use of these ligands to separate actinides from nuclear waste are discussed. (c) 2005 Elsevier Ltd. All rights reserved.

Language support for immigrant children: a study of state schools in the UK and US

In recent decades, immigrants, refugees and asylum seekers have sought a new way of life in large numbers, often leaving their countries of origin behind in search of places that offer a better way of life. The purpose of this study was to investigate how elementary and middle school students in state schools in Reading, England (primarily speakers of Asian languages), and Richmond, Virginia (primarily speakers of Spanish), were supported academically, when most children's first language was not English. The authors were interested in exploring whether or not there were cultural or structural differences in the way each country helped or hindered these students as they progressed through the school systems. Three UK schools in a district of approximately 100,000 and three US schools in a district of approximately 250,000 were the focus of this exploration from 2000 to 2003. Findings indicated that there were cultural and legislative differences and similarities. Teachers and administrators in both countries attempted to provide services with limited and sometimes diminishing resources. Community support varied based on resources, attitudes toward various ethnic groups, and the coping strategies adopted by these groups in their new environments. Marked differences appeared with regard to the manner in which assessments took place and how the results were made available to the public.

Weight of evidence needed to substantiate a health effect for probiotics and prebiotics: regulatory considerations in Canada, EU, and US

Successful and responsible introduction of probiotic and prebiotic products into the worldwide marketplace requires labelling for health benefits that meets consumer needs, adheres to regulatory standards and does not overextend scientific evidence. Regulations differ among countries, but underlying all is an emphasis on scientific credibility of any statements of health benefits. This paper considers the value of different types of evidence offered in substantiation of efficacy and reviews different regulatory approaches to labelling for health claims. Limitations of in vitro, animal and different types of human studies used for efficacy substantiation for probiotics and prebiotics are discussed.

Ferric and ferrous iron in nitroso-myoglobin: computer simulations of stable and metastable states and their infrared spectra

The binding of NO to iron is involved in the biological function of many heme proteins. Contrary to ligands like CO and O-2, which only bind to ferrous (Fe-II) iron, NO binds to both ferrous and ferric (Fe-II) iron. In a particular protein, the natural oxidation state can therefore be expected to be tailored to the required function. Herein, we present an ob initio potential-energy surface for ferric iron interacting with NO. This potential-energy surface exhibits three minima corresponding to eta'-NO coordination (the global minimum), eta(1)-ON coordination and eta(2) coordination. This contrasts with the potential-energy surface for Fe-II-NO, which ex- hibits only two minima (the eta(2) coordination mode for Fe-II is a transition state, not a minimum). In addition, the binding energies of NO are substantially larger for Fe-III than for Fe-II. We have performed molecular dynamics simulations for NO bound to ferric myoglobin (Mb(III)) and compare these with results obtained for Mb(II). Over the duration of our simulations (1.5 ns), all three binding modes are found to be stable at 200 K and transiently stable at 300 K, with eventual transformation to the eta(1)-NO global-minimum conformation. We discuss the implication of these results related to studies of rebinding processes in myoglobin.

Inequality of educational opportunity in India: changes over time and across states

This paper documents the extent of inequality of educational opportunity in India spanning the period 1983–2004 using National Sample Surveys. We build on recent developments in the literature that have operationalized concepts of inequality of opportunity theory and construct several indices of inequality of educational opportunity for an adult sample. Kerala stands out as the least opportunity-unequal state. Rajasthan, Gujarat, and Uttar Pradesh experienced large-scale falls in the ranking of inequality of opportunities. By contrast, West Bengal and Orissa made significant progress in reducing inequality of opportunity. We also examine the links between progress toward equality of opportunity and a selection of pro-poor policies.

Conductance and relaxations of gelatin films in the glassy and rubbery states

The dielectric constant, epsilon', and the dielectric loss, epsilon'', for gelatin films were measured in the glassy and rubbery states over a frequency range from 20 Hz to 10 MHz; epsilon' and epsilon'' were transformed into M* formalism (M* = 1/(epsilon' - i epsilon'') = M' + iM''; i, the imaginary unit). The peak of epsilon'' was masked probably due to dc conduction, but the peak of M'', e.g. the conductivity relaxation, for the gelatin used was observed. By fitting the M'' data to the Havriliak-Negami type equation, the relaxation time, tauHN, was evaluated. The value of the activation energy, Etau, evaluated from an Arrhenius plot of 1/tauHN, agreed well with that of Esigma evaluated from the DC conductivity sigma0 both in the glassy and rubbery states, indicating that the conductivity relaxation observed for the gelatin films was ascribed to ionic conduction. The value of the activation energy in the glassy state was larger than that in the rubbery state.

Effect of pair interactions on transition probabilities between inactive and active states: achieving collective behaviour via pair interactions in social insects

To understand the evolution of well-organized social behaviour, we must first understand the mechanism by which collective behaviour establishes. In this study, the mechanisms of collective behaviour in a colony of social insects were studied in terms of the transition probability between active and inactive states, which is linked to mutual interactions. The active and inactive states of the social insects were statistically extracted from the velocity profiles. From the duration distributions of the two states, we found that 1) the durations of active and inactive states follow an exponential law, and 2) pair interactions increase the transition probability from inactive to active states. The regulation of the transition probability by paired interactions suggests that such interactions control the populations of active and inactive workers in the colony.

Long-run restrictions and survey forecasts of output, consumption and investment

We consider the extent to which long-horizon survey forecasts of consumption, investment and output growth are consistent with theory-based steady-state values, and whether imposing these restrictions on long-horizon forecasts will enhance their accuracy. The restrictions we impose are consistent with a two-sector model in which the variables grow at different rates in steady state. The restrictions are imposed by exponential-tilting of simple auxiliary forecast densities. We show that imposing the consumption-output restriction yields modest improvements in the long-horizon output growth forecasts, and larger improvements in the forecasts of the cointegrating combination of consumption and output: the transformation of the data on which accuracy is assessed plays an important role.

Geometric polarimetry − part I: spinors and wave states

A new formal approach for representation of polarization states of coherent and partially coherent electromagnetic plane waves is presented. Its basis is a purely geometric construction for the normalised complex-analytic coherent wave as a generating line in the sphere of wave directions, and whose Stokes vector is determined by the intersection with the conjugate generating line. The Poincare sphere is now located in physical space, simply a coordination of the wave sphere, its axis aligned with the wave vector. Algebraically, the generators representing coherent states are represented by spinors, and this is made consistent with the spinor-tensor representation of electromagnetic theory by means of an explicit reference spinor we call the phase flag. As a faithful unified geometric representation, the new model provides improved formal tools for resolving many of the geometric difficulties and ambiguities that arise in the traditional formalism.

Stability and related properties of vacua and ground states

We consider the formal non-relativistic limit (nrl) of the : phi(4):(s+1) relativistic quantum field theory (rqft), where s is the space dimension. Following the work of R. Jackiw [R. Jackiw, in: A. Ali, P. Hood-bhoy (Eds.), Beg Memorial Volume, World Scientific, Singapore, 1991], we show that, for s = 2 and a given value of the ultraviolet cutoff K, there are two ways to perform the nrl: (i) fixing the renormalized mass m(2) equal to the bare mass m(0)(2); (ii) keeping the renormalized mass fixed and different from the bare mass mo. In the (infinite-volume) two-particle sector the scattering amplitude tends to zero as K -> infinity in case (i) and, in case (ii), there is a bound state, indicating that the interaction potential is attractive. As a consequence, stability of matter fails for our boson system. We discuss why both alternatives do not reproduce the low-energy behaviour of the full rqft. The singular nature of the nrl is also nicely illustrated for s = 1 by a rigorous stability/instability result of a different nature. (C) 2007 Elsevier Inc. All rights reserved.

Coherent and semiclassical states in a magnetic field in the presence of the Aharonov-Bohm solenoid

A new approach to constructing coherent states (CS) and semiclassical states (SS) in a magnetic-solenoid field is proposed. The main idea is based on the fact that the AB solenoid breaks the translational symmetry in the xy-plane; this has a topological effect such that there appear two types of trajectories which embrace and do not embrace the solenoid. Due to this fact, one has to construct two different kinds of CS/SS which correspond to such trajectories in the semiclassical limit. Following this idea, we construct CS in two steps, first the instantaneous CS (ICS) and then the time-dependent CS/SS as an evolution of the ICS. The construction is realized for nonrelativistic and relativistic spinning particles both in (2 + 1) and (3 + 1) dimensions and gives a non-trivial example of SS/CS for systems with a nonquadratic Hamiltonian. It is stressed that CS depending on their parameters (quantum numbers) describe both pure quantum and semiclassical states. An analysis is represented that classifies parameters of the CS in such respect. Such a classification is used for the semiclassical decompositions of various physical quantities.