Regimes of conformational transitions of a diblock polyampholyte

The conformational properties of symmetric flexible diblock polyampholytes are investigated by scaling theory and molecular dynamics simulations. The electrostatically driven coil-globule transition of a symmetric diblock polyampholyte is found to consist of three regimes identified with increasing electrostatic interaction strength. In the first (folding) regime the electrostatic attraction causes the chain to fold through the overlap of the two blocks, while each block is slightly stretched by self-repulsion. The second (weak association or scrambled egg) regime is the classical collapse of the chain into a globule dominated by the fluctuation-induced attractions between oppositely charged sections of the chain. The structure of the formed globule can be represented as a dense packing of the charged chain sections (electrostatic attraction blobs). The third (strong association or ion binding) regime starts with direct binding of oppositely charged monomers (dipole formation), followed by a cascade of multipole formation (quadrupole, hexapole, octupole, etc.), leading to multiplets analogous to those found in ionomers. The existence of the multiplet cascade has also been confirmed in the simulations of solutions of short polymers with only one single charge (either positive or negative) in the middle of each chain. We use scaling theory to estimate the average chain size and the electrostatic correlation length as functions of the chain length, strength of electrostatic interactions, charge fraction, and solvent quality. The theoretically predicted scaling laws of these conformational properties are in very good agreement with our simulation results.

Analysis of the courtship behavior of the Navel Orangeworm, Amyelois transitella (Walker) (Lepidoptera: Pyralidae), with a commentary on methods for the analysis of sequences of behavioral transitions

The courtship behavior of the navel orangeworm, Amyelois transitella, was examined in a wind tunnel. Sixty nine courtship sequences were analyzed and successful sequences divided into two categories: rapid courtship sequences, which involved few breaks in contact, short or no periods of male/female chasing and lasted <10 s between initial contact and mating; and prolonged courtship sequences, which involved many breaks in contact, extended periods of male/female chasing and lasted >10 s. Fifty six (81%) courtships were successful (50.7% rapid courtship and 30.4% prolonged courtship); the remaining 13 (18.8%) sequences were failed courtships. Of failed courtships, 9 (13.0%) were due to males losing contact with females during courtship chases and 4 (5.8%) due to females flying away immediately after male contact. Of all courtship sequences involving a break in contact during a chase, 38.5% resulted in an unsuccessful mating attempt. These findings contrast with previous studies of the courtship behavior of the navel orangeworm, potentially indicating that the type of bioassay used to study courtship may have a large effect on the behavioral sequences displayed. We evaluate several diagnostic techniques for the analysis of sequences of behavioral transitions.

High-temperature order–disorder transitions in the skutterudites CoGe1.5Q1.5 (Q=S, Te)

The temperature dependence of anion ordering in the skutterudites CoGe1.5Q1.5 (Q=S, Te) has been investigated by powder neutron diffraction. Both materials adopt a rhombohedral structure at room temperature (space group R-3 ) in which the anions are ordered trans to each other within Ge2Q2 rings. In CoGe1.5S1.5, anion ordering is preserved up to the melting point of 950 °C. However, rhombohedral CoGe1.5Te1.5 undergoes a phase transition at 610 °C involving a change to cubic symmetry (space group Im-3). In the high-temperature modification, there is a statistical distribution of anions over the available sites within the Ge2Te2 rings. The structural transition involves a reduction in the degree of distortion of the Ge2Te2 rings which progressively transform from a rhombus to a rectangular shape. The effect of this transition on the thermoelectric properties has been investigated.

Caring responsibilities, change and transitions in young people's family lives in Zambia

Despite diversity in family dynamics within and between societies, globally, it is adults who are usually relied upon to care for family members who are sick, disabled or have other care needs. Young people in Zambia and other African countries affected by the HIV epidemic are under increasing pressure to obtain a good education and employment to support their families, whilst some also have to cope with the loss of parents and care for relatives with little external support. This article discusses the findings of qualitative research that explored the experiences of young people (aged 14-30) who had significant family caring responsibilities and those without such responsibilities in Zambia. Interviews and life-mapping methods were conducted with a total of 35 young people living in rural and urban areas, 12 parents and relatives and 12 professionals. We analyse young people's experiences and perceptions of socially expected transitions, such as completing education and earning an income to support themselves and their families, in addition to more unpredictable changes in young people's family lives. ‘Critical moments’ (Thomson et al, 2002), such as bereavement and loss of parents and other family members, disinheritance of assets and property grabbing, migration and mobility between different relatives homes, parental divorce and separation, often had significant impacts on young people’s ability to navigate their pathways to adulthood according to wider social norms and expectations. A more relational conceptualisation of youth transitions is needed that takes account of young people's caring responsibilities and changing family dynamics.

Abrupt transitions in the NAO control of explosive North Atlantic cyclone development

Explosive cyclones are intense extra-tropical low pressure systems featuring large deepening rates. In the Euro-Atlantic sector, they are a major source of life-threatening weather impacts due to their associated strong wind gusts, heavy precipitation and storm surges. The wintertime variability of the North Atlantic cyclonic activity is primarily modulated by the North Atlantic Oscillation (NAO). In this study, we investigate the interannual and multi-decadal variability of explosive North Atlantic cyclones using track density data from two reanalysis datasets (NCEP and ERA-40) and a control simulation of an atmosphere/ocean coupled General Circulation Model (GCM—ECHAM5/MPIOM1). The leading interannual and multi-decadal modes of variability of explosive cyclone track density are characterized by a strengthening/weakening pattern between Newfoundland and Iceland, which is mainly modulated by the NAO at both timescales. However, the NAO control of interannual cyclone variability is not stationary in time and abruptly fluctuates during periods of 20–25 years long both in NCEP and ECHAM5/MPIOM1. These transitions are accompanied by structural changes in the leading mode of explosive cyclone variability, and by decreased/enhanced baroclinicity over the sub-polar/sub-tropical North Atlantic. The influence of the ocean is apparently important for both the occurrence and persistence of such anomalous periods. In the GCM, the Atlantic Meridional Overturning Circulation appears to influence the large-scale baroclinicity and explosive cyclone development over the North Atlantic. These results permit a better understanding of explosive cyclogenesis variability at different climatic timescales and might help to improve predictions of these hazardous events.

Phase transitions of frozen camu-camu (Myrciaria dubia (HBK) McVaugh) pulp: Effect of cryostabilizer addition

Camu-camu is a tropical fruit with very high vitamin C content and commercialized as frozen pulp. Enthalpies of freezing, temperatures of the onset of ice melting, and glass transition temperatures of the maximally freeze-concentrated phase (T`(g)) of camu-camu pulp and of samples containing maltodextrin (DE20) and sucrose were measured by differential scanning calorimetry. Maltodextrin exhibited the largest freeze stabilization potential, increasing T`(g) from -58.2 degrees C (natural pulp) to -39.6 degrees C when 30% (w/w) maltodextrin DE 20 was added. Sucrose showed negligible effect on T`(g) but enhanced considerably the freezing point depression and less amount of ice was formed.

Phase transitions of cassava starch dispersions prepared with glycerol solutions

The aim of this work was to study the glass transition, the glass transition of the maximally freeze-concentrated fractions, the ice melting and the gelatinization phenomenon in dispersions of starch prepared using glycerol- water solutions. The starch concentration was maintained constant at 50 g cassava starch/100 g starch dispersions, but the concentration of the glycerol solutions was variable (C-g= 20, 40, 60, 80 and 100 mass/mass%). The phase transitions of these dispersions were studied by calorimetric methods, using a conventional differential scanning calorimeter (DSC) and a more sensitive equipment (micro-DSC). Apparently, in the glycerol diluted solutions (20 and 40%), the glycerol molecules interacted strongly with the glucose molecules of starch. While in the more concentrated glycerol domains (C-g> 40%), the behaviour was controlled by migration of water molecules from the starch granules, due to a hypertonic character of glycerol, which affected all phase transitions.

Growth of EuTe islands on SnTe by molecular beam epitaxy

Semiconductor magnetic quantum dots are very promising structures, with novel properties that find multiple applications in spintronic devices. EuTe is a wide gap semiconductor with NaCl structure, and strong magnetic moments S=7/2 at the half filled 4f(7) electronic levels. On the other hand, SnTe is a narrow gap semiconductor with the same crystal structure and 4% lattice mismatch with EuTe. In this work, we investigate the molecular beam epitaxial growth of EuTe on SnTe after the critical thickness for island formation is surpassed, as a previous step to the growth of organized magnetic quantum dots. The topology and strain state of EuTe islands were studied as a function of growth temperature and EuTe nominal layer thickness. Reflection high energy electron diffraction (RHEED) was used in-situ to monitor surface morphology and strain state. RHEED results were complemented and enriched with atomic force microscopy and grazing incidence X-ray diffraction measurements made at the XRD2 beamline of the Brazilian Synchrotron. EuTe islands of increasing height and diameter are obtained when the EuTe nominal thickness increases, with higher aspect ratio for the islands grown at lower temperatures. As the islands grow, a relaxation toward the EuTe bulk lattice parameter was observed. The relaxation process was partially reverted by the growth of the SnTe cap layer, vital to protect the EuTe islands from oxidation. A simple model is outlined to describe the distortions caused by the EuTe islands on the SnTe buffer and cap layers. The SnTe cap layers formed interesting plateau structures with easily controlled wall height, that could find applications as a template for future nanostructures growth. (C) 2010 Elsevier B.V. All rights reserved.

Quartz recrystallization regimes, c-axis texture transitions and fluid inclusion reequilibration in a prograde greenschist to amphibolite facies mylonite zone (Ribeira Shear Zone, SE Brazil)

The crystal-plastic behavior of quartz mylonites from the Ribeira Shear Zone (SE Brazil), a major strike-slip structure that was active during a prograde metamorphic phase related to the Neoproterozoic Brasiliano-Pan African Orogeny, was investigated using a multi-method approach. Geothermobarometry results indicate deformational conditions ranging from similar to 300 to similar to 630 degrees C and 500-700 MPa. A strong correlation between mapped metamorphic zones and a dominance of different dynamic recrystallization mechanisms of quartz occurs within the mylonite zone. Bulging recrystallization (BLG) dominates within the chlorite zone between 300 and 410 degrees C, subgrain rotation recrystallization (SGR) operates within the biotite zone from 410 to 520 degrees C, and grain boundary migration recrystallization (GBM) dominates in the garnet zone above 520 degrees C. The development of quartz c-axis textures is mainly governed by temperature and dynamic recrystallization mechanisms. Textures from BLG zone mylonites are characterized by maxima around Z; SGR zone mylonites display single girdles or asymmetric type I crossed girdles; and GBM zone mylonites comprise maxima around Y and intermediate between X and Z. The scarcity or absence of water-bearing fluid inclusions in quartz mylonites from the SGR and GBM zones, which are dominated by carbonic inclusions, suggests water-deficient conditions, whereas BLG zone mylonites are dominated by water-bearing inclusions. This evidence indicates that water was available in the protoliths but has been eliminated with increasing deformation and deformation temperature. No effect of the water content variation on the quartz microstructural and recrystallized grain size evolution was detected, and little influence on c-axis texture development was observed. Most of the fluid inclusion densities were reequilibrated during the shear zone exhumation history, recording a decompression in the range of 300-500 MPa, while microstructural reequilibration effects related to the prograde metamorphism are largely preserved. Fluid inclusion microstructures and densities from two SGR zone samples preserved evidence for a near isothermal compression within the interior of the Ribeira Shear Zone during the prograde metamorphism. (C) 2009 Elsevier B.V. All rights reserved.

Bootstrap percolation on homogeneous trees has 2 phase transitions

We study the threshold theta bootstrap percolation model on the homogeneous tree with degree b + 1, 2 <= theta <= b, and initial density p. It is known that there exists a nontrivial critical value for p, which we call p(f), such that a) for p > p(f), the final bootstrapped configuration is fully occupied for almost every initial configuration, and b) if p < p(f) , then for almost every initial configuration, the final bootstrapped configuration has density of occupied vertices less than 1. In this paper, we establish the existence of a distinct critical value for p, p(c), such that 0 < p(c) < p(f), with the following properties: 1) if p <= p(c), then for almost every initial configuration there is no infinite cluster of occupied vertices in the final bootstrapped configuration; 2) if p > p(c), then for almost every initial configuration there are infinite clusters of occupied vertices in the final bootstrapped configuration. Moreover, we show that 3) for p < p(c), the distribution of the occupied cluster size in the final bootstrapped configuration has an exponential tail; 4) at p = p(c), the expected occupied cluster size in the final bootstrapped configuration is infinite; 5) the probability of percolation of occupied vertices in the final bootstrapped configuration is continuous on [0, p(f)] and analytic on (p(c), p(f) ), admitting an analytic continuation from the right at p (c) and, only in the case theta = b, also from the left at p(f).

New Relativistic Atomic Natural Orbital Basis Sets for Lanthanide Atoms with Applications to the Ce Diatom and LuF3

New basis sets of the atomic natural orbital (ANO) type have been developed for the lanthanide atoms La-Lu. The ANOs have been obtained from the average density matrix of the ground and lowest excited states of the atom, the positive ions, and the atom in an electric field. Scalar relativistic effects are included through the use of a Douglas-Kroll-Hess Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using second-order perturbation theory (CASSCF/CASPT2). The basis sets are applied in calculations of ionization energies and some excitation energies. Computed ionization energies have an accuracy better than 0.1 eV in most cases. Two molecular applications are inluded as illustration: the cerium diatom and the LuF3 molecule. In both cases it is shown that 4f orbitals are not involved in the chemical bond in contrast to an earlier claim for the latter molecule.

Um balanço da responsabilidade social no Brasil

A idéia de responsabilidade social vem sempre associada a uma mudança na forma das empresas se comportarem. Algo “a mais” em suas próprias rotinas. Como combinar esse conceito com o sentimento real, procedente e crescente no meio empresarial da excessiva carga tributária que pesa sobre suas próprias organizações? Minha intenção com este texto é sugerir uma resposta ao que parece um beco sem saída.

Designing for workstyle transitions: interaction design tools for software engineering

Supervisor: Duarte Nuno Jardim Nunes