The role of oxygen in the interaction of emeraldine base polyaniline with Cu(II) or Fe(III) ions in NMP solution

The influence of molecular oxygen in the interactions of emeraldine base form of polyaniline (EB-PANI) with Fe(III) or Cu(II) ions in 1-methyl-2-pyrrolidinone (NMP) solutions has been investigated by UV-vis-NIR, resonance Raman and electron paramagnetic resonance (EPR) spectroscopies. Through the set of spectroscopic results it was possible to rationalize the role Of O(2) and to construct a scheme of preferential routes occurring in the interaction of EB-PANI with Fe(III) or Cu(II). Solutions of 4.0 mmol L(-1) EB-PANI with 0.8, 2.0 and 20 mmol L(-1) Fe(III) or Cu(II) ions in NMP were investigated and the main observed reactions were EB-PANI oxidation to pernigraniline (PB-PANI) and EB-PANI doping process by pseudo-protonation, or by a two-step redox process. In the presence Of O(2), PB-PANI is observed in all Fe(III)/EB solutions and EB-PANI doping only occurs in solutions with high Fe(III) concentrations through pseudo-protonation. On the other hand, emeraldine salt (ES-PANI) is formed in all Fe(III)/EB solutions under N(2) atmosphere and, in this case, doping occurs both by the pseudo-protonation and two-step redox mechanisms. In all Cu(II)/EB solutions PB-PANI is formed both in the presence and absence of O(2), and only for solutions with high Cu(II) concentrations doping process occurs in a very low degree. The most important result from EPR spectra was providing evidence for redox steps. The determined Cu(II) signal areas under oxygen are higher than under N(2) and, further. the initial metal proportions (1:2:20) are maintained in these spectra, indicating that Cu(I) formed are re-oxidized by O(2) and. so, Cu(II) ions are being recycled. Consistently, for the solutions prepared under nitrogen, the corresponding areas and proportions in the spectra are much lower, confirming that a partial reduction of Cu(II) ions actually occurs. (C) 2009 Elsevier B.V. All rights reserved.

Generalized pseudo-likelihood estimates for markov random fields on lattice

In this paper we generalize Besag's pseudo-likelihood function for spatial statistical models on a region of a lattice. The correspondingly defined maximum generalized pseudo-likelihood estimates (MGPLEs) are natural extensions of Besag's maximum pseudo-likelihood estimate (MPLE). The MGPLEs connect the MPLE and the maximum likelihood estimate. We carry out experimental calculations of the MGPLEs for spatial processes on the lattice. These simulation results clearly show better performances of the MGPLEs than the MPLE, and the performances of differently defined MGPLEs are compared. These are also illustrated by the application to two real data sets.

Therapeutic Discourse and the American Public Philosophy: On American Liberalism's Troubled Relationship with Psychology

I explore the main currents of postwar American liberalism. One, sociological, emerged in response to the danger of mass movements. Articulated primarily by political sociologists and psychologists and ascendant from the mid-fifties till the mid-seventies, it heralded the "end of ideology." It emphasized stability, elitism, positive science and pluralism; it recast normatively sound politics as logrolling and hard bargaining. I argue that these normative features, attractive when considered in isolation, taken together led to a vicious ad hominem style in accounting for views outside the postwar consensus. It used pseudo-scientific literature in labeling populists, Progressives, Taft conservatives, Goldwaterites, the New Left and others "pathological," viz. mentally ill. Hence, "therapeutic discourse." I argue that philosophical liberalism, which reasserts the role of political theory in working out norms and adjudicating disagreement, is a more profitable way of thinking about and defending from critics liberalism. I take the philosopher John Rawls as the tradition's modern representative. This inquiry is important because the themes of sociological liberalism are making a comeback in American public discourse, and with them perhaps the baggage of therapeutic discourse. I present a cautionary tale.

The effects of clustered data on standard error estimates in covariance structure analysis : a field data application

Purpose – The purpose of this article is to present an empirical analysis of complex sample data with regard to the biasing effect of non-independence of observations on standard error parameter estimates. Using field data structured in the form of repeated measurements it is to be shown, in a two-factor confirmatory factor analysis model, how the bias in SE can be derived when the non-independence is ignored.

Design/methodology/approach – Three estimation procedures are compared: normal asymptotic theory (maximum likelihood); non-parametric standard error estimation (naïve bootstrap); and sandwich (robust covariance matrix) estimation (pseudo-maximum likelihood).

Findings – The study reveals that, when using either normal asymptotic theory or non-parametric standard error estimation, the SE bias produced by the non-independence of observations can be noteworthy.

Research limitations/implications – Considering the methodological constraints in employing field data, the three analyses examined must be interpreted independently and as a result taxonomic generalisations are limited. However, the study still provides “case study” evidence suggesting the existence of the relationship between non-independence of observations and standard error bias estimates.

Originality/value – Given the increasing popularity of structural equation models in the social sciences and in particular in the marketing discipline, the paper provides a theoretical and practical insight into how to treat repeated measures and clustered data in general, adding to previous methodological research. Some conclusions and suggestions for researchers who make use of partial least squares modelling are also drawn.

Substrates and inhibitors of human multidrug resistance associated proteins and the implications in drug development

Human contains 49 ATP-binding cassette (ABC) transporter genes and the multidrug resistance associated proteins (MRP1/ABCC1, MRP2/ABCC2, MRP3/ABCC3, MRP4/ABCC4, MRP5/ABCC5, MRP6/ABCC6, MRP7/ABCC10, MRP8/ABCC11 and MRP9/ABCC12) belong to the ABCC family which contains 13 members. ABCC7 is cystic fibrosis transmembrane conductance regulator; ABCC8 and ABCC9 are the sulfonylurea receptors which constitute the ATP-sensing subunits of a complex potassium channel. MRP10/ABCC13 is clearly a pseudo-gene which encodes a truncated protein that is highly expressed in fetal human liver with the highest similarity to MRP2/ABCC2 but without transporting activity. These transporters are localized to the apical and/or basolateral membrane of the hepatocytes, enterocytes, renal proximal tubule cells and endothelial cells of the blood-brain barrier. MRP/ABCC members transport a structurally diverse array of important endogenous substances and xenobiotics and their metabolites (in particular conjugates) with different substrate specificity and transport kinetics. The human MRP/ABCC transporters except MRP9/ABCC12 are all able to transport organic anions, such as drugs conjugated to glutathione, sulphate or glucuronate. In addition, selected MRP/ABCC members may transport a variety of endogenous compounds, such as leukotriene C(4) (LTC(4) by MRP1/ABCC1), bilirubin glucuronides (MRP2/ABCC2, and MRP3/ABCC3), prostaglandins E1 and E2 (MRP4/ABCC4), cGMP (MRP4/ABCC4, MRP5/ABCC5, and MRP8/ABCC11), and several glucuronosyl-, or sulfatidyl steroids. In vitro, the MRP/ABCC transporters can collectively confer resistance to natural product anticancer drugs and their conjugated metabolites, platinum compounds, folate antimetabolites, nucleoside and nucleotide analogs, arsenical and antimonial oxyanions, peptide-based agents, and in concert with alterations in phase II conjugating or biosynthetic enzymes, classical alkylating agents, alkylating agents. Several MRP/ABCC members (MRPs 1-3) are associated with tumor resistance which is often caused by an increased efflux and decreased intracellular accumulation of natural product anticancer drugs and other anticancer agents. Drug targeting of these transporters to overcome MRP/ABCC-mediated multidrug resistance may play a role in cancer chemotherapy. Most MRP/ABCC transporters are subject to inhibition by a variety of compounds. Based on currently available preclinical and limited clinical data, it can be expected that modulation of MRP members may represent a useful approach in the management of anticancer and antimicrobial drug resistance and possibly of inflammatory diseases and other diseases. A better understanding of their substrates and inhibitors has important implications in development of drugs for treatment of cancer and inflammation.

The influence of geometry and wall character of pores on the permeation of ions and water through desalination membranes

The transport of water and ions across mimicked nanotube membranes with pseudo atoms is studied using molecular dynamics simulations under equilibrium conditions and hydrostatic pressure. Different pore surface properties are constructed by assigning partial charges on the sites of specified atoms to explore the influence of charges and polarity. The energetics of water and ion transports through the nanopores was calculated to evaluate their filterability to water. The simulation results show that the free energy barriers to water and ion conductions much depend on the charges at the pore entrance and the dipole within the pore. The membranes with hydrophobic pores and negatively charged entrances would be very efficient in the water transport and ion rejection. The charges and dipoles of the pore wall and the aligned dipoles of water molecules in the pore can create a significant force on ions.

Approaches to the synthesis of peptide substituted frameworks

The 1,3 dipolar cycloaddition between carbonyl ylids (generated from cyclobutene epoxides flanked by esters) and norbornyl alkenes – the ACE reaction – offers a facile method for the construction of polynorbornyl molecular frameworks. This reaction has, as described in this dissertation, underpinned the construction of molecular frameworks that have peptides and amino acids attached. Such highly rigid peptide-frameworks are of use in the field of peptidomimetics; the template molecule governs the final positioning of any attached groups such that a precise arrangement of amino acids can be achieved without the need to construct entire proteins. In the course of any ACE reaction the ester flanked cyclobutene epoxide is transformed to a 1,3 dipole, the esters serve to stablise this reactive intermediate and are as a consequence incorporated in the reaction product. Modification of these esters provides pseudo-equatorial points for peptide attachment. These methyl esters were replaced with tert-butyl esters to provide pseudo-axial attachment points that could be selectively addressed. The optimal strategy for peptide-framework construction involved direct condensation of carboxyl protected amino acids to bicyclo[2.2.1]hept-5-ene-2-endo-carboxylic acid as well as condensation of amino acids to cyclobutene epoxides derived from this acid. The ACE reaction of (±) bicycloheptene-2-endo-carboxylic acid derivatives with cyclobutene epoxides synthesised from such racemic acid derivatives provided a mixture of enantiomers and meso compounds. In order to control the position of the attachment points – and hence the final location of the attached peptides – the ACE reaction required chiral starting materials. Accordingly, all peptidoframeworks were derived from the chiral (2S)-(-)-bicycloheptene carboxylic acid. The ACE reaction of this (S)-norbornene with the (S)-epoxide provided a peptide framework in which the attached amino acids were positioned pseudo-axially. Deprotection of the amino acid allowed peptide chain building in the pseudo-axial direction. Using this strategy a framework with an alanine residue and a triglycine peptide was synthesised. By combining this strategy with the ter-butyl ester variant a framework with pseudo-axial alanine and pseudo-equatorial glycine residues was manufactured.

The star and celebrity confessional

In this book the different manifestations, meanings, and processes of the star and celebrity confessional will be explored.

The confessional is taken to be any moment in which a star, celebrity, or fan engages in revelatory acts that are considered to be authentic, heart-felt, and honest. These confessional encounters can take place in an interview, through performance and presentation events, online, and in ‘unscripted’ encounters. A star may break down in tears, or reveal a previously unknown truth about their private life. However, this authenticity is often found to have been manufactured, or is timed to occur against a new release or product launch. Alternatively, the desire to confess may be seen to draw attention to the centrality of pseudo forms of emotion in contemporary culture and the obsessional behaviour it produces. In this book authors consider acts of confession by celebrities such as Tom Cruise, Michael Jackson, Jade Goody, Britney Spears, Sarah Jessica Parker, Tracey Emin, and Russell Crowe.

Kinetic effects of halide ions on the morphological evolution of silver nanoplates

Time-resolved extinction spectroscopy is employed to study the reaction kinetics in the shape-conversion reaction involving halide ions (including Cl-, Br- and I-) etching (sculpturing) silver nanoplates. A series of time-resolved extinction spectra are obtained during the in situ etching process and the evolution of surface plasmon resonance (SPR) of the silver nanoparticles is analyzed. Spectral analysis indicates that the conversion of nanoprisms starts simultaneously with the emergence of nanodisks when the halide ions are added. The etching rate of different halide ions is evaluated through the in-plane dipole resonance peak intensity of silver nanoplates vs. the reaction time (dI/dt). The relationship between the etching rate and the halide ion concentration shows that the halide ion etching reaction can be considered as a pseudo-first-order reaction. The effect of different halide ions on the shape-conversion of silver nanoplates is compared in detail. The activation energy of the etching reaction is calculated, which indicates that the etching ability of different halide ions is on the order of Cl - < I- < Br-.

A new re-ranking method using enhanced pseudo-relevance feedback for content-based medical image retrieval

We propose a novel re-ranking method for content-based medical image retrieval based on the idea of pseudo-relevance feedback (PRF). Since the highest ranked images in original retrieval results are not always relevant, a naive PRF based re-ranking approach is not capable of producing a satisfactory result. We employ a two-step approach to address this issue. In step 1, a Pearson's correlation coefficient based similarity update method is used to re-rank the high ranked images. In step 2, after estimating a relevance probability for each of the highest ranked images, a fuzzy SVM ensemble based approach is adopted to re-rank the images. The experiments demonstrate that the proposed method outperforms two other re-ranking methods.

Why web-based pseudo relevance feedback systems fail

 We review pseudo-relevance feedback as a mechanism for expanding short texts. Where short texts exhibit evolving concepts, topics and other characteristics, Web-based feedback systems were touted as the most ideal way of enriching the feature space of short texts. However, we note from a recent implementation of a Web-based pseudo-relevance feedback that it would only perform well under clinical situations. Further improvements to address fundamental noise in Web documents did not show significant improvements leading us to conclude that relevance feedback using Web documents directly are unsuitable for real-world conditions. In this paper, we present Eddi, which is a recent system that provides an exemplar of a typical pseudo-relevance feedback system. We first show the conditions in which Eddi will work and then discuss the situations where it would fail. We then present the variations to Eddi from our attempt to improve the robustness of Eddi's algorithm when dealing with complex Web documents. We then present the results from all variations to show the lack of robustness for pseudo-relevance feedback with Web documents.

Comparisons of seismic rock slope stability assessments between the Hoek-Brown and Mohr-Coulomb failure criteria

Current investigations have shown that earthquakes can trigger significant damages of equipment, property infrastructure and environment. This is a persistent cause of economic loss for any country, especially for the loss of life. The conventional method for slope stability design is to utilize limit equilibrium method (LEM) in conjunction with the pseudo-static (PS) approach. However, the LEM has a significant drawback which is to determine the slip surface before factor of safety calculation. The numerical upper and lower bound limit analysis method employed in this paper can avoid this limitation. In this study, the presented slope stability evaluations considering earthquake effects based on the finite difference method will be discussed and compared with the results from the numerical limit analysis methods.

Photocatalytic degradation of phenanthrene on soil surfaces in the presence of nanometer anatase TiO2 under UV-light

The effect of nanometer anatase TiO2 was investigated on the photocatalytic degradation of phenanthrene on soil surfaces under a variety of conditions. After being spiked with phenanthrene, soil samples loaded with different amounts of TiO2 (0 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, and 4 wt.%) were exposed to UV-light irradiation for 25 hr. The results indicated that the photocatalytic degradation of phenanthrene followed the pseudo first-order kinetics. TiO2 significantly accelerated the degradation of phenanthrene with the half-life reduced from 45.90 to 31.36 hr for TiO2 loading of 0 wt.% and 4 wt.%, respectively. In addition, the effects of H2O2, light intensity and humic acid on the degradation of phenanthrene were investigated. The degradation of phenanthrene increased with the concentration of H2O2, light intensity and the concentration of humic acids. It has been demonstrated that the photocatalytic method in the presence of nanometer anatase TiO2 was a very promising technology for the treatments of soil polluted with organic substances in the future.

Invader impact clarifies the roles of top-down and bottom-up effects on tropical snake populations

Disentangling the effects of prey limitation (bottom-up) and predation (top-down) processes on natural populations is difficult, but the perturbations introduced by an invasive species can provide pseudo-experimental evidence on this issue.