Lead and aluminum bonding in Pb-Al metaphosphate glasses

The bonding properties of cations in phosphate glasses determine many short- and medium-range structural features in the glass network, hence influencing bulk properties. In this work, Pb-Al-metaphosphate glasses (1 - x)Pb-(PO(3))(2)center dot xAI(PO(3))(3) with 0 <= - x <= 1 were analyzed to determine the effect of the substitution of Pb by Al on the glass structure in the metaphosphate composition. The glass transition temperature and density were measured as a function of the Al concentration. The vibrational and structural properties were probed by Raman spectroscopy and nuclear magnetic resonance of (31)P, (27)Al, and (207)Pb. Aluminum incorporates homogeneously in the glass creating a stiffer and less packed network. The average coordination number for Al decreases from 5.9 to 5.0 as x increases from 0.1 to 1, indicating more covalent Al-O bonds. The coordination number of Pb in these glasses is greater than 8, showing an increasing ionic behavior for compositions richer in Al. A quantitative analysis of the phosphate speciation shows definite trends in the bonding of AlO(n) groups and phosphate tetrahedra. In glasses with x < 0.48, phosphate groups share preferentially only one nonbridging O corner with an AlO(n) coordination polyhedron. For x > 0.48 more than one nonbridging O can be linked to AlO(n) polyhedra. There is no corner sharing of O between AlO(n) and PbO(n) polyhedra nor between AlO(n) themselves throughout the compositional range. The PbO(n) coordination polyhedra show considerable nonbridging O sharing, with each O participating in the coordination sphere of at least two Pb. The bonding preferences determined for Al are consistent with the behavior observed in Na-Al and Ca-Al metaphosphates, indicating this may be a general behavior for ternary phosphate glasses.

Efficient solutions to factored MDPs with imprecise transition probabilities

When modeling real-world decision-theoretic planning problems in the Markov Decision Process (MDP) framework, it is often impossible to obtain a completely accurate estimate of transition probabilities. For example, natural uncertainty arises in the transition specification due to elicitation of MOP transition models from an expert or estimation from data, or non-stationary transition distributions arising from insufficient state knowledge. In the interest of obtaining the most robust policy under transition uncertainty, the Markov Decision Process with Imprecise Transition Probabilities (MDP-IPs) has been introduced to model such scenarios. Unfortunately, while various solution algorithms exist for MDP-IPs, they often require external calls to optimization routines and thus can be extremely time-consuming in practice. To address this deficiency, we introduce the factored MDP-IP and propose efficient dynamic programming methods to exploit its structure. Noting that the key computational bottleneck in the solution of factored MDP-IPs is the need to repeatedly solve nonlinear constrained optimization problems, we show how to target approximation techniques to drastically reduce the computational overhead of the nonlinear solver while producing bounded, approximately optimal solutions. Our results show up to two orders of magnitude speedup in comparison to traditional ""flat"" dynamic programming approaches and up to an order of magnitude speedup over the extension of factored MDP approximate value iteration techniques to MDP-IPs while producing the lowest error of any approximation algorithm evaluated. (C) 2011 Elsevier B.V. All rights reserved.

Minimizing the object dimensions in circle and sphere packing problems

Given a fixed set of identical or different-sized circular items, the problem we deal with consists on finding the smallest object within which the items can be packed. Circular, triangular, squared, rectangular and also strip objects are considered. Moreover, 2D and 3D problems are treated. Twice-differentiable models for all these problems are presented. A strategy to reduce the complexity of evaluating the models is employed and, as a consequence, instances with a large number of items can be considered. Numerical experiments show the flexibility and reliability of the new unified approach. (C) 2007 Elsevier Ltd. All rights reserved.

THE LOWER CENTRAL AND DERIVED SERIES OF THE BRAID GROUPS OF THE FINITELY-PUNCTURED SPHERE

Motivated in part by the study of Fadell-Neuwirth short exact sequences, we determine the lower central and derived series for the braid groups of the finitely-punctured sphere. For n >= 1, the class of m-string braid groups B(m)(S(2)\{x(1), ... , x(n)}) of the n-punctured sphere includes the usual Artin braid groups B(m) (for n = 1), those of the annulus, which are Artin groups of type B (for n = 2), and affine Artin groups of type (C) over tilde (for n = 3). We first consider the case n = 1. Motivated by the study of almost periodic solutions of algebraic equations with almost periodic coefficients, Gorin and Lin calculated the commutator subgroup of the Artin braid groups. We extend their results, and show that the lower central series (respectively, derived series) of B(m) is completely determined for all m is an element of N (respectively, for all m not equal 4). In the exceptional case m = 4, we obtain some higher elements of the derived series and its quotients. When n >= 2, we prove that the lower central series (respectively, derived series) of B(m)(S(2)\{x(1), ... , x(n)}) is constant from the commutator subgroup onwards for all m >= 3 (respectively, m >= 5). The case m = 1 is that of the free group of rank n - 1. The case n = 2 is of particular interest notably when m = 2 also. In this case, the commutator subgroup is a free group of infinite rank. We then go on to show that B(2)(S(2)\{x(1), x(2)}) admits various interpretations, as the Baumslag-Solitar group BS(2, 2), or as a one-relator group with non-trivial centre for example. We conclude from this latter fact that B(2)(S(2)\{x(1), x(2)}) is residually nilpotent, and that from the commutator subgroup onwards, its lower central series coincides with that of the free product Z(2) * Z. Further, its lower central series quotients Gamma(i)/Gamma(i+1) are direct sums of copies of Z(2), the number of summands being determined explicitly. In the case m >= 3 and n = 2, we obtain a presentation of the derived subgroup, from which we deduce its Abelianization. Finally, in the case n = 3, we obtain partial results for the derived series, and we prove that the lower central series quotients Gamma(i)/Gamma(i+1) are 2-elementary finitely-generated groups.

The classification and the conjugacy classes of the finite subgroups of the sphere braid groups

Let n >= 3. We classify the finite groups which are realised as subgroups of the sphere braid group B(n)(S(2)). Such groups must be of cohomological period 2 or 4. Depending on the value of n, we show that the following are the maximal finite subgroups of B(n)(S(2)): Z(2(n-1)); the dicyclic groups of order 4n and 4(n - 2); the binary tetrahedral group T*; the binary octahedral group O*; and the binary icosahedral group I(*). We give geometric as well as some explicit algebraic constructions of these groups in B(n)(S(2)) and determine the number of conjugacy classes of such finite subgroups. We also reprove Murasugi`s classification of the torsion elements of B(n)(S(2)) and explain how the finite subgroups of B(n)(S(2)) are related to this classification, as well as to the lower central and derived series of B(n)(S(2)).

Nicorandil protects cardiac mitochondria against permeability transition induced by ischemia-reperfusion

Ischemia followed by reperfusion is known to negatively affect mitochondrial function by inducing a deleterious condition termed mitochondrial permeability transition. Mitochondrial permeability transition is triggered by oxidative stress, which occurs in mitochondria during ischemia-reperfusion as a result of lower antioxidant defenses and increased oxidant production. Permeability transition causes mitochondrial dysfunction and can ultimately lead to cell death. A drug able to minimize mitochondrial damage induced by ischemia-reperfusion may prove to be clinically effective. We aimed to analyze the effects of nicorandil, an ATP-sensitive potassium channel agonist and vasodilator, on mitochondrial function of rat hearts and cardiac HL-1 cells submitted to ischemia-reperfusion. Nicorandil decreased mitochondrial swelling and calcium uptake. It also decreased reactive oxygen species formation and thiobarbituric acid reactive substances levels, a lipid peroxidation biomarker. We thus confirm previous reports that nicorandil inhibits mitochondrial permeability transition and demonstrate that nicorandil inhibits this process by preventing oxidative damage and mitochondrial calcium overload induced by ischemia-reperfusion, resulting in improved cardiomyocyte viability. These results may explain the good clinical results obtained when using nicorandil in the treatment of ischemic heart disease.

Solvatochromic Shift of the pi -> pi* Transition in All-Trans, Cis-13, Cis-11, Cis-9, and Cis-7 Retinal Isomers Induced by Water and Methanol

The solvatochromic shift of the lowest singlet it pi -> pi* electronic transition in the all-trans, cis-13, cis-11, cis-9, and cis-7 retinal isomers were computed under the influence of water, methanol, and benzene solvents. Excitation energies were calculated in gas phase and in solution. The calculations in solution were performed considering the sequential Monte Carlo (MC) /Quantum Mechanical approach. The MC simulations were performed considering the full retinal isomer molecules and 900 water molecules, 900 methanol, or 400 benzene ones. The OPLS/AA parametrization was chosen for retinal, methanol, and benzene molecules and the SPC model was used for water one. From the MC calculations 100 independent configurations were selected, with 100 solvent molecules in thermodynamical equilibrium at T = 298.15 K. Average point-charges were obtained from those independent configurations for water, methanol, and benzene solvent. TDDFT and CASSCF//CASPT2 methodologies were used to compute the vertical excitation energy of the retinal isomers in different environment. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110: 2076-2087, 2010

Excited Electronic States, Transition Probabilities, and Radiative Lifetimes of CAs: A Theoretical Contribution and Challenge to Experimentalists

High-level CASSCF/MRCI calculations with a quintuple-zeta quality basis set are reported by characterizing for the first time a manifold of electronic states of the CAs radical yet to be investigated experimentally. Along with the potential energy curves and the associated spectroscopic constants, the dipole moment functions for selected electronic states as well as the transition dipole moment functions for the most relevant electronic transitions are also presented. Estimates of radiative transition probabilities and lifetimes complement this investigation, which also assesses the effect of spin-orbit interaction on the A (2)Pi state. Whenever pertinent, comparisons of similarities and differences with the isovalent CN and CP radicals are made.

N3-Dye-Induced Visible Laser Anatase-to-Rutile Phase Transition on Mesoporous TiO(2) Films

Titanium dioxide has been extensively used in photocatalysis and dye-sensitized solar cells, where control of the anatase-to-rutile phase transformation may allow the realization of more efficient devices exploiting the synergic effects at anatase/rutile interfaces. Thus, a systematic study showing the proof of concept of a dye-induced morphological transition and an anatase-to-rutile transition based on visible laser (532 nm) and nano/micro patterning of mesoporous anatase (Degussa P25 TiO(2)) films is described for the first time using a confocal Raman microscope. At low laser intensities, only the bleaching of the adsorbed N3 dye was observed. However, high enough temperatures to promote melting/densification processes and create a deep hole at the focus and an extensive phase transformation in the surrounding material were achieved using Is laser pulses of 25-41 mW/cm(2), in resonance with the MLCT band. The dye was shown to play a key role, being responsible for the absorption and efficient conversion of the laser light into heat. As a matter of fact, the dye is photothermally decomposed to amorphous carbon or to gaseous species (CO(x), NO(x), and H(2)O) under a N(2) or O(2) atmosphere, respectively.

Application of Microelectrode Voltammetry to Study the Properties of Surfactant Solutions: Alkyltrimethylammonium Bromides

Microelectrode cyclic voltammetry (MV) has been employed to investigate the micellar properties of solutions of homologous alkyltrimethylammonium bromides, RMe(3)ABr, R = C(10), C(12), and C(14), in water and in the presence of added NaBr. The micellar self-diffusion coefficient was calculated from the limiting current for the reversible electron transfer of micelle-bound ferrocene. From the values of this property, other parameters were calculated, including the micellar hydrodynamic radius, RH, and aggregation number, N(agg); the latter was also theoretically calculated. We determined the values of the diffusion coefficient as a function of various experimental variables and observed the following trends: The diffusion coefficient decreases as a function of increasing surfactant concentration (no additional electrolyte added); it decreases as a function of increasing surfactant concentration at fixed NaBr concentration; and it shows a complex dependence (increase then decrease) on the NaBr concentration at a fixed RMe(3)ABr concentration. The value of the intermicellar interaction parameter decreases and then increases as a function of increasing NaBr concentration. These results are discussed in terms of intermicellar,interactions and the effect of NaBr on the micellar surface charge density and sphere-to-rod geometry change. The NaBr concentration required to induce the latter change increases rapidly as a function of decreasing the length of R: no geometry change was detected for C(10)Me(3)ABr. Values of N(agg) increase as I function of increasing the length of R and are in good agreement with both literature values and values that were calculated theoretically. Thus, MV is a convenient and simple technique for obtaining fundamental properties of surfactant solutions, including additive-induced changes of micellar parameters (N(agg)) and morphology changes.

Can mass dissociation patterns of transition-metal complexes be predicted from electrochemical data?

The Cooks kinetic method has been very convenient to correlate the relative dissociation rates obtained by collision-induced fragmentation experiments with the energies of two related bonds in molecules and complexes in the gas phase. Reliable bond energy data are, however, not always available, particularly for polynuclear transition-metal complexes, such as the triruthenium acetate clusters of the general formula [Ru(3) (mu(3)-O)(mu-CH(3)COO)(6)(py)(2)(L)](+), where L = ring substituted N-heterocyclic ligands. Accordingly, their gas-phase collision-induced tandem mass spectrometry (CID MS/MS) dissociation patterns have been analyzed pursuing a relationship with the more easily accessible redox potentials (E(1/2)) and Lever`s E(L) parameters. In fact, excellent linear correlations of In(1/2A(L)/A(py)), where A(py) and A(L) are the abundance of the fragments retaining the pyridine (py) and L ligand, respectively, with E(1/2) and E(L) were found. This result shows that those electrochemical parameters are correlated with bond energies and can be used in the analysis of the dissociation data. Such modified Cooks method can be used, for example, to determine the electronic effects of substituents on the metal-ligand bonds for a series of transition-metal complexes. Copyright (C) 2008 John Wiley & Sons, Ltd.

Testing linear cointegration against smooth-transition cointegration

This paper studies a smooth-transition (ST) type cointegration. The proposed ST cointegration allows for regime switching structure in a cointegrated system. It nests the linear cointegration developed by Engle and Granger (1987) and the threshold cointegration studied by Balke and Fomby (1997). We develop F-type tests to examine linear cointegration against ST cointegration in ST-type cointegrating regression models with or without time trends. The null asymptotic distributions of the tests are derived with stationary transition variables in ST cointegrating regression models. And it is shown that our tests have nonstandard limiting distributions expressed in terms of standard Brownian motion when regressors are pure random walks, while have standard asymptotic distributions when regressors contain random walks with nonzero drift. Finite-sample distributions of those tests are studied by Monto Carlo simulations. The small-sample performance of the tests states that our F-type tests have a better power when the system contains ST cointegration than when the system is linearly cointegrated. An empirical example for the purchasing power parity (PPP) data (monthly US dollar, Italy lira and dollar-lira exchange rate from 1973:01 to 1989:10) is illustrated by applying the testing procedures in this paper. It is found that there is no linear cointegration in the system, but there exits the ST-type cointegration in the PPP data.

Gravitational self-localization for spherical masses

In this work, I consider the center-of-mass wave function for a homogenous sphere under the influence of the self-interaction due to Newtonian gravity. I solve for the ground state numerically and calculate the average radius as a measure of its size. For small masses, M≲10−17 kg, the radial size is independent of density, and the ground state extends beyond the extent of the sphere. For masses larger than this, the ground state is contained within the sphere and to a good approximation given by the solution for an effective radial harmonic-oscillator potential. This work thus determines the limits of applicability of the point-mass Newton Schrödinger equations for spherical masses. In addition, I calculate the fringe visibility for matter-wave interferometry and find that in the low-mass case, interferometry can in principle be performed, whereas for the latter case, it becomes impossible. Based on this, I discuss this transition as a possible boundary for the quantum-classical crossover, independent of the usually evoked environmental decoherence. The two regimes meet at sphere sizes R≈10−7 m, and the density of the material causes only minor variations in this value.

Parenthood in transition : Somali-born parents' experiences of and needs for parenting support programmes

BACKGROUND: Pre- and post-migration trauma due to forced migration may impact negatively on parents' ability to care for their children. Little qualitative work has examined Somali-born refugees' experiences. The aim of this study is to explore Somali-born refugees' experiences and challenges of being parents in Sweden, and the support they need in their parenting. METHODS: A qualitative descriptive study was undertaken. Data were collected from four focus group discussions (FGDs) among 23 Somali-born mothers and fathers living in a county in central Sweden. Qualitative content analysis has been applied. RESULTS: A main category, Parenthood in Transition, emerged as a description of a process of parenthood in transition. Two generic categories were identified: Challenges, and Improved parenting. Challenges emerged from leaving the home country and being new and feeling alienated in the new country. In Improved parenting, an awareness of opportunities in the new country and ways to improve their parenting was described, which includes how to improve their communication and relationship with their children. The parents described a need for information on how to culturally adapt their parenting and obtain support from the authorities. CONCLUSIONS: Parents experienced a process of parenthood in transition. They were looking to the future and for ways to improve their parenting. Schools and social services can overcome barriers that prevent lack of knowledge about the new country's systems related to parenthood. Leaving the home country often means separation from the family and losing the social network. We suggest that staff in schools and social services offer parent training classes for these parents throughout their children's childhood, with benefits for the child and family.