XPS studies of directly fluorinated HDPE: problems and solutions

X-ray photoelectron spectroscopy (XPS) applied to the study of fluorinated polymer surfaces presents several problems related both to peak assignment and to degradation. In this work, we analyse extensively the question of XPS peak assignments in this kind of surfaces. We conclude that in this kind of surfaces using binding energy differences between fluorine and carbon is better than using absolute binding energies. Also a useful relation between fluorine photoelectron energy vs. polymer composition expressed through the atomic ratio fluorine/carbon (F/C) was found. A protocol for data treatment is proposed and applied to a XPS study of the degradation induced by X-ray on high-density polyethylene surfaces modified by direct fluorination. Results obtained for the degradation, namely the atomic ratio F/C obtained by two different methods, combined with angle resolved X-ray photoelectron spectroscopy (ARXPS) were used to study the fluorine concentration profile in depth, producing self-consistent results.     

Effects of age and schooling on the acquisition of elementary quantitative skills.

The influence of school- and age-related variables was examined separately on 2 tasks involving elementary quantitative skills: conservation of number and mental addition. Performance on these tasks was compared by using a cutoff design with 3 groups of kindergarten and Grade 1 children who differed in age but not amount of schooling (grade), in schooling but not age, or in both age and schooling. The effects of age and schooling were distinct. On conservation of number, performance improved as a function of age but not schooling. On mental arithmetic, accuracy improved with schooling rather than age but children's use of various solution procedures (e.g., retrieval, counting) was not influenced by schooling. Thus, in the domain of elementary mathematical skills, the influence of schooling can be very specific, and age-related variables other than schooling play an important role in the development of elementary mathematical skills. Results illustrate the utility of the cutoff design for investigating instructional and developmental influences on cognitive development. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Energy efficiency, carbon emissions and economic development in Venezuela

Venezuela's vast natural resource base has largely shaped the nation's economic and energy-use patterns. Major opportunities exist for improving the efficiency of energy use in Venezuela and, consequently, restraining the growth of energy-related carbon emissions. This paper presents a detailed report of one potential development path for Venezuela and estimates the ensuing levels of energy demand and CO₂ emissions associated with pursuing this path through the year 2025. The results indicate that by adopting a development strategy that incorporates structural changes in the economy, fuel-switching measures and improved end-use efficiencies, Venezuela can introduce energy efficiency and carbon restraints as part of its economic development process.     

The ontogeny and significance of infants' facial expressions in the first 9 months of life.

Four studies examined aspects of the differential emotions theory (DET) hypothesis of expressive behavior development. In Study 1, facial-expressive movements of 108 2.5–9-mo-old infants were video recorded in positive and negative mother–infant interactions (conditions). As expected, Max-specified full-face and partial expressions of interest, joy, sadness, and anger were morphologically stable between the 2 ages. Studies 1 and 2 confirmed predicted differential responding to mother sadness and anger expressions and to composite positive and negative conditions. Discrete negative expressions exceeded negative blends, and the amount of both expression types remained stable across ages. Studies 3 and 4 provided varying degrees of support for the social validity of Max-specified infant negative affect expressions. Conclusions include revisions and clarifications of DET. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Coupling GIS with Hydrologic and Hydraulic Flood Modelling

Geographic Information Systems (GIS) have been recognised as a powerful means to integrate and analyse data from various sources in the context of comprehensive floodplain management. As part of this comprehensive approach to floodplain management, it is very important to be able to predict the consequences of different scenarios in terms of flooded areas and associated risk. Hydrologic and hydraulic modelling plays a crucial role and there is much to gain in incorporating these modelling capabilities in GIS. This is still a rather complex task and research is being done on the full integration of these models. Interfacing between these models and GIS may be a very efficient way of overcoming the difficulties and getting very good results in terms of engineering practice. This paper presents results based on the use of Intergraph GIS coupled with Idrisi GIS. Using these two systems substantially increased the flexibility of using GIS as a tool for flood studies. A lumped (XSRAIN) and a distributed (OMEGA) hydrologic models were used to simulate flood hydrographs. The well known HEC-2 Hydraulic model was used to compute flooded areas. These models were applied in the Livramento catchment with very good results. The computation of flooded areas for different flood scenarios, and its representation in GIS, can be used in the assessment of affected property and associated damages. This is a very useful GIS-based approach to floodplain management.     

Differential contribution of dorsal and ventral medial prefrontal cortex to the acquisition and extinction of conditioned fear in rats.

The emotional reactivity of rats with lesions of the dorsal portion of medial prefrontal cortex (mPFC) was examined using a classical fear conditioning paradigm. Conditioned fear behavior (freezing responses) was measured during both the acquisition and extinction phases of the task. Lesions enhanced fear reactivity to both the conditioned stimulus (CS) and contextual stimuli during both phases, suggesting that dorsal mPFC lesions produce a general increase in fear reactivity in response to fear conditioning. M. A. Morgan, L. M. Romanski, and J. E. LeDoux (1993) found that lesions just ventral to the present lesions had no effect during acquisition of the same task and prolonged the fear response to the CS (but not the context) during extinction. Thus, both dorsal and ventral regions of mPFC are involved in the fear system, but each modulates different aspects of fear responsivity. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Quantitative methods for scoring cell migration and invasion in filter-based assays

The ability of cells to traverse pores in a biocompatible filter provides means for examining cell chemoattraction. Filter-based assays also permit rapid, quantitative assessment of the in vitro migratory and invasive potential of tumor cells. Scoring migration has relied on visual counting of stained cells which appear on the underside of the filter and determining a true percentage score involves arduous counting of cells on both filter surfaces. Visual counting of random fields may be unreliable, and counting all fields is laborious. In the present study we developed and compared two alternative methods for scoring cell numbers in filter-based assays, a colorimetric assay of toluidine blue binding, and a radioassay of cells prelabeled with [3H]thymidine. Each method was evaluated for sensitivity, variability, ease of use and efficiency, and suitability for use in assays of cell migration and invasion. The radiolabeling method proved to be sensitive and reliable and was the most efficient technique. Although less sensitive and specific, the colorimetric dye method offered a rapid and reliable, nonradioactive alternative with the distinct advantage of preserving intact cultures for follow-up visual assessments. We conclude that colorimetric and radiolabel scoring of filter-based assays are reliable and efficient semiautomated methods which provide means to obtain more complete assessments of cell migration and invasion.     

Medium and substitution pattern effects on the action of hydroxyflavones as photoprotectors against singlet molecular oxygen-mediated photooxidation of fats

The ability of mono-, di-, tri-and tetra-hydroxyflavones (7-and 3-hy-droxyflavones, 7, 8-dihydroxyflavone, baicalein and fisetin) to act as photoprotectors against singlet molecular oxygen [O²(Δ_g)]-initiated photooxidation of fats has been established by a kinetic study. The overall quenching rate constants for a series of five hydroxyflavones perfectly parallel their respective behaviour as inhibitors of the sensitized photooxidation of linoleic acid. The best antioxidative effect was exerted by 7-hydroxyflavone which does not chemically react with O²(¹Δ_g). Nevertheless for the remaining flavonoids of the series, the physical deactivation of O²(¹Δ_g) largely prevails over the chemical process. As for the cases of phenols and related hydroxy-aromatic derivatives, the ionization of the -OH group in the flavones, dramatically accelerates the rate of photooxidation. Under these conditions, the 7-hydroxyflavone also reacts effectively with O²(¹Δ_g). Given that flavonoids are natural oil components, this medium effect should be taken into account during the oil-refining process, in order to avoid the flavonoid photodestruction.     

Molecular dynamics simulations of polyphosphazenes: poly[bis(chloro)phosphazene][NPCl2] n

Suitable parameter sets for the CHARMm force field were derived for the structural units in polychlorophosphazene [P=N, P N, P Cl] using the Dinur Hagler energy second derivative procedure based on quantum mechanical SCI calculations using the 6–31G^* basis set. To validate the reliability of the parameter set, structural results obtained with CHARMm for the adopted model compounds (OP₂NCl₅ and OP₃N₂Cl₅) were compared with those derived fromab initio quantum mechanics using the 6–31G^* basis set. Application of molecular dynamics (MD) simulations in combinatioin with the available X-ray diffraction data provided structural and conformational information on the polymer. The calculation made using the periodic boundary conditions (PBC) agree well with the polychlorophosphazene ordered in a monoclinic unit cell (a=5.98,b=12.99,c=4.92 A; β=111.7). This model was stabilized mainly by the image atoms contribution to the electrostatic energy term and had aquasi-planar conformation of the backbone chain (glide symmetry). The MD calculations also provided evidence that the difference between single and double PN bonds is less marked than that measured experimentally. This result is, however, in agreement with more recent and accurate X-ray studies on poly(methylphosphazene). Validation of the polymer model provided a complete picture, otherwise experimentally inaccessible, of the internal fluctuations of the polymeric chains.