A rebirth of physical activity in parents : applying a theory-based approach

Physical inactivity is a serious concern both nationally and internationally. Despite the numerous benefits of performing regular physical activity, many individuals lead sedentary lifestyles. Of concern, though, is research showing that some population sub-groups are less likely to be active, such as parents of young children. Although there is a vast amount of research dedicated to understanding people.s physical activity-related behaviours, there is a paucity of research examining those factors that influence parental physical activity. More importantly, research applying theoretical models to understand physical activity decision-making among this at-risk population is limited. Given the current obesity epidemic, the decline in physical activity with parenthood, and the many social and health benefits associated with regular physical activity, it is important that adults with young children are sufficiently active. In light of the dearth of research examining parental physical activity and the scant research applying a theory-based approach to gain this understanding, the overarching aim of the current program of research was to adopt a mixed methods approach as well as use sound theoretical frameworks to understand the regular physical activity behaviour of mothers and fathers with young children. This program of research comprised of three distinct stages: a qualitative stage exploring individual, social, and psychological factors that influence parental regular physical activity (Stage 1); a quantitative stage identifying the important predictors of parental regular physical activity intentions and behaviour using sound theoretical frameworks and testing a single-item measure for assessing parental physical activity behaviour (Stage 2); and a qualitative stage exploring strategies for an intervention program aimed at increasing parental regular physical activity (Stage 3). As a thesis by publication, eight papers report the findings of this program of research; these papers are presented according to the distinct stages of investigation that guided this program of research. Stage One of the research program comprised a qualitative investigation using a focus group/interview methodology with parents of children younger than 5 years of age (N = 40; n = 21 mothers, n = 19 fathers) (Papers 1, 2, and 3). Drawing broadly on a social constructionist approach (Paper 1), thematic analytic methods revealed parents. understandings of physical activity (e.g., requires effort), patterns of physical activity-related behaviours (e.g., grab it when you can, declining physical activity habits), and how constructions of social role expectations might influence parents. physical activity decision making (e.g., creating an active family culture, guilt and selfishness). Drawing on the belief-based framework of the TPB (Paper 2), thematic content analytic methods revealed parents. commonly held beliefs about the advantages (e.g., improves parenting practices), disadvantages (e.g., interferes with commitments), barriers (e.g., time), and facilitators (e.g., social support) to performing regular physical activity. Parents. normative beliefs about social approval from important others or groups (e.g., spouse/partner) were also identified. Guided by theories of social support, Paper Three identified parents. perceptions about the specific social support dimensions that influence their physical activity decision making. Thematic content analysis identified instrumental (e.g., providing childcare, taking over chores), emotional (e.g., encouragement, companionship), and informational support (e.g., ideas and advice) as being important to the decision-making of parents in relation to their regular physical activity behaviour. The results revealed also that having support for being active is not straightforward (e.g., guilt-related issues inhibited the facilitative nature of social support for physical activity). Stage Two of the research program comprised a quantitative examination of parents. physical activity intentions and behaviour (Papers 4, 5, 6, and 7). Parents completed an extended TPB questionnaire at Time 1 (N = 580; n = 288 mothers, n = 292 fathers) and self-reported their physical activity at Time 2, 1 week later (N = 458; n = 252 mothers, n = 206 fathers). Paper Four revealed key behavioural (e.g., improving parenting practices), normative (e.g., people I exercise with), and control (e.g., lack of time) beliefs as significant independent predictors of parental physical activity. A test of the TPB augmented to include the constructs of self-determined motivation and planning was assessed in Paper Five. The findings revealed that the effect of self-determined motivation on intention was fully mediated by the TPB variables and the impact of intention on behaviour was partially mediated by the planning variables. Slight differences in the model.s motivational sequence between the sexes were also noted. Paper Six investigated, within a TPB framework, a range of social influences on parents. intentions to be active. For both sexes, attitude, perceived behavioural control, group norms, friend general support, and an active parent identity predicted intentions, with subjective norms and family support further predicting mothers. intentions and descriptive norms further predicting fathers. intentions. Finally, the measurement of parental physical activity was investigated in Paper Seven of Stage Two. The results showed that parents are at risk of low levels of physical activity, with the findings also revealing validation support for a brief single-item physical activity measure. Stage Three of the research program comprised a qualitative examination of parents. (N = 12; n = 6 mothers, n = 6 fathers) ideas for strategies that may be useful for developing and delivering an intervention program aimed at increasing parental physical activity (Paper 8). Parents revealed a range of strategies for what to include in a physical activity intervention designed for parents of young children. For example, parents identified persuasion and information type messages, problem-solving strategies that engage parents in generating a priority list of their lifestyle commitments, and behavioural modification techniques such as goal setting and incentives. Social intervention strategies (e.g., social comparison, counselling) and environmental approaches (e.g., community-based integrative parent/child programs) were also identified as was a skill-based strategy in helping parents generate a flexible life/family plan. Additionally, a range of strategies for how to best deliver a parental physical activity intervention was discussed. Taken as a whole, Paper Eight found that adopting a multifaceted approach in both the design and implementation of a resultant physical activity intervention may be useful in helping to increase parental physical activity. Overall, this program of research found support for parents as a unique group who hold both similar and distinctive perceptions about regular physical activity to the general adult population. Thus, these findings highlight the importance of targeting intervention strategies for parents of young children. Additionally, the findings suggest that it might also be useful to tailor some messages specifically to each sex. Effective promotion of physical activity in parents of young children is essential given the low rate of activity in this population. Results from this program of research highlight parents as an at-risk group for inactivity and provide an important first step in identifying the factors that influence both mothers. and fathers. physical activity decision making. These findings, in turn, provide a foundation on which to build effective intervention programs aimed at increasing parents. regular physical activity which is essential for ensuring the health and well-being of parents with young children.

Flexible high voltage pulsed power supply for plasma applications

Demands for delivering high instantaneous power in a compressed form (pulse shape) have widely increased during recent decades. The flexible shapes with variable pulse specifications offered by pulsed power have made it a practical and effective supply method for an extensive range of applications. In particular, the release of basic subatomic particles (i.e. electron, proton and neutron) in an atom (ionization process) and the synthesizing of molecules to form ions or other molecules are among those reactions that necessitate large amount of instantaneous power. In addition to the decomposition process, there have recently been requests for pulsed power in other areas such as in the combination of molecules (i.e. fusion, material joining), gessoes radiations (i.e. electron beams, laser, and radar), explosions (i.e. concrete recycling), wastewater, exhausted gas, and material surface treatments. These pulses are widely employed in the silent discharge process in all types of materials (including gas, fluid and solid); in some cases, to form the plasma and consequently accelerate the associated process. Due to this fast growing demand for pulsed power in industrial and environmental applications, the exigency of having more efficient and flexible pulse modulators is now receiving greater consideration. Sensitive applications, such as plasma fusion and laser guns also require more precisely produced repetitive pulses with a higher quality. Many research studies are being conducted in different areas that need a flexible pulse modulator to vary pulse features to investigate the influence of these variations on the application. In addition, there is the need to prevent the waste of a considerable amount of energy caused by the arc phenomena that frequently occur after the plasma process. The control over power flow during the supply process is a critical skill that enables the pulse supply to halt the supply process at any stage. Different pulse modulators which utilise different accumulation techniques including Marx Generators (MG), Magnetic Pulse Compressors (MPC), Pulse Forming Networks (PFN) and Multistage Blumlein Lines (MBL) are currently employed to supply a wide range of applications. Gas/Magnetic switching technologies (such as spark gap and hydrogen thyratron) have conventionally been used as switching devices in pulse modulator structures because of their high voltage ratings and considerably low rising times. However, they also suffer from serious drawbacks such as, their low efficiency, reliability and repetition rate, and also their short life span. Being bulky, heavy and expensive are the other disadvantages associated with these devices. Recently developed solid-state switching technology is an appropriate substitution for these switching devices due to the benefits they bring to the pulse supplies. Besides being compact, efficient, reasonable and reliable, and having a long life span, their high frequency switching skill allows repetitive operation of pulsed power supply. The main concerns in using solid-state transistors are the voltage rating and the rising time of available switches that, in some cases, cannot satisfy the application’s requirements. However, there are several power electronics configurations and techniques that make solid-state utilisation feasible for high voltage pulse generation. Therefore, the design and development of novel methods and topologies with higher efficiency and flexibility for pulsed power generators have been considered as the main scope of this research work. This aim is pursued through several innovative proposals that can be classified under the following two principal objectives. • To innovate and develop novel solid-state based topologies for pulsed power generation • To improve available technologies that have the potential to accommodate solid-state technology by revising, reconfiguring and adjusting their structure and control algorithms. The quest to distinguish novel topologies for a proper pulsed power production was begun with a deep and through review of conventional pulse generators and useful power electronics topologies. As a result of this study, it appears that efficiency and flexibility are the most significant demands of plasma applications that have not been met by state-of-the-art methods. Many solid-state based configurations were considered and simulated in order to evaluate their potential to be utilised in the pulsed power area. Parts of this literature review are documented in Chapter 1 of this thesis. Current source topologies demonstrate valuable advantages in supplying the loads with capacitive characteristics such as plasma applications. To investigate the influence of switching transients associated with solid-state devices on rise time of pulses, simulation based studies have been undertaken. A variable current source is considered to pump different current levels to a capacitive load, and it was evident that dissimilar dv/dts are produced at the output. Thereby, transient effects on pulse rising time are denied regarding the evidence acquired from this examination. A detailed report of this study is given in Chapter 6 of this thesis. This study inspired the design of a solid-state based topology that take advantage of both current and voltage sources. A series of switch-resistor-capacitor units at the output splits the produced voltage to lower levels, so it can be shared by the switches. A smart but complicated switching strategy is also designed to discharge the residual energy after each supply cycle. To prevent reverse power flow and to reduce the complexity of the control algorithm in this system, the resistors in common paths of units are substituted with diode rectifiers (switch-diode-capacitor). This modification not only gives the feasibility of stopping the load supply process to the supplier at any stage (and consequently saving energy), but also enables the converter to operate in a two-stroke mode with asymmetrical capacitors. The components’ determination and exchanging energy calculations are accomplished with respect to application specifications and demands. Both topologies were simply modelled and simulation studies have been carried out with the simplified models. Experimental assessments were also executed on implemented hardware and the approaches verified the initial analysis. Reports on details of both converters are thoroughly discussed in Chapters 2 and 3 of the thesis. Conventional MGs have been recently modified to use solid-state transistors (i.e. Insulated gate bipolar transistors) instead of magnetic/gas switching devices. Resistive insulators previously used in their structures are substituted by diode rectifiers to adjust MGs for a proper voltage sharing. However, despite utilizing solid-state technology in MGs configurations, further design and control amendments can still be made to achieve an improved performance with fewer components. Considering a number of charging techniques, resonant phenomenon is adopted in a proposal to charge the capacitors. In addition to charging the capacitors at twice the input voltage, triggering switches at the moment at which the conducted current through switches is zero significantly reduces the switching losses. Another configuration is also introduced in this research for Marx topology based on commutation circuits that use a current source to charge the capacitors. According to this design, diode-capacitor units, each including two Marx stages, are connected in cascade through solid-state devices and aggregate the voltages across the capacitors to produce a high voltage pulse. The polarity of voltage across one capacitor in each unit is reversed in an intermediate mode by connecting the commutation circuit to the capacitor. The insulation of input side from load side is provided in this topology by disconnecting the load from the current source during the supply process. Furthermore, the number of required fast switching devices in both designs is reduced to half of the number used in a conventional MG; they are replaced with slower switches (such as Thyristors) that need simpler driving modules. In addition, the contributing switches in discharging paths are decreased to half; this decrease leads to a reduction in conduction losses. Associated models are simulated, and hardware tests are performed to verify the validity of proposed topologies. Chapters 4, 5 and 7 of the thesis present all relevant analysis and approaches according to these topologies.

Identification of early-stage colorectal cancer patients at risk of relapse post-resection by immunobead reverse transcription-PCR analysis of peritoneal lavage fluid for malignant cells

Purpose: Colorectal cancer patients diagnosed with stage I or II disease are not routinely offered adjuvant chemotherapy following resection of the primary tumor. However, up to 10% of stage I and 30% of stage II patients relapse within 5 years of surgery from recurrent or metastatic disease. The aim of this study was to determine if tumor-associated markers could detect disseminated malignant cells and so identify a subgroup of patients with early-stage colorectal cancer that were at risk of relapse. Experimental Design: We recruited consecutive patients undergoing curative resection for early-stage colorectal cancer. Immunobead reverse transcription-PCR of five tumor-associated markers (carcinoembryonic antigen, laminin γ2, ephrin B4, matrilysin, and cytokeratin 20) was used to detect the presence of colon tumor cells in peripheral blood and within the peritoneal cavity of colon cancer patients perioperatively. Clinicopathologic variables were tested for their effect on survival outcomes in univariate analyses using the Kaplan-Meier method. A multivariate Cox proportional hazards regression analysis was done to determine whether detection of tumor cells was an independent prognostic marker for disease relapse. Results: Overall, 41 of 125 (32.8%) early-stage patients were positive for disseminated tumor cells. Patients who were marker positive for disseminated cells in post-resection lavage samples showed a significantly poorer prognosis (hazard ratio, 6.2; 95% confidence interval, 1.9-19.6; P = 0.002), and this was independent of other risk factors. Conclusion: The markers used in this study identified a subgroup of early-stage patients at increased risk of relapse post-resection for primary colorectal cancer. This method may be considered as a new diagnostic tool to improve the staging and management of colorectal cancer. © 2006 American Association for Cancer Research.

A study of environmental and management drivers of non-CO2 greenhouse gas emissions in Australian agro-ecosystems

Australian climate, soils and agricultural management practices are significantly different from those of the northern hemisphere nations. Consequently, experimental data on greenhouse gas production from European and North American agricultural soils and its interpretation are unlikely to be directly applicable to Australian systems. A programme of studies of non-CO2 greenhouse gas emissions from agriculture has been established that is designed to reduce uncertainty of non-CO2 greenhouse gas emissions in the Australian National Greenhouse Gas Inventory and provide outputs that will enable better on-farm management practices for reducing non-CO2 greenhouse gas emissions, particularly nitrous oxide. The systems being examined and their locations are irrigated pasture (Kyabram Victoria), irrigated cotton (Narrabri, NSW), irrigated maize (Griffith, NSW), rain-fed wheat (Rutherglen, Victoria) and rain-fed wheat (Cunderdin, WA). The field studies include treatments with and without fertilizer addition, stubble burning versus stubble retention, conventional cultivation versus direct drilling and crop rotation to determine emission factors and treatment possibilities for best management options. The data to date suggest that nitrous oxide emissions from nitrogen fertilizer, applied to irrigated dairy pastures and rain-fed winter wheat, appear much lower than the average of northern hemisphere grain and pasture studies. More variable emissions have been found in studies of irrigated cotton/vetch/wheat rotation and substantially higher emissions from irrigated maize.

Thermal stability of crandallite CaAl3(PO4)2(OH)5•(H2O) – a ‘cave’ mineral from the Jenolan Caves

Thermogravimetry combined with evolved gas mass spectrometry has been used to characterise the mineral crandallite CaAl3(PO4)2(OH)5•(H2O) and to ascertain the thermal stability of this ‘cave’ mineral. X-ray diffraction proves the presence of the mineral and identifies the products after thermal decomposition. The mineral crandallite is formed through the reaction of calcite with bat guano. Thermal analysis shows that the mineral starts to decompose through dehydration at low temperatures at around 139°C while dehydroxylation occurs over the temperature range 200 to 700°C with loss of OH units. The critical temperature for OH loss is around 416°C and above this temperature the mineral structure is altered. Some minor loss of carbonate impurity occurs at 788°C. This study shows the mineral is unstable above 139°C. This temperature is well above the temperature in caves, which have a maximum temperature of 15°C. A chemical reaction for the synthesis of crandallite is offered and the mechanism for the thermal decomposition is given.

Numerical modelling of non-load bearing light gauge cold-formed steel frame walls under fire conditions

Recently an innovative composite panel system was developed, where a thin insulation layer was used externally between two plasterboards to improve the fire performance of light gauge cold-formed steel frame walls. In this research, finite-element thermal models of both the traditional light gauge cold-formed steel frame wall panels with cavity insulation and the new light gauge cold-formed steel frame composite wall panels were developed to simulate their thermal behaviour under standard and realistic fire conditions. Suitable apparent thermal properties of gypsum plasterboard, insulation materials and steel were proposed and used. The developed models were then validated by comparing their results with available fire test results. This article presents the details of the developed finite-element models of small-scale non-load-bearing light gauge cold-formed steel frame wall panels and the results of the thermal analysis. It has been shown that accurate finite-element models can be used to simulate the thermal behaviour of small-scale light gauge cold-formed steel frame walls with varying configurations of insulations and plasterboards. The numerical results show that the use of cavity insulation was detrimental to the fire rating of light gauge cold-formed steel frame walls, while the use of external insulation offered superior thermal protection to them. The effects of real fire conditions are also presented.

Tuning the reduction power of supported gold nanoparticle photocatalysts for selective reductions by manipulating wavelength of visible light irradiation

Gold nanoparticles supported on CeO2 were found to be efficient photocatalysts for three selective reductions of organic compounds at ambient temperatures, under irradiation of visible light; their reduction ability can be tuned by manipulating the irradiation wavelength.

Evaluation of an Australian solar community : implications for education and training

1.1 Background What is renewable energy education and training? A cursory exploration of the International Solar Energy Society website (www.ises.org) reveals numerous references to education and training, referring collectively to concepts of the transfer and exchange of information and good practices, awareness raising and skills development. The purposes of such education and training relate to changing policy, stimulating industry, improving quality control and promoting the wider use of renewable energy sources. The primary objective appears to be to accelerate a transition to a better world for everyone (ISEE), as the greater use of renewable energy is seen as key to climate recovery; world poverty alleviation; advances in energy security, access and equality; improved human and environmental health; and a stabilized society. The Solar Cities project – Habitats of Tomorrow – aims at promoting the greater use of renewable energy within the context of long term planning for sustainable urban development. The focus is on cities or communities as complete systems; each one a unique laboratory allowing for the study of urban sustainability within the context of a low carbon lifestyle. The purpose of this paper is to report on an evaluation of a Solar Community in Australia, focusing specifically on the implications (i) for our understandings and practices in renewable energy education and training and (ii) for sustainability outcomes. 1.2 Methodology The physical context is a residential Ecovillage (a Solar Community) in sub-tropical Queensland, Australia (latitude 28o south). An extensive Architectural and Landscape Code (A&LC) ‘premised on the interconnectedness of all things’ and embracing ‘both local and global concerns’ governs the design and construction of housing in the estate: all houses are constructed off-ground (i.e. on stumps or stilts) and incorporate a hybrid approach to the building envelope (mixed use of thermal mass and light-weight materials). Passive solar design, gas boosted solar water heaters and a minimum 1kWp photovoltaic system (grid connected) are all mandatory, whilst high energy use appliances such as air conditioners and clothes driers are not permitted. Eight families participated in an extended case study that encompassed both quantitative and qualitative approaches to better understand sustainable housing (perceived as a single complex technology) through its phases of design, construction and occupation. 1.3 Results The results revealed that the level of sustainability (i.e. the performance outcomes in terms of a low-carbon lifestyle) was impacted on by numerous ‘players’ in the supply chain, such as architects, engineers and subcontractors, the housing market, the developer, product manufacturers / suppliers / installers and regulators. Three key factors were complicit in the level of success: (i) systems thinking; (ii) informed decision making; and (iii) environmental ethics and business practices. 1.4 Discussion The experiences of these families bring into question our understandings and practices with regard to education and training. Whilst increasing and transferring knowledge and skills is essential, the results appear to indicate that there is a strong need for expanding our education efforts to incorporate foundational skills in complex systems and decision making processes, combined with an understanding of how our individual and collective values and beliefs impact on these systems and processes.

Integrating efficient filtration and visible-light photocatalysis by loading Ag-doped zeolite Y particles on aluminia nanofiber membrane

Filtration membrane technology has already been employed to remove various organic effluents produced from the textile, paper, plastic, leather, food and mineral processing industries. To improve membrane efficiency and alleviate membrane fouling, an integrated approach is adopted that combines membrane filtration and photocatalysis technology. In this study, alumina nanofiber (AF) membranes with pore size of about 10 nm (determined by the liquid-liquid displacement method) have been synthesized through an in situ hydrothermal reaction, which permitted a large flux and achieved high selectivity. Silver nanoparticles (Ag NPs) are subsequently doped on the nanofibers of the membranes. Silver nanoparticles can strongly absorb visible light due to the surface plasmon resonance (SPR) effect, and thus induce photocatalytic degradation of organic dyes, including anionic, cationic and neutral dyes, under visible light irradiation. In this integrated system, the dyes are retained on the membrane surface, their concentration in the vicinity of the Ag NPs are high and thus can be efficiently decomposed. Meanwhile, the usual flux deterioration caused by the accumulation of the filtered dyes in the passage pores can be avoided. For example, when an aqueous solution containing methylene blue is processed using an integrated membrane, a large flux of 200 L m-2 h-1 and a stable permeating selectivity of 85% were achieved. The combined photocatalysis and filtration function leads to superior performance of the integrated membranes, which have a potential to be used for the removal of organic pollutants in drinking water.

Influence of field size on pupil diameter under photopic and mesopic light levels

Purpose: We investigated the interaction between adapting field size and luminance on pupil diameter when cones alone (photopic) or rods and cones (mesopic) were active. Method: Circular achromatic targets (1o to 24o diameter) were presented to eight young participants on a rectangular projector screen. The accommodative influence on pupil diameter was minimized using cycloplegia in the fixing right eye and the consensual pupil reflex was measured in the left eye. Target luminance was adjusted for each stimulus such that corneal flux density (product of field area and luminance) was constant at 3600 cd.deg2m-2 (photopic condition) and 1.49 cd.deg2m-2 (mesopic condition). Results: There were no statistically significant effects of adaptive field size on pupil diameter for either condition. Conclusion: If corneal flux density is kept constant, there will be no change in pupil diameter as the size of the stimulus field increases at either mesopic or photopic lighting levels up to at least 24°.

Regulating coal seam gas in Queensland : lessons in an adaptive environmental management approach?

The current regulatory approach to coal seam gas projects in Queensland is based on the philosophy of adaptive environmental management. This method of “learning by doing” is implemented in Queensland primarily through the imposition of layered monitoring and reporting duties on the coal seam gas operator alongside obligations to compensate and “make good” harm caused. The purpose of this article is to provide a critical review of the Queensland regulatory approach to the approval and minimisation of adverse impacts from coal seam gas activities. Following an overview of the hallmarks of an effective adaptive management approach, this article begins by addressing the mosaic of approval processes and impact assessment regimes that may apply to coal seam gas projects. This includes recent Strategic Cropping Land reforms. This article then turns to consider the preconditions for land access in Queensland and the emerging issues for landholders relating to the negotiation of access and compensation agreements. This article then undertakes a critical review of the environmental duties imposed on coal seam gas operators relating to hydraulic fracturing, well head leaks, groundwater management and the disposal and beneficial use of produced water. Finally, conclusions are drawn regarding the overall effectiveness of the Queensland framework and the lessons that may be drawn from Queensland’s adaptive environmental management approach.

Productivity performance of Singapore’s retail sector : a two-stage non-parametric approach

This paper seeks to identify and quantify sources of the lagging productivity in Singapore’s retail sector as reported in the Economic Strategies Committee 2010 report. A two-stage analysis is adopted. In the first stage, the Malmquist productivity index is employed which provides measures of productivity change, technological change and efficiency change. In the second stage, technical efficiency estimates are regressed against explanatory variables based on a truncated regression model. Sources of technical efficiency were attributed to quality of workers while product assortment and competition negatively impacted on efficiency.

Toward non-invasive detection of concealed energetic materials in-field under ambient-light conditions

Spatially offset Raman spectroscopy (SORS) is demonstrated for the non-contact detection of energetic materials concealed within non-transparent, diffusely scattering containers. A modified design of an inverse SORS probe has been developed and tested. The SORS probe has been successfully used for the detection of various energetic substances inside different types of plastic containers. The tests have been successfully conducted under incandescent and fluorescent background lights as well as under daylight conditions, using a non-contact working distance of 6 cm. The interrogation times for the detection of the substances were less than 1 minute in each case, highlighting the suitability of the device for near real-time detection of concealed hazards in the field. The device has potential applications in forensic analysis and homeland security investigations.

Functionalised zinc oxide nanowire gas sensors : enhanced NO2 gas sensor response by chemical modification of nanowire surfaces

Surface coating with an organic self-assembled monolayer (SAM) can enhance surface reactions or the absorption of specific gases and hence improve the response of a metal oxide (MOx) sensor toward particular target gases in the environment. In this study the effect of an adsorbed organic layer on the dynamic response of zinc oxide nanowire gas sensors was investigated. The effect of ZnO surface functionalisation by two different organic molecules, tris(hydroxymethyl)aminomethane (THMA) and dodecanethiol (DT), was studied. The response towards ammonia, nitrous oxide and nitrogen dioxide was investigated for three sensor configurations, namely pure ZnO nanowires, organic-coated ZnO nanowires and ZnO nanowires covered with a sparse layer of organic-coated ZnO nanoparticles. Exposure of the nanowire sensors to the oxidising gas NO2 produced a significant and reproducible response. ZnO and THMA-coated ZnO nanowire sensors both readily detected NO2 down to a concentration in the very low ppm range. Notably, the THMA-coated nanowires consistently displayed a small, enhanced response to NO2 compared to uncoated ZnO nanowire sensors. At the lower concentration levels tested, ZnO nanowire sensors that were coated with THMA-capped ZnO nanoparticles were found to exhibit the greatest enhanced response. ΔR/R was two times greater than that for the as-prepared ZnO nanowire sensors. It is proposed that the ΔR/R enhancement in this case originates from the changes induced in the depletion-layer width of the ZnO nanoparticles that bridge ZnO nanowires resulting from THMA ligand binding to the surface of the particle coating. The heightened response and selectivity to the NO2 target are positive results arising from the coating of these ZnO nanowire sensors with organic-SAM-functionalised ZnO nanoparticles.

Homo- and heteronuclear meso,meso-(E)-Ethene-1,2-diyl-Linked Diporphyrins : preparation, X-ray crystal structure, electronic absorption and emission spectra and density functional theory calculations

Homo-and heteronuclear meso,meso-(E)-ethene-1,2-diyl-linked diporphyrins have been prepared by the Suzuki coupling of porphyrinylboronates and iodovinylporphyrins. Combinations comprising 5,10,15-triphenylporphyrin (TriPP) on both ends of the ethene-1,2-diyl bridge M 210 (M 2=H 2/Ni, Ni 2, Ni/Zn, H 4, H 2Zn, Zn 2) and 5,15-bis(3,5-di-tert-butylphenyl)porphyrinato-nickel(II) on one end and H 2, Ni, and ZnTriPP on the other (M 211), enable the first studies of this class of compounds possessing intrinsic polarity. The compounds were characterized by electronic absorption and steady state emission spectra, 1H NMR spectra, and for the Ni 2 bis(TriPP) complex Ni 210, single crystal X-ray structure determination. The crystal structure shows ruffled distortions of the porphyrin rings, typical of Ni II porphyrins, and the (E)-C 2H 2 bridge makes a dihedral angle of 50° with the mean planes of the macrocycles. The result is a stepped parallel arrangement of the porphyrin rings. The dihedral angles in the solid state reflect the interplay of steric and electronic effects of the bridge on interporphyrin communication. The emission spectra in particular, suggest energy transfer across the bridge is fast in conformations in which the bridge is nearly coplanar with the rings. Comparisons of the fluorescence behaviour of H 410 and H 2Ni10 show strong quenching of the free base fluorescence when the complex is excited at the lower energy component of the Soret band, a feature associated in the literature with more planar conformations. TDDFT calculations on the gas-phase optimized geometry of Ni 210 reproduce the features of the experimental electronic absorption spectrum within 0.1 eV. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.