Electron-accepting conjugated materials based on 2-Vinyl-4,5- dicyanoimidazoles for application in organic electronics

We report the Heck coupling of 2-vinyl-4,5-dicyanoimidazole (vinazene) with selected di- and trihalo aromatics in an effort to prepare linear and branched electron-accepting conjugated materials for application in organic electronics. By selecting the suitable halo-aromatic moiety, it is possible to tune the HOMO - LUMO energy levels, absorption, and emission properties for a specific application. In this regard, materials with strong photoluminescence from blue → green → red are reported that may have potential application in organic light-emitting diodes (OLEDs). Furthermore, derivatives with strong absorption in the visible spectrum, coupled with favorable HOMO-LUMO levels, have been used to prepare promising organic photovoltaic devices (OPVs) when combined with commercially available semiconducting donor polymers.

Synthesis, characterization and comparative study of thiophene- benzothiadiazole based donor-acceptor-donor (D-A-D) materials

The synthesis and characterization of solution processable donor-acceptor-donor (D-A-D) based conjugated molecules with varying ratios of thiophene as donor (D) and benzothiadiazole as acceptor (A) are reported. Optical, electrochemical, thermal, morphological and organic thin film transistor (OTFT) device properties of these materials were investigated. The thermal and polarized optical microscope analysis indicates that the materials having higher D/A ratios exhibit both liquid crystalline (LC) and OTFT behavior. AFM analysis of the materials having D/A ratios of 3 and 4 (3T1B and 4T1B) show well ordered structures, resulting from strong π-π interchain interactions compared to the other molecules in this study. A XRD patterns for 3T1B and 4T1B thin films also shows high crystalline ordering. Solution processed OTFTs of 3T1B and 4T1B have shown un-optimized charge carrier mobilities of 2 × 10 -2 cm 2 V -1 s -1 and 4 × 10 -3 cm 2 V -1 s -1, respectively on bare Si/SiO 2 substrate.

Isoindigo dye incorporated copolymers with naphthalene and anthracene: promising materials for stable organic field effect transistors

In this paper, we report the design and synthesis of isoindigo based low band gap polymer semiconductors, poly{N,N′-(2-octyldodecyl)-isoindigo-alt- naphthalene} (PISD-NAP) and poly{N,N′-(2-octyldodecyl)-isoindigo-alt- anthracene} (PISD-ANT). A series of donor-acceptor (D-A) copolymers can be prepared where donor and acceptor conjugated blocks can be attached alternately using organometallic coupling. In these polymers, an isoindigo dye acceptor moiety has been attached alternately with naphthalene and anthracene donor comonomer blocks by Suzuki coupling. PISD-NAP and PISD-ANT exhibit excellent solution processibility and good film-forming properties. Gel permeation chromatography exhibits a higher molecular mass with lower polydispersity. UV-vis-NIR absorption of these polymers exhibits a wide absorption band ranging from 300 nm to 800 nm, indicating the low band gap nature of the polymers. Optical band gaps calculated from the solid state absorption cutoff value for PISD-NAP and PISD-ANT are around 1.80 eV and 1.75 eV, respectively. Highest occupied molecular orbital (HOMO) values calculated respectively for PISD-NAP and PISD-ANT thin films on glass substrate by photoelectron spectroscopy in air (PESA) are 5.66 eV and 5.53 eV, indicative of the good stability of these materials in organic electronic device applications. These polymers exhibit p-channel charge transport characteristics when used as the active semiconductor in organic thin-film transistor (OTFT) devices in ambient conditions. The highest hole mobility of 0.013 cm2 V-1 s-1 is achieved in top contact and bottom-gate OTFT devices for PISD-ANT, whereas polymer PISD-NAP exhibited a hole mobility of 0.004 cm2 V -1 s-1. When these polymer semiconductors were used as a donor and PC71BM as an acceptor in OPV devices, the highest power conversion efficiency (PCE) of 1.13% is obtained for the PISD-ANT polymer.

Achieving transparency in carbon labelling for construction materials – Lessons from current assessment standards and carbon labels

The construction industry is one of the largest sources of carbon emissions. Manufacturing of raw materials, such as cement, steel and aluminium, is energy intensive and has considerable impact on carbon emissions level. Due to the rising recognition of global climate change, the industry is under pressure to reduce carbon emissions. Carbon labelling schemes are therefore developed as meaningful yardsticks to measure and compare carbon emissions. Carbon labelling schemes can help switch consumer-purchasing habits to low-carbon alternatives. However, such switch is dependent on a transparent scheme. The principle of transparency is highlighted in all international greenhouse gas (GHG) standards, including the newly published ISO 14067: Carbon footprint of products – requirements and guidelines for quantification and communication. However, there are few studies which systematically investigate the transparency requirements in carbon labelling schemes. A comparison of five established carbon labelling schemes, namely the Singapore Green Labelling Scheme, the CarbonFree (the U.S.), the CO2 Measured Label and the Reducing CO2 Label (UK), the CarbonCounted (Canada), and the Hong Kong Carbon Labelling Scheme is therefore conducted to identify and investigate the transparency requirements. The results suggest that the design of current carbon labels have transparency issues relating but not limited to the use of a single sign to represent the comprehensiveness of the carbon footprint. These transparency issues are partially caused by the flexibility given to select system boundary in the life cycle assessment (LCA) methodology to measure GHG emissions. The primary contribution of this study to the construction industry is to reveal the transparency requirements from international GHG standards and carbon labels for construction products. The findings also offer five key strategies as practical implications for the global community to improve the performance of current carbon labelling schemes on transparency.

Clinical utility of exhaled nitric oxide

Lower airway inflammation is generally classified as eosinophilic or neutrophilic. In conditions where eosinophilic inflammation predominates such as asthma in children, corticosteroids are usually beneficial. Traditionally, lower airway eosinophilia is measured using cellular count (through bronchoalveolar lavage or induced sputum). Both methods have limited applicability in children. When instruments to measure fractional exhaled nitric oxide (FeNO) became available, it presented an attractive option as it provided a non-invasive method of measuring eosinophilic inflammation suitable for children and adult. Not surprisingly, proposals have been made that FeNO measurement can be clinically used in many scenarios including monitoring the response to anti-inflammatory medications, to verify the adherence to treatment, and to predict upcoming asthma exacerbations. This thesis addresses the utility of FeNO levels in various scenarios, specifically in relation to asthma control and cough, a contentious aspect of the diagnosis of asthma. The thesis consists of a series of systematic reviews (related to the main question) and original studies in children. The over-arching aim of the thesis is to determine if FeNO is a clinically useful tool in the management of asthma and common asthma symptoms. The specific aims of the thesis were, to: 1. Determine if children with asthma have more severe acute respiratory symptoms at presentation with an asthma exacerbation and at days 7, 10 and 14 using validated scales. We also examined if children with asthma were more likely to have a persistent cough on day 14 than children with protracted bronchitis and/or controls. 2. Evaluate the efficacy of tailoring asthma interventions based on sputum analysis in comparison to clinical symptoms (with or without spirometry/peak flow) for asthma related outcomes in children and adults. 3. Evaluate the efficacy of tailoring asthma interventions based on exhaled nitric oxide in comparison to clinical symptoms (with or without spirometry/peak flow) for asthma related outcomes in children and adults. 4. Determine if adjustment of asthma medications based on FeNO levels (compared to management based on clinical symptoms) reduces severe exacerbations in children with asthma. 5. Examine the relationship between FeNO and exercise induced broncho-constriction and cough in children The aims above are addressed in respective chapters and all but one has been published/submitted. A synopsis of the findings are: In study-1 (Aim 1), we found that children with protracted bronchitis had the most severe acute respiratory infection symptoms and higher percentage of respiratory morbidity at day 14 in comparison to children with asthma and healthy controls. The systematic review of study-2 (Aim 2) included 246 randomised adult participants (no children) with 221 completing the trials. In the meta-analysis, a significant reduction in number of participants who had one or more asthma exacerbations occurred when treatment was based on sputum eosinophils in comparison to clinical symptoms. In the systematic review of study-3 (Aim 3), we found no significant difference between the intervention group (treatment adjusted based on FeNO) and control group (treatment adjusted based on clinical symptoms) for the primary outcome of asthma exacerbations or for the other outcomes (clinical symptoms, FeNO level and spirometry). In post-hoc analysis, a significant reduction in mean final daily dose ICS per adult was found in the group where treatment was based on FeNO in comparison to clinical symptoms. In contrast, in the paediatric studies, there was a significant increase in ICS dose in the FeNO strategy arm. Thus, controversy remains of the benefit or otherwise of utilising exhaled nitric oxide (FeNO) in routine clinical practice. FeNO levels are dependent on atopy and none of the 7 published trials have considered atopic status in FeNO levels when medications were adjusted. In study-4 (Aim 4), 64 children with asthma were recruited. Their asthma medications were adjusted according to either FeNO levels or usual clinical care utilising a management hierarchy taking into account atopy. It was concluded that tailoring of asthma medications in accordance to FeNO levels (compared to usual management), taking into account atopy status, reduced the number of children with severe exacerbations. However, a FeNO-based strategy resulted in higher daily ICS doses and had no benefit on asthma control. In study-5 (Aim 5), 33 children with cough and 17 controls were recruited. They were randomised to undertake an exercise challenge on day 1, or dry powder mannitol challenge on day 1 (with alternative challenge being done on day 2). In addition, a 24 hour cough meter, skin prick test, capsaicin cough sensitivity test and cough diary were undertaken. The change in cough frequency post exercise was significantly increased in the children with cough. FeNO decreases post exercise regardless of whether EIB is present or not. Limitations in the studies were addressed in the respective chapters. In summary, the studies from this thesis have provided new information on: • The severity of respiratory symptoms was increased in the early phase of the asthma exacerbation but not in the later recovery phase when compared with controls. • The utility of FeNO in the management of children with asthma. • The relationship of FeNO, cough and EIB in children. • Systematic reviews on the efficacy of tailoring asthma interventions based on eosinophilic inflammatory markers (sputum analysis and FeNO) in comparison to clinical symptoms.

Engineering thin film semiconductor gas sensors to increase sensitivity and decrease operation temperature

Thin film nanostructured gas sensors typically operate at temperatures above 400°C, but lower temperature operation is highly desirable, especially for remote area field sensing as this reduces significantly power consumption. We have investigated a range of sensor materials based on both pure and doped tungsten oxide (mainly focusing on Fe-doping), deposited using both thermal evaporation and electron-beam evaporation, and using a variety of post-deposition annealing. The films show excellent sensitivity at operating temperatures as low as 150°C for detection of NO2. There is a definite relationship between the sensitivity and the crystallinity and nanostructure obtained through the deposition and heat treatment processes, as well as variations in the conductivity caused both by doping and heat treatmetn. The ultimate goal of this work is to control the sensing properties, including selectivity to specific gases through the engineering of the electronic properties and the nanostructure of the films.