Adsorption thermodynamics and kinetics study for the self-assembly of 1,8,15,22-tetraaminophthalocyanatocobalt(II) on glassy carbon surface

Spontaneous adsorption of 1,8,15,22-tetraaminophthalocyanatocobalt(II) (4α-CoIITAPc) on glassy carbon (GC) electrode leads to the formation of a stable self-assembled monolayer (SAM). Since the SAM of 4α-CoIITAPc is redox active, its adsorption on GC electrode was followed by cyclic voltammetry. SAM of 4α-CoIITAPc on GC electrode shows two pairs of well-defined redox peaks corresponding to CoIII/CoII and CoIIIPc−1/CoIIIPc−2. The surface coverage (Γ) value, calculated by integrating the charge under CoII oxidation, was used to study the adsorption thermodynamics and kinetics of 4α-CoIITAPc on GC surface. Cyclic voltammetric studies show that the adsorption of 4α-CoIITAPc on GC electrode has reached the saturation coverage (Γs) within 3 h. The Γs value for the SAM of 4α-CoIITAPc on GC electrode was found to be 2.37 × 10−10 mol cm−2. Gibbs free energy (ΔGads) and adsorption rate constant (kad) for the adsorption of 4α-CoIITAPc on GC surface were found to be −16.76 kJ mol−1 and 7.1 M−1 s−1, respectively. The possible mechanism for the self-assembly of 4α-CoIITAPc on GC surface is through the addition of nucleophilic amines to the olefinic bond on the GC surface in addition to a meager contribution from π stacking. The contribution of π stacking was confirmed from the adsorption of unsubstituted phthalocyanatocobalt(II) (CoPc) on GC electrode. Raman spectra for the SAM of 4α-CoIITAPc on carbon surface shows strong stretching and breathing bands of Pc macrocycle, pyrrole ring and isoindole ring. Raman and CV studies suggest that 4α-CoIITAPc is adopting nearly a flat orientation or little bit tilted orientation.

Electrochemical and spectral studies of self-assembled monolayer of 1,8,15,22-tetraaminophthalocyanatocobalt(II) on indium tin oxide surface

Self-assembled monolayer (SAM) of 1,8,15,22-tetraaminophthalocyanatocobalt(II) (4α-CoIITAPc) was prepared on indium tin oxide (ITO) electrode by spontaneous adsorption from dimethylformamide (DMF) solution containing 4α-CoIITAPc. The SAM of 4α-CoIITAPc formed on ITO electrode was characterized by cyclic voltammetry, Raman and UV–visible spectroscopic techniques. The cyclic voltammogram (CV) of 4α-CoIITAPc SAM shows two pairs of well-defined redox peaks corresponding to CoIII/CoII and CoIIIPc−1/CoIIIPc−2. The surface coverage (Γ) was calculated by integrating the charge under the anodic wave corresponding to CoII oxidation and it was found to be 2.25 × 10−10 mol cm−2. Raman spectrum obtained for the SAM of 4α-CoIITAPc on ITO surface shows strong stretching and breathing bands of Pc macrocycle, pyrrole ring and isoindole ring. Further, the –NH2 bending mode of vibration was absent for the SAM of 4α-CoIITAPc on ITO surface which indirectly confirmed that all the amino groups of 4α-CoIITAPc are involved in bonding with ITO surface. UV–visible spectrum for the SAM of 4α-CoIITAPc on ITO surface shows an intense B-band, Q-band and n–π∗ transition with slight broadening when compared to that of 4α-CoIITAPc in DMF.

Selective electrochemical epinephrine sensor using self-assembled monomolecular film of 1,8,15,22-tetraaminophthalocyanatonickel(II) on gold electrode

This article describes the highly sensitive and selective determination of epinephrine (EP) using self-assembled monomolecular film (SAMF) of 1,8,15,22-tetraamino-phthalocyanatonickel(II) (4α-NiIITAPc) on Au electrode. The 4α-NiIITAPc SAMF modified electrode was prepared by spontaneous adsorption of 4α-NiIITAPc from dimethylformamide solution. The modified electrode oxidizes EP at less over potential with enhanced current response in contrast to the bare Au electrode. The standard heterogeneous rate constant (k°) for the oxidation of EP at 4α-NiIITAPc SAMF modified electrode was found to be 1.94×10−2 cm s−1 which was much higher than that at the bare Au electrode. Further, it was found that 4α-NiIITAPc SAMF modified electrode separates the voltammetric signals of ascorbic acid (AA) and EP with a peak separation of 250 mV. Using amperometric method the lowest detection limit of 50 nM of EP was achieved at SAMF modified electrode. Simultaneous amperometric determination of AA and EP was also achieved at the SAMF modified electrode. Common physiological interferents such as uric acid, glucose, urea and NaCl do not interfere within the potential window of EP oxidation. The present 4α-NiIITAPc SAMF modified electrode was also successfully applied to determine the concentration of EP in commercially available injection.

Facile dearomatisation of porphyrins using palladium-catalysed hydrazination: the 5,15-diiminoporphodimethenes and their redox products

The synthesis, electronic absorption and 1H NMR spectra of a suite of novel porphyrinoids derived from meso-bromoporphyrins by palladium-catalysed aminations using ethyl and tert-butylcarbazates are reported. Instead of the expected carbazate-substituted porphyrins, a facile oxidative dearomatisation of the porphyrin ring occurs in high yield, especially for the nickel(II) complexes, resulting in high yields of 5,15-diiminoporphodimethenes (DIPDs). The analogous zinc(II) and free base DIPDs were also characterised, the former by X-ray crystallography. The oxidation and reduction reactions of DIPDs and their precursor carbazate porphyrins were studied. Density Functional Theory (DFT) was used to calculate the optimised geometries and frontier molecular orbitals of DIPD Ni8c and bis(azocarboxylate) 19c, and Time Dependent DFT calculations allowed the prediction of electronic absorption spectra, whose characteristics corresponded well with those of the observed solution spectra. In the latter case, the calculated low-energy absorptions were unlike those of a typical porphyrin, due to the near-degeneracy of the highest filled frontier orbitals, and the wide energy separation between the unfilled orbitals. This feature was present in the observed spectrum.

Basic personal values underlie and give coherence to political values: A cross national study in 15 countries

Do the political values of the general public form a coherent system? What might be the source of coherence? We view political values as expressions, in the political domain, of more basic personal values. Basic personal values (e.g., security, achievement, benevolence, hedonism) are organized on a circular continuum that reflects their conflicting and compatible motivations. We theorize that this circular motivational structure also gives coherence to political values. We assess this theorizing with data from 15 countries, using eight core political values (e.g., free enterprise, law and order) and ten basic personal values. We specify the underlying basic values expected to promote or oppose each political value. We offer different hypotheses for the 12 non-communist and three post-communist countries studied, where the political context suggests different meanings of a basic or political value. Correlation and regression analyses support almost all hypotheses. Moreover, basic values account for substantially more variance in political values than age, gender, education, and income. Multidimensional scaling analyses demonstrate graphically how the circular motivational continuum of basic personal values structures relations among core political values. This study strengthens the assumption that individual differences in basic personal values play a critical role in political thought.

Information Security and Privacy : Proceedings of the 9th Australasian Conference, ACISP 2004, Sydney, Australia, July 13-15, 2004.

Preface The 9th Australasian Conference on Information Security and Privacy (ACISP 2004) was held in Sydney, 13–15 July, 2004. The conference was sponsored by the Centre for Advanced Computing – Algorithms and Cryptography (ACAC), Information and Networked Security Systems Research (INSS), Macquarie University and the Australian Computer Society. The aims of the conference are to bring together researchers and practitioners working in areas of information security and privacy from universities, industry and government sectors. The conference program covered a range of aspects including cryptography, cryptanalysis, systems and network security. The program committee accepted 41 papers from 195 submissions. The reviewing process took six weeks and each paper was carefully evaluated by at least three members of the program committee. We appreciate the hard work of the members of the program committee and external referees who gave many hours of their valuable time. Of the accepted papers, there were nine from Korea, six from Australia, five each from Japan and the USA, three each from China and Singapore, two each from Canada and Switzerland, and one each from Belgium, France, Germany, Taiwan, The Netherlands and the UK. All the authors, whether or not their papers were accepted, made valued contributions to the conference. In addition to the contributed papers, Dr Arjen Lenstra gave an invited talk, entitled Likely and Unlikely Progress in Factoring. This year the program committee introduced the Best Student Paper Award. The winner of the prize for the Best Student Paper was Yan-Cheng Chang from Harvard University for his paper Single Database Private Information Retrieval with Logarithmic Communication. We would like to thank all the people involved in organizing this conference. In particular we would like to thank members of the organizing committee for their time and efforts, Andrina Brennan, Vijayakrishnan Pasupathinathan, Hartono Kurnio, Cecily Lenton, and members from ACAC and INSS.

Stand-out progress from our corporate first-movers

In May, the National Business Leaders Forum on Sustainable Development meets for the 10th time. More than ever business leadership is needed to help us all address the challenges around climate change, water availability and species loss. Here’s a quick look at some committed corporate stars...

Genomewide screens in ankylosing spondylitis

Efforts to identify genes other than HLA-B27 in AS have been driven by the strength of the evidence from genetic epidemiology studies indicating that HLA-B27, although a major gene in AS, is clearly not the only significant gene operating. This is the case for both genetic determinants of disease-susceptibility and phenotypic characteristics such as disease severity and associated disease features. In this chapter the genetic epidemiology of AS and the gene-mapping studies performed to date will be reviewed and the future direction of research in this field discussed.

Identification of 15 new psoriasis susceptibility loci highlights the role of innate immunity

To gain further insight into the genetic architecture of psoriasis, we conducted a meta-analysis of 3 genome-wide association studies (GWAS) and 2 independent data sets genotyped on the Immunochip, including 10,588 cases and 22,806 controls. We identified 15 new susceptibility loci, increasing to 36 the number associated with psoriasis in European individuals. We also identified, using conditional analyses, five independent signals within previously known loci. The newly identified loci shared with other autoimmune diseases include candidate genes with roles in regulating T-cell function (such as RUNX3, TAGAP and STAT3). Notably, they included candidate genes whose products are involved in innate host defense, including interferon-mediated antiviral responses (DDX58), macrophage activation (ZC3H12C) and nuclear factor (NF)-κB signaling (CARD14 and CARM1). These results portend a better understanding of shared and distinctive genetic determinants of immune-mediated inflammatory disorders and emphasize the importance of the skin in innate and acquired host defense. © 2012 Nature America, Inc. All rights reserved.

Growth hormone resistance and somatomedins in children with end-stage liver disease awaiting transplantation

Background: The success of orthotopic liver transplantation as treatment for end-stage liver disease has prompted investigation of strategies to maintain or improve nutrition and growth in children awaiting transplantation, because malnutrition is an adverse prognostic factor. The purpose of this study was to evaluate the effect of recombinant human growth hormone therapy on body composition and indices of liver function in patients awaiting transplant. Methods: The study was designed as a placebo- controlled, double-blind, crossover trial. Patients received 0.2 U/kg growth hormone, subcutaneously, or placebo daily for 28 days during two treatment periods, separated by a 2-week washout period. Ten patients (mean age, 3.06 ± 1.15 years; range, 0.51-11.65 years, five men), with extrahepatic biliary atresia (n = 8) or two with Alagille's syndrome (n = 2), with end-stage liver disease, completed the trial while awaiting orthotopic liver transplantation. Height, weight, total body potassium, total body fat, resting energy expenditure, respiratory quotient, hematologic and multiple biochemical profile, number of albumin infusions, insulin-like growth factor-1 and 1, growth hormone binding protein (GHBP), and insulin-like growth factor binding protein-1 (IGFBP-1) and insulin-like growth factor binding protein (IGFBP-3) were measured at the beginning and end of each treatment period. Results: Growth hormone treatment was associated with a significant decline in serum bilirubin (-34.6 ± 16.5 μmol/l vs. 18.2 ± 11.59 μmol/l; p < 0.02) but there was no significant effect on any anthropometric or body composition measurements, or on any biochemical or hematologic parameters. Conclusions: These children with end-stage liver disease displayed growth hormone resistance, particularly in relation to the somatomedin axis. Exogenous growth hormone administration may be of limited value in these patients

Electronic Properties of the Vortex State in Cuprate Superconductors

The superconducting state of the cuprates in the presence of a magnetic field has been investigated very actively in the past few years through measurements of electrical and thermal transport, ac conductivity, specific heat, and other quantities. The observed behavior is not well understood; it probes the nature of quasiparticies, vortices, and their interactions in a superconductor with nodes in the pair amplitude. We summarize here experimental results and our attempts to understand the phenomena.

Electronic Structure of Vacancy Ordered Spinels, $GaMo_{4}S_{8}$ and $GaV_{4}S_{8}$, from ab Initio Calculations

We report ab initio calculations for the band dispersions and total as well as partial densities of states for vacancy ordered, clustered spinels, GaMo4S8 and GaV4S8. Results are presented for the high temperature cubic phase for both compounds. Additionally, we discuss results of similar calculations for GaMo4S8 in an idealized cubic structure, as well as the nonmagnetic and the ferromagnetic states of the low temperature rhombohedral structure. Comparison of these results allows us to discuss the unusual aspects of the electronic structure of this interesting class of compounds, and provide estimates of the crystal-field and exchange splitting strengths.

In search of inorganic nonlinear optical materials for second harmonic generation

In a search for inorganic oxide materials showing second-order nonlinear optical (NLO) susceptibility, we investigated several berates, silicates, and a phosphate containing trans-connected MO6, octahedral chains or MO5 square pyramids, where, M = d(0): Ti(IV), Nb(V), or Ta(V), Our investigations identified two new NLO structures: batisite, Na2Ba(TiO)(2)Si4O12, containing trans-connected TiO5 octahedral chains, and fresnoite, Ba2TiOSi2O7, containing square-pyramidal TiO5. Investigation of two other materials containing square-pyramidal TiO5 viz,, Cs2TiOP2O7 and Na4Ti2Si8O22. 4H(2)O, revealed that isolated TiO5, square pyramids alone do not cause a second harmonic generation (SHG) response; rather, the orientation of TiO5 units to produce -Ti-O-Ti-O- chains with alternating long and short Ti-O distances in the fresnoite structure is most likely the origin of a strong SHG response in fresnoite,

Social media in selected Australian federal and state election campaigns, 2010-15

Campaigning in Australian election campaigns at local, state, and federal levels is fundamentally affected by the fact that voting is compulsory in Australia, with citizens who are found to have failed to cast their vote subject to fines. This means that - contrary to the situation in most other nations – elections are decided not by which candidate or party has managed to encourage the largest number of nominal supporters to make the effort to cast their vote, but by some 10-20% of genuine ‘swinging voters’ who change their party preferences from one election to the next. Political campaigning is thus aimed less at existing party supporters (so-called ‘rusted on’ voters whose continued support for the party is essentially taken for granted) than at this genuinely undecided middle of the electorate. Over the past decades, this has resulted in a comparatively timid, vague campaigning style from both major party blocs (the progressive Australian Labor Party [ALP] and the conservative Coalition of the Liberal and National Parties [L/NP]). Election commitments that run the risk of being seen as too partisan and ideological are avoided as they could scare away swinging voters, and recent elections have been fought as much (or more) on the basis of party leaders’ perceived personas as they have on stated policies, even though Australia uses a parliamentary system in which the Prime Minister and state Premiers are elected by their party room rather than directly by voters. At the same time, this perceived lack of distinctiveness in policies between the major parties has also enabled the emergence of new, smaller parties which (under Australia’s Westminster-derived political system) have no hope of gaining a parliamentary majority but could, in a close election, come to hold the balance of power and thus exert disproportionate influence on a government which relies on their support.