Excited-state dynamics in diketopyrrolopyrrole-based copolymer for organic photovoltaics investigated by transient optical spectroscopy

We investigate the photoexcited state dynamics in a donor-acceptor copolymer, poly{3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]- pyrrole-1,4-dione-alt-naphthalene} (pDPP-TNT), by picosecond fluorescence and femtosecond transient absorption spectroscopies. Timeresolved fluorescence lifetime measurements of pDPP-TNT thin films reveal that the lifetime of the singlet excited state is 185 ± 5 ps and that singlet-singlet annihilation occurs at excitation photon densities above 6 × 1017 photons/cm3. From the results of singlet-singlet annihilation analysis, we estimate that the single-singlet annihilation rate constant is (6.0 ± 0.2) × 109cm3 s-1 and the singlet diffusion length is -7 nm. From the comparison of femtosecond transient absorption measurements and picosecond fluorescence measurements, it is found that the time profile of the photobleaching signal in the charge-transfer (CT) absorption band coincides with that of the fluorescence intensity and there is no indication of long-lived species, which clearly suggests that charged species, such as polaron pairs and triplet excitons, are not effectively photogenerated in the neat pDPP-TNT polymer.

Characterization of 67 mitochondrial tRNA gene rearrangements in the Hymenoptera suggests that mitochondrial tRNA gene position is selectively neutral

We present entire sequences of two hymenopteran mitochondrial genomes and the major portion of three others. We combined these data with nine previously sequenced hymenopteran mitochondrial genomes. This allowed us to infer and analyze the evolution of the 67 mitochondrial gene rearrangements so far found in this order. All of these involve tRNA genes, whereas four also involve larger (protein-coding or ribosomal RNA) genes. We find that the vast majority of mitochondrial gene rearrangements are independently derived. A maximum of four of these rearrangements represent shared, derived organizations, whereas three are convergently derived. The remaining mitochondrial gene rearrangements represent new mitochondrial genome organizations. These data are consistent with the proposal that there are an enormous number of alternative mitochondrial genome organizations possible and that mitochondrial genome organization is, for the most part, selectively neutral. Nevertheless, some mitochondrial genes appear less mobile than others. Genes close to the noncoding region are generally more mobile but only marginally so. Some mitochondrial genes rearrange in a pattern consistent with the duplication/random loss model, but more mitochondrial genes move in a pattern inconsistent with this model. An increased rate of mitochondrial gene rearrangement is not tightly associated with the evolution of parasitism. Although parasitic lineages tend to have more mitochondrial gene rearrangements than nonparasitic lineages, there are exceptions (e.g., Orussus and Schlettererius). It is likely that only a small proportion of the total number of mitochondrial gene rearrangements that have occurred during the evolution of the Hymenoptera have been sampled in the present study.

Relics, 2007, in touring exhibition, Selectively Revealed, 2012

“Selectively Revealed investigates the blurry line between the public and the private in artistic practice. The artist is presented as voyeur, muse, subject, performer and social commentator. Using a variety of screen based practices, each artist pushes and pulls at the notion of what is private and what is public, choosing precisely what, when, how or when not to reveal their subjects or themselves. Ultimately, everything is presented for scrutiny; an innermost feeling, a personal moment, a fear or failure, an everyday encounter, an experience of rapture, a banal endeavour. Much is revealed, celebrated and critiqued.” Sarah Bond (Asialink) and Clare Needham (Experimenta)

Alloying gold with copper makes for a highly selective visible-light photocatalyst for the reduction of nitroaromatics to anilines

Finely control of product selectivity is an essential issue in organic chemical production. In the synthesis of functionalized anilines via reduction of the corresponding nitroarenes, the challenge is to selectively reduce only the nitro group in the presence of other reducible functional groups in nitroarene molecules at a high reaction rate. Normally, the nitroarene is reduced stepwise through a series of intermediates that remain as byproducts, increasing the aniline synthesis cost. Here we report that alloying small amounts of copper into gold nanoparticles can alter the reaction pathway of the catalytic reduction under visible-light irradiation at ambient temperature, allowing nitroaromatics to be transformed directly to anilines in a highly selective manner. The reasons for the high efficiency of the photocatalytic reduction under these comparatively benign conditions as well as the light-excited reaction mechanisms are discussed. This photocatalytic process avoids byproducts, exhibits a high reaction rate and excellent substituent tolerance, and can be used for the synthesis of many useful functionalized anilines under environmentally benign conditions. Switching of the reaction pathway simply by tailoring the bimetallic alloy NPs of the photocatalysts is effective for engineering of product chemoselectivity.

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.

Raman spectroscopy of kaolinites using different excitation wavelengths

The Raman spectra of both low- and high-defect kaolinites in the hydroxyl stretching and low-wavenumber region were obtained with excitation at three visible wavelengths of 633, 514 and 442 nm and a UV wavelength of 325 nm. The UV-excited spectra were comparable to those excited by the visible wavelengths. The Raman spectra show hydroxyl stretching bands at 3621 cm-1 attributed to the inner hydroxyl, at 3692 and 3684 cm-1 attributed to the longitudinal and transverse optic modes of the inner surface hydroxyls and at 3668 and 3653 cm-1 assigned to the out-of phase vibrations of the inner surface hydroxyls. Two bands were observed in the spectral profile at 3695 cm-1 for the high-defect kaolinite at 3698 and 3691 cm-1 and were assigned to TO/LO splitting. An increase in relative intensity of the transverse optic mode is observed with decrease in laser wavelength. The intensity of the out-of-phase vibrations at 3668 and 3653 cm-1 of the inner surface hydroxyls shows a linear relationship with the longitudinal and transverse optic modes. In the low-wavenumber region excellent correlation was found between the experimentally determined and the calculated band positions.

Predicting behaviour to reduce stroke risk in at-risk populations : the role of beliefs

Aims: Changing behaviour to reduce stroke risk is a difficult prospect made particularly complex because of psychological factors. This study examined predictors of intentions and behaviours to reduce stroke risk in a sample of at-risk individuals, seeking to find how knowledge and health beliefs influenced both intention and actual behaviour to reduce stroke risk. Methods: A repeated measures design was used to assess behavioural intentions at time 1 (T1) and subsequent behaviour (T2). One hundred and twenty six respondents completed an online survey at T1, and behavioural follow-up data were collected from approximately 70 participants 1 month later. Predictors were stroke knowledge, demographic variables, and beliefs about stroke that were derived from an expanded health belief model. Dependent measures were: exercise and weight loss, and intention to engage in these behaviours to reduce stroke risk. Findings: Multiple hierarchical regression analyses showed that, for exercise and weight loss respectively, different health beliefs predicted intention to control stroke risk. The most important exercise-related health beliefs were benefits, susceptibility, and self-efficacy; for weight loss, the most important beliefs were barriers, and to a lesser degree, susceptibility and subjective norm. Conclusions: Health beliefs may play an important role in stroke prevention, particularly beliefs about susceptibility because these emerged for both behaviours. Stroke education and prevention programmes that selectively target the health beliefs relevant to specific behaviours may prove most efficacious.

Reducing MRI gradient coil vibration with rib stiffeners

This work investigates the effect of rib stiffeners on the free and forced vibration of a gradient coil in a Magnetic Resonance Imaging (MRI) scanner. Several reinforcement schemes are studied in this paper. One scheme utilizes the existing holes in the gradient coil structure (typically reserved for magnetic shims) to produce the reinforcement. Non-ferrous, non-magnetic carbon fibre rib stiffeners are employed to fill these holes in several ways to strengthen a gradient coil. Another scheme replaces the inner half of the gradient coil material with a grid of interconnected axial and circumferential rib stiffeners. It is found that the structural stiffness of the gradient coil increases substantially when the coil is reinforced by carbon fibre rib stiffeners. The reinforcement affects the noise and vibration response of the gradient coil structure in the following ways. It increases the frequency range of forced response of the gradient coil at low frequencies due to the increased resonant frequency of the fundamental mode of the coil. Secondly, it reduces the forced response amplitude of the coil structure (which is governed by the structural stiffness of the coil). Thirdly, it reduces the number of natural modes in the low and medium frequency range and therefore lessens the chance of the coil structure being excited resonantly by magnetic resonance signal acquisition sequences. It is shown that gradient coils modelled by solid finite element models have higher stiffness along the coil’s circumference and lower stiffness in the axial direction than those using shell finite element models.

Real time detectionof airborne fungal spores and investigations into their dynamics in indoor air

Concern regarding the health effects of indoor air quality has grown in recent years, due to the increased prevalence of many diseases, as well as the fact that many people now spend most of their time indoors. While numerous studies have reported on the dynamics of aerosols indoors, the dynamics of bioaerosols in indoor environments are still poorly understood and very few studies have focused on fungal spore dynamics in indoor environments. Consequently, this work investigated the dynamics of fungal spores in indoor air, including fungal spore release and deposition, as well as investigating the mechanisms involved in the fungal spore fragmentation process. In relation to the investigation of fungal spore dynamics, it was found that the deposition rates of the bioaerosols (fungal propagules) were in the same range as the deposition rates of nonbiological particles and that they were a function of their aerodynamic diameters. It was also found that fungal particle deposition rates increased with increasing ventilation rates. These results (which are reported for the first time) are important for developing an understanding of the dynamics of fungal spores in the air. In relation to the process of fungal spore fragmentation, important information was generated concerning the airborne dynamics of the spores, as well as the part/s of the fungi which undergo fragmentation. The results obtained from these investigations into the dynamics of fungal propagules in indoor air significantly advance knowledge about the fate of fungal propagules in indoor air, as well as their deposition in the respiratory tract. The need to develop an advanced, real-time method for monitoring bioaerosols has become increasingly important in recent years, particularly as a result of the increased threat from biological weapons and bioterrorism. However, to date, the Ultraviolet Aerodynamic Particle Sizer (UVAPS, Model 3312, TSI, St Paul, MN) is the only commercially available instrument capable of monitoring and measuring viable airborne micro-organisms in real-time. Therefore (for the first time), this work also investigated the ability of the UVAPS to measure and characterise fungal spores in indoor air. The UVAPS was found to be sufficiently sensitive for detecting and measuring fungal propagules. Based on fungal spore size distributions, together with fluorescent percentages and intensities, it was also found to be capable of discriminating between two fungal spore species, under controlled laboratory conditions. In the field, however, it would not be possible to use the UVAPS to differentiate between different fungal spore species because the different micro-organisms present in the air may not only vary in age, but may have also been subjected to different environmental conditions. In addition, while the real-time UVAPS was found to be a good tool for the investigation of fungal particles under controlled conditions, it was not found to be selective for bioaerosols only (as per design specifications). In conclusion, the UVAPS is not recommended for use in the direct measurement of airborne viable bioaerosols in the field, including fungal particles, and further investigations into the nature of the micro-organisms, the UVAPS itself and/or its use in conjunction with other conventional biosamplers, are necessary in order to obtain more realistic results. Overall, the results obtained from this work on airborne fungal particle dynamics will contribute towards improving the detection capabilities of the UVAPS, so that it is capable of selectively monitoring and measuring bioaerosols, for which it was originally designed. This work will assist in finding and/or improving other technologies capable of the real-time monitoring of bioaerosols. The knowledge obtained from this work will also be of benefit in various other bioaerosol applications, such as understanding the transport of bioaerosols indoors.

Layered titanate nanofibers as efficient adsorbents for removal of toxic radioactive and heavy metal ions from water

Titanate nanofibers with two formulas, Na2Ti3O7 and Na1.5H0.5Ti3O7, respectively, exhibit ideal properties for removal of radioactive and heavy metal ions in wastewater, such as Sr2+ , Ba2+ (as substitute of 226Ra2+), and Pb2+ ions. These nanofibers can be fabricated readily by a reaction between titania and caustic soda and have structures in which TiO6 octahedra join each other to form layers with negative charges; the sodium cations exist within the interlayer regions and are exchangeable. They can selectively adsorb the bivalent radioactive ions and heavy metal ions from water through ion exchange process. More importantly, such sorption finally induces considerable deformation of the layer structure, resulting in permanent entrapment of the toxic bivalent cations in the fibers so that the toxic ions can be safely deposited. This study highlights that nanoparticles of inorganic ion exchangers with layered structure are potential materials for efficient removal of the toxic ions from contaminated water.

The new wave : a Brisbane perspective : La Boite Theatre Company's distinctive contribution

In 1967 Brisbane Repertory Theatre made a decision that was to change the city's cultural landscape in a significant and lasting way. Faced with crippling theatre rental costs, Brisbane Rep. found a realistic solution by converting one of its properties - an old Queenslander - into a unique theatre space. The theatre-in-the box that emerged, aptly called La Boite, opened on 23 June 1967 with a production of John Osborne's Look Back in Anger. This experimental space excited the imagination of a new, younger audience not previously interested in Brisbane Rep's essentially conservative fare. It attracted a new group of directors and actors keen to be part of a changing repertoire that embraced more radical, non-mainstream productions, some of which were of Australian plays. The decade after 1967 was a period of change and development unprecedented in La Boite's history. Since then the company has sustained and grown its commitment to Australian plays and the commissioning of new works. To what extent was this most significance moment in La Boite's transformational journey influenced by southern 'new waves' of change? With the benefit of hindsight, it is now time for a re-consideration of Brisbane's distinctive contribution to the New Wave.

From China with love

Like the Montagues and the Capulets, the East and West have had a great many affairs that have stirred suspicions of one another. But for those of us fortunate enough to cross the cultural divide, Gillian Lawson says there is much about which to be curious, excited and anxious.

Flexible high-power multi DC-DC converters for train systems

This thesis reports on the investigations, simulations and analyses of novel power electronics topologies and control strategies. The research is financed by an Australian Research Council (ARC) Linkage (07-09) grant. Therefore, in addition to developing original research and contributing to the available knowledge of power electronics, it also contributes to the design of a DC-DC converter for specific application to the auxiliary power supply in electric trains. Specifically, in this regard, it contributes to the design of a 7.5 kW DC-DC converter for the industrial partner (Schaffler and Associates Ltd) who supported this project. As the thesis is formatted as a ‘thesis by publication’, the contents are organized around published papers. The research has resulted in eleven papers, including seven peer reviewed and published conference papers, one published journal paper, two journal papers accepted for publication and one submitted journal paper (provisionally accepted subject to few changes). In this research, several novel DC-DC converter topologies are introduced, analysed, and tested. The similarity of all of the topologies devised lies in their ‘current circulating’ switching state, which allows them to store some energy in the inductor, as extra inductor current. The stored energy may be applied to enhance the performance of the converter in the occurrence of load current or input voltage disturbances. In addition, when there is an alternating load current, the ability to store energy allows the converter to perform satisfactorily despite frequently and highly varying load current. In this research, the capability of current storage has been utilised to design topologies for specific applications, and the enhancement of the performance of the considered applications has been illustrated. The simplest DC-DC converter topology, which has a ‘current circulating’ switching state, is the Positive Buck-Boost (PBB) converter (also known as the non-inverting Buck-Boost converter). Usually, the topology of the PBB converter is operating as a Buck or a Boost converter in applications with widely varying input voltage or output reference voltage. For example, in electric railways (the application of our industrial partner), the overhead line voltage alternates from 1000VDC to 500VDC and the required regulated voltage is 600VDC. In the course of this research, our industrial partner (Schaffler and Associates Ltd) industrialized a PBB converter–the ‘Mudo converter’–operating at 7.5 kW. Programming the onboard DSP and testing the PBB converter in experimental and nominal power and voltage was part of this research program. In the earlier stages of this research, the advantages and drawbacks of utilization of the ‘current circulating’ switching state in the positive Buck-Boost converter were investigated. In brief, the advantages were found to be robustness against input voltage and current load disturbances, and the drawback was extra conduction and switching loss. Although the robustness against disturbances is desirable for many applications, the price of energy loss must be minimized to attract attention to the utilization of the PBB converter. In further stages of this research, two novel control strategies for different applications were devised to minimise the extra energy loss while the advantages of the positive Buck-Boost converter were fully utilized. The first strategy is Smart Load Controller (SLC) for applications with pre-knowledge or predictability of input voltage and/or load current disturbances. A convenient example of these applications is electric/hybrid cars where a master controller commands all changes in loads and voltage sources. Therefore, the master controller has a pre-knowledge of the load and input voltage disturbances so it can apply the SLC strategy to utilize robustness of the PBB converter. Another strategy aiming to minimise energy loss and maximise the robustness in the face of disturbance is developed to cover applications with unexpected disturbances. This strategy is named Dynamic Hysteresis Band (DHB), and is used to manipulate the hysteresis band height after occurrence of disturbance to reduce dynamics of the output voltage. When no disturbance has occurred, the PBB converter works with minimum inductor current and minimum energy loss. New topologies based on the PBB converter have been introduced to address input voltage disturbances for different onboard applications. The research shows that the performance of applications of symmetrical/asymmetrical multi-level diode-clamped inverters, DC-networks, and linear-assisted RF amplifiers may be enhanced by the utilization of topologies based on the PBB converter. Multi-level diode-clamped inverters have the problem of DC-link voltage balancing when the power factor of their load closes to unity. This research has shown that this problem may be solved with a suitable multi-output DC-DC converter supplying DClink capacitors. Furthermore, the multi-level diode-clamped inverters supplied with asymmetrical DC-link voltages may improve the quality of load voltage and reduce the level of Electromagnetic Interference (EMI). Mathematical analyses and experiments on supplying symmetrical and asymmetrical multi-level inverters by specifically designed multi-output DC-DC converters have been reported in two journal papers. Another application in which the system performance can be improved by utilization of the ‘current circulating’ switching state is linear-assisted RF amplifiers in communicational receivers. The concept of ‘linear-assisted’ is to divide the signal into two frequency domains: low frequency, which should be amplified by a switching circuit; and the high frequency domain, which should be amplified by a linear amplifier. The objective is to minimize the overall power loss. This research suggests using the current storage capacity of a PBB based converter to increase its bandwidth, and to increase the domain of the switching converter. The PBB converter addresses the industrial demand for a DC-DC converter for the application of auxiliary power supply of a typical electric train. However, after testing the industrial prototype of the PBB converter, there were some voltage and current spikes because of switching. To attenuate this problem without significantly increasing the switching loss, the idea of Active Gate Signalling (AGS) is presented. AGS suggests a smart gate driver that selectively controls the switching process to reduce voltage/current spikes, without unacceptable reduction in the efficiency of switching.

Polymersomes, smaller than you think : ferrocene as a TEM probe to determine core structure

By incorporating ferrocene into the hydrophobic membrane of PEG-b-PCL polymersome nanoparticles it is possible to selectively visualize their core using Transmission Electron Microscopy (TEM). Two different sizes of ferrocene-loaded polymersomes with mean hydrodynamic diameters of approximately 40 and 90 nm were prepared. Image analysis of TEM pictures of these polymersomes found that the mean diameter of the core was 4–5 times smaller than the mean hydrodynamic diameter. The values obtained also allow the surface diameter and internal volume of the core to be calculated.

Vibrational spectroscopic studies of wool

Fourier transfonn (FT) Raman, Raman microspectroscopy and Fourier transform infrared (FTIR) spectroscopy have been used for the structural analysis and characterisation of untreated and chemically treated wool fibres. For FT -Raman spectroscopy novel methods of sample presentation have been developed and optimised for the analysis of wool. No significant fluorescence was observed and the spectra could be obtained routinely. The stability of wool keratin to the laser source was investigated and the visual and spectroscopic signs of sample damage were established. Wool keratin was found to be extremely robust with no signs of sample degradation observed for laser powers of up to 600 m W and for exposure times of up to seven and half hours. Due to improvements in band resolution and signal-to-noise ratio, several previously unobserved spectral features have become apparent. The assignment of the Raman active vibrational modes of wool have been reviewed and updated to include these features. The infrared spectroscopic techniques of attenuated total reflectance (ATR) and photoacoustic (P A) have been used to examine shrinkproofed and mothproofed wool samples. Shrinkproofing is an oxidative chemical treatment used to selectively modifY the surface of a wool fibre. Mothproofing is a chemical treatment applied to wool for the prevention of insect attack. The ability of PAS and A TR to vary the penetration depth by varying certain instrumental parameters was used to obtain spectra of the near surface regions of these chemically treated samples. These spectra were compared with those taken with a greater penetration depth, which therefore represent more of the bulk wool sample. The PA and ATR spectra demonstrated that oxidation was restricted to the near-surface layer of wool. Extensive curve fitting of ATR spectra of untreated wool indicated that cuticle was composed of a mixed protein conformation, but was predominately that of an a.-helix. The cortex was proposed to be a mixture of both a.helical and ~-pleated sheet protein conformations. These findings were supported by PAS depth profiling results. Raman microspectroscopy was used in an extensive investigation of the molecular structure of the wool fibre. This included determining the orientation of certain functional groups within the wool fibre and the symmetry of particular vibrations. The orientation ofbonds within the wool fibre was investigated by orientating the wool fibre axis parallel and then perpendicular to the plane of polarisation of the electric vector of the incident radiation. It was experimentally determined that the majority of C=O and N-H bonds of the peptide bond of wool lie parallel to the fibre axis. Additionally, a number of the important vibrations associated with the a-helix were also found to lie parallel to the fibre axis. Further investigation into the molecular structure of wool involved determining what effect stretching the wool fibre had on bond orientation. Raman spectra of stretched and unstretched wool fibres indicated that extension altered the orientation ofthe aromatic rings, the CH2 and CH3 groups of the amino acids. Curve fitting results revealed that extension resulted in significant destruction of the a-helix structure a substantial increase in the P-pleated sheet structure. Finally, depolarisation ratios were calculated for Raman spectra. The vibrations associated with the aromatic rings of amino acids had very low ratios which indicated that the vibrations were highly symmetrical.