Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes: Part 14. The infrared and Raman characteristics of phthalocyanine in “pinwheel-like” homoleptic bis[1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninato] rare earth(III) double-decker complexes

The infrared (IR) spectroscopic data and Raman spectroscopic properties for a series of 13 “pinwheel-like” homoleptic bis(phthalocyaninato) rare earth complexes M[Pc(α-OC5H11)4]2 [M = Y and Pr–Lu except Pm; H2Pc(α-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected and comparatively studied. Both the IR and Raman spectra for M[Pc(α-OC5H11)4]2 are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues, namely M(Pc)2 and M[Pc(OC8H17)8]2, but resemble (for IR) or are a bit more complicated (for Raman) than those of heteroleptic counterparts M(Pc)[Pc(α-OC5H11)4], revealing the decreased molecular symmetry of these double-decker compounds, namely S8. Except for the obvious splitting of the isoindole breathing band at 1110–1123 cm−1, the IR spectra of M[Pc(α-OC5H11)4]2 are quite similar to those of corresponding M(Pc)[Pc(α-OC5H11)4] and therefore are similarly assigned. With laser excitation at 633 nm, Raman bands derived from isoindole ring and aza stretchings in the range of 1300–1600 cm−1 are selectively intensified. The IR spectra reveal that the frequencies of pyrrole stretching and pyrrole stretching coupled with the symmetrical CH bending of –CH3 groups are sensitive to the rare earth ionic size, while the Raman technique shows that the bands due to the isoindole stretchings and the coupled pyrrole and aza stretchings are similarly affected. Nevertheless, the phthalocyanine monoanion radical Pc′− IR marker band of bis(phthalocyaninato) complexes involving the same rare earth ion is found to shift to lower energy in the order M(Pc)2 > M(Pc)[Pc(α-OC5H11)4] > M[Pc(α-OC5H11)4]2, revealing the weakened π–π interaction between the two phthalocyanine rings in the same order.

4th Biennal Europea De Paisatge Barcelona, Spain March 22-26, 2006

Between the 22nd and the 26th of March 2006, Barcelona hosted the 4th Biennal Europea de Paisatge (European Biennial of Landscape Architecture). It comprised a day of presentations for the Rosa Barba Prize for European Landscape Architecture, a day long symposium, and a half day discussion on IBA park projects. Approximately 300 people attended, including sizable groups from Barcelona, France, The Netherlands, Denmark, and Germany. Only three participants from English speaking countries were present, despite simultaneous translation into English throughout.

The new epidemics

In developed countries we once thought that the scourge of infectious diseases was tamed. Antibiotics were controlling infection in individual patients, vaccines were preventing illness and great faith was placed in the capacity of science to confound the most cunning organism. However, things have changed and in the new millennium we are confronting a host of challenges to public health from infectious diseases. Epidemics mean an excess of cases in the community from that normally expected or the appearance of a new infection (Webber ####, 22) Chapter 11 outlined the background to infectious diseases and the individual strategies directed towards the control and management of infectious diseases. The aim of this chapter is to outline the impact that infectious diseases have on population health, to identify the risks of major outbreaks and to identify the strategies required to reduce the risk and to manage any possible outbreak.

Exercise-induced energy expenditure : implications for exercise prescription and obesity

Objective: Walking is commonly recommended to help with weight management. We measured total energy expenditure (TEE) and its components to quantify the impact of increasing exercise-induced energy expenditure (ExEE) on other components of TEE. Methods: Thirteen obese women underwent an 8-week walking group intervention. TEE was quantified using doubly labeled water, ExEE was quantified using heart rate monitors, daily movement was assessed by accelerometry and resting metabolic rate was measured using indirect calorimetry. Results: Four of the 13 participants achieved the target of 1500 kcal wk−1 of ExEE and all achieved 1000 kcal wk−1. The average ExEE achieved by the group across the 8 weeks was 1434 ± 237 kcal wk−1. Vigorous physical activity, as assessed by accelerometry, increased during the intervention by an average of 30 min per day. Non-exercise activity thermogenesis (NEAT) decreased, on average, by 175 kcal d−1 (−22%) from baseline to the intervention and baseline fitness was correlated with change in NEAT. Conclusions: Potential alterations in non-exercise activity should be considered when exercise is prescribed. The provision of appropriate education on how to self-monitor daily activity levels may improve intervention outcomes in groups who are new to exercise. Practice implications: Strategies to sustain incidental and light physical activity should be offered to help empower individuals as they develop and maintain healthy and long-lasting lifestyle habits.

Quality of life after total laparoscopic hysterectomy versus total abdominal hysterectomy for stage I endometrial cancer (LACE) : a randomised trial

Background: The two-stage Total Laparoscopic Hysterectomy (TLH) versus Total Abdominal Hysterectomy (TAH) for stage I endometrial cancer (LACE) randomised controlled trial was initiated in 2005. The primary objective of stage 1 was to assess whether TLH results in equivalent or improved QoL up to 6 months after surgery compared to TAH. The primary objective of stage 2 was to test the hypothesis that disease-free survival at 4.5 years is equivalent for TLH and TAH. Results addressing the primary objective of stage 1 of the LACE trial are presented here. Methods: The first 361 LACE participants (TAH n= 142, TLH n=190) were enrolled in the QoL substudy at 19 centres across Australia, New Zealand and Hong Kong, and 332 completed the QoL analysis. Randomisation was performed centrally and independently from other study procedures via a computer generated, web-based system (providing concealment of the next assigned treatment) using stratified permuted blocks of 3 and 6, and assigned patients with histologically confirmed stage 1 endometrioid endometrial adenocarcinoma and ECOG performance status <2 to TLH or TAH stratified by histological grade and study centre. No blinding of patients or study personnel was attempted. QoL was measured at baseline, 1 and 4 weeks (early), and 3 and 6 months (late) after surgery using the Functional Assessment of Cancer Therapy-General (FACT-G) questionnaire. The primary endpoint was the difference between the groups in QoL change from baseline at early and late time points (a 5% difference was considered clinically significant). Analysis was performed according to the intention-to-treat principle using generalized estimating equations on differences from baseline for the early and late QoL recovery. The LACE trial is registered with clinicaltrials.gov (NCT00096408) and the Australian New Zealand Clinical Trials Registry (CTRN12606000261516). Patients for both stages of the trial have now been recruited and are being followed up for disease-specific outcomes. Findings: The proportion of missing values at the 5%, 10% 15% and 20% differences in the FACT-G scale was 6% (12/190) in the TLH and 14% (20/142) in the TAH group. There were 8/332 conversions (2.4%, 7 of which were from TLH to TAH). In the early phase of recovery, patients undergoing TLH reported significantly greater improvement of QoL from baseline compared to TAH in all subscales except the emotional and social well-being subscales. Improvements in QoL up to 6 months post-surgery continued to favour TLH except for the emotional and social well-being of the FACT and the visual analogue scale of the EuroQoL five dimensions (EuroQoL-VAS). Length of operating time was significantly longer in the TLH group (138±43 mins), than in the TAH group at (109±34 mins; p=0.001). While the proportion of intraoperative adverse events was similar between the treatment groups (TAH 8/142, 5.6%; TLH 14/190, 7.4%; p=0.55), postoperatively, twice as many patients in the TAH group experienced adverse events of CTC grade 3+ than in the TLH group (33/142, 23.2% and 22/190, 11.6%, respectively; p=0.004). Postoperative serious adverse events occurred more frequently in patients who had a TAH (27/142, 19.0%) than a TLH (15/190, 7.9%) (p=0.002). Interpretation: QoL improvements from baseline during early and later phases of recovery, and the adverse event profile significantly favour TLH compared to TAH for patients treated for Stage I endometrial cancer.

Types of foot problems seen by Australian podiatrists

Background: Understanding frequency of foot problems can assist health care planners with resource deployment to new and emerging services such as paediatric podiatry and focus future research on the most salient foot conditions. Methods: A review of 2187 patient consultations during a three month period was conducted. Patient medical and podiatric history was coded using industry standards. All patients were recruited for convenience from a metropolitan university podiatry clinic. Results: 392 new patients were identified with mean age 40.6 years old (range 1–95), with 65% being female. Arthritic diseases, asthma, hypertension and allergies were the most common medical conditions reported. The frequency of new consultations in younger people (n = 102; 27%) exceeded those of the elderly (n = 75; 20%). Conversely, the elderly were nearly three times more prevalent in this cohort (n = 910; 43%) compared to younger people (n = 332; 16%). Conclusion: This study illustrates the diverse nature of pathology seen by podiatrists. Knowledge that skin lesions are highly prevalent is of relevance to health departments, given the aging nature of most populations. Moreover there appears to be a growing trend in the number of young people who present for care, however government funded access to these services are limited.

Choosing your niche : the social ecology of the International Baccalaureate Diploma in Australia.

The International Baccalaureate’s branding and reputation targets academic high achievers aiming for university entrance. This is an empirical examination of the growing popularity of this transnational secondary credential amongst local populations in Australia, focusing on its uptake across the community, and the discourses underpinning its spread and popularity. This paper reports on online surveys of 179 parents and 231 students in schools offering the IB as an alternative to Australian state curricula. It sets out to understand the social ecology of who chooses the IB and who it chooses. Statistically significant differences between IB and non-IB choosers were found in terms of family income, parent education, student aspirations, transnational lifestyles, and neoconservative, neoliberal and cosmopolitan beliefs. The analysis demonstrates how the reproduction of advantage is accomplished through choice behaviours in stratified educational markets.

Infrared and Raman spectroscopic characterization of the phosphate mineral fairfieldite – Ca2(Mn2+,Fe2+)2(PO4)2·2(H2O)

Raman spectroscopy complimented with infrared spectroscopy has been used to determine the molecular structure of the phosphate mineral fairfieldite. The Raman phosphate (PO4)3- stretching region shows strong differences between the fairfieldite phosphate minerals which is attributed to the cation substitution for calcium in the structure. In the infrared spectra complexity exists with multiple (PO4)2- antisymmetric stretching vibrations observed, indicating a reduction of the tetrahedral symmetry. This loss of degeneracy is also reflected in the bending modes. Strong Raman bands around 600 cm-1 are assigned to v4 phosphate bending modes. Multiple bands in the 400–450 cm-1 region assigned to m2 phosphate bending modes provide further evidence of symmetry reduction of the phosphate anion. Three broadbands for fairfieldite are found at 3040, 3139 and 3271 cm-1 and are assigned to OH stretching bands. By using a Libowitzky empirical equation hydrogen bond distances of 2.658 and 2.730 A are estimated. Vibrational spectroscopy enables aspects of the molecular structure of the fairfieldite to be ascertained.

Spectroscopic studies of the adsorption and reactions of chlorofluorocarbons (CFC-11 and CFC-12) and hydrochlorofluorocarbon (HCFC-22) on oxide surfaces

Raman and Fourier transform infrared (FT-IR) spectroscopy have been applied to a systematic investigation of the adsorption and decomposition of dichlorodifluoromethane (CCl2F2, CFC-12), fluorotrichloromethane (CCl3F, CFC-11), chlorodifluoromethane (CHClF2, HCFC-22) and molecular chlorine on oxide surfaces. Additionally, the effects of heating and ultraviolet photolysis of the CFC and HCFCs adsorbed on the oxide surfaces have been investigated. Spectral features for these species indicated a small wavenumber shift (1-6 cm-1) associated with the adsorbed phase. Some evidence, specifically the appearance of the Raman band at 507 cm-1, is presented to show that chlorine decomposition species are associated with these oxide surfaces. It was concluded that the new spectral feature (at ca. 507 cm-1) related with the decomposition of the CFC and HCFC molecules was an important indicator of the extent to which the reaction between the adsorbed CFC and HCFC and oxide surface has taken place. The extent of CFC-surface interaction has been quantified in terms of a maximum (Raman) frequency shift parameter (AM). Wavenumber shifts suggest both cation-adsorbate and non-specific adsorption interactions are occurring in the internal channels of the zeolites. Slow decomposition of the adsorbed CFCs under ultraviolet-visible photolysis (at ? > 300 nm) and/or thermal treatment was observed spectroscopically. Using FT-IR spectroscopy, the formation of gas-phase products (CO, CO2, HCl) both onyn photolysis and heating was evident. Results of these measurements are compared with the observed atmospheric reactivity of these compounds.

The University of Queensland St Lucia campus 1.22 MW photovoltaic array

At the time of its official opening on 15 July 2011, The University of Queensland 1.22 MW array was the largest flat-panel PhotoVoltaic (PV) array in Australia. This PV array consists of over 5000 Trina Solar 240 Wp polycrystalline silicon PV modules installed across four rooftops at the St Lucia campus. Grid connection was achieved with 85 12.5 kW three phase and four 5 kW single phase grid connect inverters manufactured by Power-One. The site also includes one 8.4 kWp SolFocus concentrating solar 2 axis tracking PV array. Site wide monitoring and data logging of all DC, AC and environmental quantities will allow this array to be a rich source of research data. The site will also include a 200 kW 400 kWh zinc bromine energy storage system by Redflow, and associated power quality metering and monitoring. This paper presents highlights of the project feasibility study which included a site survey, shading analysis, and technology and triple bottom line assessment. A detailed description of the final technical implementation including discussion of alterative options considered is given. Finally, example initial data showing yield, trends and early example experimental results are presented.

A 22-nt artificial microRNA mediates widespread RNA silencing in Arabidopsis

It is known that 22-nucleotide (nt) microRNAs (miRNAs) derived from asymmetric duplexes trigger phased small-interfering RNA (phasiRNA) production from complementary targets. Here we investigate the efficacy of 22-nt artificial miRNA (amiRNA)-mediated RNA silencing relative to conventional hairpin RNA (hpRNA) and 21-nt amiRNA-mediated RNA silencing. CHALCONE SYNTHASE (CHS) was selected as a target in Arabidopsis thaliana due to the obvious and non-lethal loss of anthocyanin accumulation upon widespread RNA silencing. Over-expression of CHS in the pap1-D background facilitated visual detection of both local and systemic RNA silencing. RNA silencing was initiated in leaf tissues from hpRNA and amiRNA plant expression vectors under the control of an Arabidopsis RuBisCo small subunit 1A promoter (SSU). In this system, hpRNA expression triggered CHS silencing in most leaf tissues but not in roots or seed coats. Similarly, 21-nt amiRNA expression from symmetric miRNA/miRNA* duplexes triggered CHS silencing in all leaf tissues but not in roots or seed coats. However, 22-nt amiRNA expression from an asymmetric duplex triggered CHS silencing in all tissues, including roots and seed coats, in the majority of plant lines. This widespread CHS silencing required RNA-DEPENDENT RNA POLYMERASE6-mediated accumulation of phasiRNAs from the endogenous CHS transcript. These results demonstrate the efficacy of asymmetric 22-nt amiRNA-directed RNA silencing and associated phasiRNA production and activity, in mediating widespread RNA silencing of an endogenous target gene. Asymmetric 22-nt amiRNA-directed RNA silencing requires little modification of existing amiRNA technology and is expected to be effective in suppressing other genes and/or members of gene families.