Comparative Electrochemical Study of Unsubstituted and Substituted Bis(phthalocyaninato) Rare Earth(III) Complexes

The electrochemistry of homoleptic substituted phthalocyaninato rare earth double-decker complexes M(TBPc)2 and M(OOPc)2 [M = Y, La...Lu except Pm; H2TBPc = 3(4),12(13),21(22),30(31)-tetra-tert-butylphthalocyanine, H2OOPc = 3,4,12,13,21,22,30,31-octakis(octyloxy)phthalocyanine] has been comparatively studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in CH2Cl2 containing 0.1 M tetra-n-butylammonium perchlorate (TBAP). Two quasi-reversible one-electron oxidations and three or four quasi-reversible one-electron reductions have been revealed for these neutral double-deckers of two series of substituted complexes, respectively. For comparison, unsubstituted bis(phthalocyaninato) rare earth analogues M(Pc)2 (M = Y, La...Lu except Pm; H2Pc = phthalocyanine) have also been electrochemically investigated. Two quasi-reversible one-electron oxidations and up to five quasi-reversible one-electron reductions have been revealed for these neutral double-decker compounds. The three bis(phthalocyaninato)cerium compounds display one cerium-centered redox wave between the first ligand-based oxidation and reduction. The half-wave potentials of the first and second oxidations and first reduction for double-deckers of the tervalent rare earths depend on the size of the metal center. The difference between the redox potentials of the second and third reductions for MIII(Pc)2, which represents the potential difference between the first oxidation and first reduction of [MIII(Pc)2]−, lies in the range 1.08−1.37 V and also gradually diminishes along with the lanthanide contraction, indicating enhanced π−π interactions in the double-deckers connected by the smaller, lanthanides. This corresponds well with the red-shift of the lowest energy band observed in the electronic absorption spectra of reduced double-decker [MIII(Pc′)2]− (Pc′ = Pc, TBPc, OOPc).

National numeracy tests : a graphic tells a thousand words

Mandatory numeracy tests have become commonplace in many countries, heralding a new era in school assessment. New forms of accountability and an increased emphasis on national and international standards (and benchmarks) have the potential to reshape mathematics curricula. It is noteworthy that the mathematics items used in these tests are rich in graphics. Many of the items, for example, require students to have an understanding of information graphics (e.g., maps, charts and graphs) in order to solve the tasks. This investigation classifies mathematics items in Australia’s inaugural national numeracy tests and considers the effect such standardised testing will have on practice. It is argued that the design of mathematics items are more likely to be a reliable indication of student performance if graphical, linguistic and contextual components are considered both in isolation and in integrated ways as essential elements of task design.

Tests of the elaborated intrusion theory of craving and desire : features of alcohol craving during treatment for an alcohol disorder

Objectives. We tested predictions from the elaborated intrusion (EI) theory of desire, which distinguishes intrusive thoughts and elaborations, and emphasizes the importance of imagery. Secondarily, we undertook preliminary evaluations of the Alcohol Craving Experience (ACE) questionnaire, a new measure based on EI Theory. Methods. Participants (N ¼ 232) were in correspondence-based treatment trials for alcohol abuse or dependence. The study used retrospective reports obtained early in treatment using the ACE, and daily self-monitoring of urges, craving, mood and alcohol consumption. Results. The ACE displayed high internal consistency and test – retest reliability and sound relationships with self-monitored craving, and was related to Baseline alcohol dependence, but not to consumption. Imagery during craving was experienced by 81%,with 2.3 senses involved on average. More frequent imagery was associated with longer episode durations and stronger craving. Transient intrusive thoughts were reported by 87% of respondents, and were more common if they frequently attempted to stop alcohol cognitions. Associations between average daily craving and weekly consumption were seen. Depression and negative mood were associated with more frequent, stronger and longer lasting desires for alcohol. Conclusions. Results supported the distinction of automatic and controlled processes in craving, together with the importance of craving imagery. They were also consistent with prediction of consumption from cross-situational averages of craving, and with positive associations between craving and negative mood. However, this study’s retrospective reporting and correlational design require that its results be interpreted cautiously. Research using ecological momentary measures and laboratory manipulations is needed before confident inferences about causality can be made.

Dopamine and visually regulated eye growth in chick

Retinal image properties such as contrast and spatial frequency play important roles in the development of normal vision. For example, visual environments comprised solely of low contrast and/or low spatial frequencies induce myopia. The visual image is processed by the retina and it then locally controls eye growth. In terms of the retinal neurotransmitters that link visual stimuli to eye growth, there is strong evidence to suggest involvement of the retinal dopamine (DA) system. For example, effectively increasing retinal DA levels by using DA agonists can suppress the development of form-deprivation myopia (FDM). However, whether visual feedback controls eye growth by modulating retinal DA release, and/or some other factors, is still being elucidated. This thesis is chiefly concerned with the relationship between the dopaminergic system and retinal image properties in eye growth control. More specifically, whether the amount of retinal DA release reduces as the complexity of the image degrades was determined. For example, we investigated whether the level of retinal DA release decreased as image contrast decreased. In addition, the effects of spatial frequency, spatial energy distribution slope, and spatial phase on retinal DA release and eye growth were examined. When chicks were 8-days-old, a cone-lens imaging system was applied monocularly (+30 D, 3.3 cm cone). A short-term treatment period (6 hr) and a longer-term treatment period (4.5 days) were used. The short-term treatment tests for the acute reduction in DA release by the visual stimulus, as is seen with diffusers and lenses, whereas the 4.5 day point tests for reduction in DA release after more prolonged exposure to the visual stimulus. In the contrast study, 1.35 cyc/deg square wave grating targets of 95%, 67%, 45%, 12% or 4.2% contrast were used. Blank (0% contrast) targets were included for comparison. In the spatial frequency study, both sine and square wave grating targets with either 0.017 cyc/deg and 0.13 cyc/deg fundamental spatial frequencies and 95% contrast were used. In the spectral slope study, 30% root-mean-squared (RMS) contrast fractal noise targets with spectral fall-off of 1/f0.5, 1/f and 1/f2 were used. In the spatial alignment study, a structured Maltese cross (MX) target, a structured circular patterned (C) target and the scrambled versions of these two targets (SMX and SC) were used. Each treatment group comprised 6 chicks for ocular biometry (refraction and ocular dimension measurement) and 4 for analysis of retinal DA release. Vitreal dihydroxyphenylacetic acid (DOPAC) was analysed through ion-paired reversed phase high performance liquid chromatography with electrochemical detection (HPLC-ED), as a measure of retinal DA release. For the comparison between retinal DA release and eye growth, large reductions in retinal DA release possibly due to the decreased light level inside the cone-lens imaging system were observed across all treated eyes while only those exposed to low contrast, low spatial frequency sine wave grating, 1/f2, C and SC targets had myopic shifts in refraction. Amongst these treatment groups, no acute effect was observed and longer-term effects were only found in the low contrast and 1/f2 groups. These findings suggest that retinal DA release does not causally link visual stimuli properties to eye growth, and these target induced changes in refractive development are not dependent on the level of retinal DA release. Retinal dopaminergic cells might be affected indirectly via other retinal cells that immediately respond to changes in the image contrast of the retinal image.

EPR, UV-visible and near infrared spectroscopic characterization of dolomite

Dolomite mineral samples having white and light green colours of Indian origin have been characterized by EPR, optical and NIR spectroscopy. The optical spectrum exhibits a number of electronic bands due to presence of Fe(III) ions in the mineral. From EPR studies, the parameters of g for Fe(III) and g, A and D for Mn(II) are evaluated and the data confirm that the ions are in distorted octahedron. Optical absorption studies reveal that Fe(III) is in distorted octahedron. The bands in NIR spectra are due to the overtones and combinations of water molecules. Thus EPR and optical absorption spectral studies have proven useful for the study of the chemistry of dolomite.

Optical absorption and EPR studies on tenorite mineral

Optical absorption and EPR studies of the mineral tenorite, a cupric oxide, which originated from Mexico and contains 54.40 wt% of CuO. EPR spectral results indicate two Cu(II) closely interacting ions to give a d2 type structure. The calculated spin Hamiltonian at Rt and LNT are g = 2.160 and D = 125 G . The intensity of resonance line is not the same in low and high field regions. The optical absorption spectrum is due to Cu(II) which three sets of energies indicating Cu(II) in two independent tetragonal C4v symmetry, in addition to d2 structure of octahedral coordination. The octahedral and tetragonal field parameters are compared with those reported for several other copper containing minerals.

Distortional buckling tests of cold-formed steel compression members at elevated temperatures

In recent times, light gauge cold-formed steel sections have been used extensively since they have a very high strength to weight ratio compared with thicker hot-rolled steel sections. However, they are susceptible to various buckling modes including a distortional mode and hence show complex behaviour under fire conditions. Therefore a research project based on detailed experimental studies was undertaken to investigate the distortional buckling behaviour of light gauge cold-formed steel compression members under simulated fire conditions. More than 150 axial compression tests were undertaken at uniform ambient and elevated temperatures. Two types of cross sections were selected with nominal thicknesses of 0.60, 0.80, and 0.95 mm. Both low (G250) and high (G550) strength steels were used. Distortional buckling tests were conducted at six different temperatures in the range of 20 to 800°C. The ultimate loads of compression members subject to distortional buckling were then used to review the adequacy of the current design rules at ambient and elevated temperatures. This paper presents the details of this experimental study and the results.