Fabrication and characterization of plasma polymer thin films from monoterpene alcohols for applications in organic electronics and biotechnology

After more than twenty years of basic and applied research, the use of nanotechnology in the design and manufacture of nanoscale materials is rapidly increasing, particularly in commercial applications that span from electronics across renewable energy areas, and biomedical devices. Novel polymers are attracting significant attention for they promise to provide a low−cost high−performance alternative to existing materials. Furthermore, these polymers have the potential to overcome limitations imposed by currently available materials thus enabling the development of new technologies and applications that are currently beyond our reach. This work focuses on the development of a range of new low−cost environmentally−friendly polymer materials for applications in areas of organic (flexible) electronics, optics, and biomaterials. The choice of the monomer reflects the environmentally−conscious focus of this project. Terpinen−4−ol is a major constituent of Australian grown Melaleuca alternifolia (tea tree) oil, attributed with the oil's antimicrobial and anti−inflammatory properties. Plasma polymerisation was chosen as a deposition technique for it requires minimal use of harmful chemicals and produces no hazardous by−products. Polymer thin films were fabricated under varied process conditions to attain materials with distinct physico−chemical, optoelectrical, biological and degradation characteristics. The resultant materials, named polyterpenol, were extensively characterised using a number of well−accepted and novel techniques, and their fundamental properties were defined. Polyterpenol films were demonstrated to be hydrocarbon rich, with variable content of oxygen moieties, primarily in the form of hydroxyl and carboxyl functionalities. The level of preservation of original monomer functionality was shown to be strongly dependent on the deposition energy, with higher applied power increasing the molecular fragmentation and substrate temperature. Polyterpenol water contact angle contact angle increased from 62.7° for the 10 W samples to 76.3° for the films deposited at 100 W. Polymers were determined to resist solubilisation by water, due to the extensive intermolecular and intramolecular hydrogen bonds present, and other solvents commonly employed in electronics and biomedical processing. Independent of deposition power, the surface topography of the polymers was shown to be smooth (Rq <0.5 nm), uniform and defect free. Hardness of polyterpenol coatings increased from 0.33 GPa for 10 W to 0.51 GPa for 100 W (at 500 μN load). Coatings deposited at higher input RF powers showed less mechanical deformation during nanoscratch testing, with no considerable damage, cracking or delamination observed. Independent of the substrate, the quality of film adhesion improved with RF power, suggesting these coatings are likely to be more stable and less susceptible to wear. Independent of fabrication conditions, polyterpenol thin films were optically transparent, with refractive index approximating that of glass. Refractive index increased slightly with deposition power, from 1.54 (10 W) to 1.56 (100 W) at 500 nm. The optical band gap values declined with increasing power, from 2.95 eV to 2.64 eV, placing the material within the range for semiconductors. Introduction of iodine impurity reduced the band gap of polyterpenol, from 2.8 eV to 1.64 eV, by extending the density of states more into the visible region of the electromagnetic spectrum. Doping decreased the transparency and increased the refractive index from 1.54 to 1.70 (at 500 nm). At optical frequencies, the real part of permittivity (k) was determined to be between 2.34 and 2.65, indicating a potential low-k material. These permittivity values were confirmed at microwave frequencies, where permittivity increased with input RF energy – from 2.32 to 2.53 (at 10 GHz ) and from 2.65 to 2.83 (at 20 GHz). At low frequencies, the dielectric constant was determined from current−voltage characteristics of Al−polyterpenol−Al devices. At frequencies below 100 kHz, the dielectric constant varied with RF power, from 3.86 to 4.42 at 1 kHz. For all samples, the resistivity was in order of 10⁸−10⁹ _m (at 6 V), confirming the insulating nature of polyterpenol material. In situ iodine doping was demonstrated to increase the conductivity of polyterpenol, from 5.05 × 10⁻⁸ S/cm to 1.20 × 10⁻⁶ S/cm (at 20 V). Exposed to ambient conditions over extended period of time, polyterpenol thin films were demonstrated to be optically, physically and chemically stable. The bulk of ageing occurred within first 150 h after deposition and was attributed to oxidation and volumetric relaxation. Thermal ageing studies indicated thermal stability increased for the films manufactured at higher RF powers, with degradation onset temperature associated with weight loss shifting from 150 ºC to 205 ºC for 10 W and 100 W polyterpenol, respectively. Annealing the films to 405 °C resulted in full dissociation of the polymer, with minimal residue. Given the outcomes of the fundamental characterisation, a number of potential applications for polyterpenol have been identified. Flexibility, tunable permittivity and loss tangent properties of polyterpenol suggest the material can be used as an insulating layer in plastic electronics. Implementation of polyterpenol as a surface modification of the gate insulator in pentacene-based Field Effect Transistor resulted in significant improvements, shifting the threshold voltage from + 20 V to –3 V, enhancing the effective mobility from 0.012 to 0.021 cm²/Vs, and improving the switching property of the device from 10⁷ to 10⁴. Polyterpenol was demonstrated to have a hole transport electron blocking property, with potential applications in many organic devices, such as organic light emitting diodes. Encapsulation of biomedical devices is also proposed, given that under favourable conditions, the original chemical and biological functionality of terpinen−4−ol molecule can be preserved. Films deposited at low RF power were shown to successfully prevent adhesion and retention of several important human pathogens, including P. aeruginosa, S. aureus, and S. epidermidis, whereas films deposited at higher RF power promoted bacterial cell adhesion and biofilm formation. Preliminary investigations into in vitro biocompatibility of polyterpenol demonstrated the coating to be non−toxic for several types of eukaryotic cells, including Balb/c mice macrophage and human monocyte type (HTP−1 non-adherent) cells. Applied to magnesium substrates, polyterpenol encapsulating layer significantly slowed down in vitro biodegradation of the metal, thus increasing the viability and growth of HTP−1 cells. Recently, applied to varied nanostructured titanium surfaces, polyterpenol thin films successfully reduced attachment, growth, and viability of P. aeruginosa and S. aureus.

Bioactivity of tea tree oil from Melaleuca alternifolia against sheep lice (Bovicola ovis Schrank) in vitro

Tea tree oil (TTO) from the Australian native plant Melaleuca alternifolia has wide ranging bio-active properties, including insecticidal and repellent activity against arthropods. Furthermore, composition of commercially available Australian TTO is specified under an International Organization for Standardization standard (ISO 4730), reducing the potential for variable effects often noted with botanical pesticides. The effect of TTO, meeting the ISO standard for terpinen-4-ol chemotype, was tested against sheep lice (Bovicola ovis Schrank) in a series of laboratory studies. Immersion of wool for 60s in formulations containing concentrations of 1% TTO and above caused 100% mortality of adult lice and eggs. Exposure to vapours from TTO, delivered as droplets in fumigation chambers and when applied to wool also caused high mortality in both lice and eggs. The main active component of TTO in the fumigant tests was terpinen-4-ol. Treated surface assays and tests with wool where the formulation was allowed to dry before exposure of lice indicated low persistence. These studies demonstrate that TTO is highly toxic to sheep lice and active at concentrations that suggest potential for the development of TTO-based ovine lousicides. (C) 2012 Elsevier B.V. All rights reserved.

Mechanism of improvement in oil spreadability of aluminium alloy-graphite particle composites

The spreadability of SAE-30 oil on Al-12 Si base (LM-13) alloy containing dispersed graphite particles about 50 μm average size in its matrix is found to be greater than on either LM-13 with no graphite or brass. It is also found that the spreadability on LM-13 base alloys increase with increasing volume of graphite dispersion in the matrix of these alloys. Further increases in the spreadability of oil on machined LM-13-graphite particle composite test surfaces occur if these are rubbed initially against control discs of either LM-13 or grey cast iron. The formation of a triboinduced graphite-rich layer, confirmed by esca, appears to be responsible for the improved oil spreadability on the rubbed test surfaces of LM-13 base alloys as compared to the as-machined test surfaces prior to rubbing. The triboinduced layer of graphite is apparently responsible for the observed reduction in the friction, wear and seizing tendency of triboelements made from aluminium alloy-graphite particle composites.

Photographic reproduction of oil painting portrait of Samuel Meyer Ehrenberg Portraits Men

Original painting with Louis Rosenzweig, New Haven, CT

Effect of phenolic-rich plant materials on protein and lipid oxidation reactions

The antioxidant activity of natural plant materials rich in phenolic compounds is being widely investigated for protection of food products sensitive to oxidative reactions. In this thesis plant materials rich in phenolic compounds were studied as possible antioxidants to prevent protein and lipid oxidation reactions in different food matrixes such as pork meat patties and corn oil-in water emulsions. Loss of anthocyanins was also measured during oxidation in corn oil-in-water emulsions. In addition, the impact of plant phenolics on amino acid level was studied using tryptophan as a model compound to elucidate their role in preventing the formation of tryptophan oxidation products. A high-performance liquid chromatography (HPLC) method with ultraviolet and fluorescence detection (UV-FL) was developed that enabled fast investigation of formation of tryptophan derived oxidation products. Byproducts of oilseed processes such as rapeseed (Brassica rapa L.), camelina (Camelina sativa) and soy meal (Glycine max L.) as well as Scots pine bark (Pinus sylvestris) and several reference compounds were shown to act as antioxidants toward both protein and lipid oxidation in cooked pork meat patties. In meat, the antioxidant activity of camelina, rapeseed and soy meal were more pronounced when used in combination with a commercial rosemary extract (Rosmarinus officinalis). Berry phenolics such as black currant (Ribes nigrum) anthocyanins and raspberry (Rubus idaeus) ellagitannins showed potent antioxidant activity in corn oil-in-water emulsions toward lipid oxidation with and without β-lactoglobulin. The antioxidant effect was more pronounced in the presence of β-lactoglobulin. The berry phenolics also inhibited the oxidation of tryptophan and cysteine side chains of β-lactoglobulin. The results show that the amino acid side chains were oxidized prior the propagation of lipid oxidation, thereby inhibiting fatty acid scission. In addition, the concentration and color of black currant anthocyanins decreased during the oxidation. Oxidation of tryptophan was investigated in two different oxidation models with hydrogen peroxide (H2O2) and hexanal/FeCl2. Oxidation of tryptophan in both models resulted in oxidation products such as 3a-hydroxypyrroloindole-2-carboxylic acid, dioxindolylalanine, 5-hydroxy-tryptophan, kynurenine, N-formylkynurenine and β-oxindolylalanine. However, formation of tryptamine was only observed in tryptophan oxidized in the presence of H2O2. Pine bark phenolics, black currant anthocyanins, camelina meal phenolics as well as cranberry proanthocyanidins (Vaccinium oxycoccus) provided the best antioxidant effect toward tryptophan and its oxidation products when oxidized with H2O2. The tryptophan modifications formed upon hexanal/FeCl2 treatment were efficiently inhibited by camelina meal followed by rapeseed and soy meal. In contrast, phenolics from raspberry, black currant, and rowanberry (Sorbus aucuparia) acted as weak prooxidants. This thesis contributes to elucidating the effects of natural phenolic compounds as potential antioxidants in order to control and prevent protein and lipid oxidation reactions. Understanding the relationship between phenolic compounds and proteins as well as lipids could lead to the development of new, effective, and multifunctional antioxidant strategies that could be used in food, cosmetic and pharmaceutical applications.

Photograph of oil painting portrait of Samuel Loewen; Berlin Portraits Men

Handwritten description on verso

Consequences of Corymbia (Myrtaceae) hybridisation on leaf-oil profiles

The present study examines patterns of heritability of plant secondary metabolites following hybridisation among three genetically homogeneous taxa of spotted gum (Corymbia henryi (S.T.Blake) K.D.Hill & L.A.S.Johnson, C. citriodora subsp. variegata (F.Muell.) K.D.Hill & L.A.S.Johnson and C. citriodora (Hook.) K.D.Hill & L.A.S.Johnson subsp. citriodora (section Maculatae), and their congener C. torelliana (F.Muell.) K.D.Hill & L.A.S.Johnson (section Torellianae)). Hexane extracts of leaves of all four parent taxa were statistically distinguishable (ANOSIM: global R = 0.976, P = 0.008). Hybridisation patterns varied among the taxa studied, with the hybrid formed with C. citriodora subsp. variegata showing an intermediate extractive profile between its parents, whereas the profiles of the other two hybrids were dominated by that of C. torelliana. These different patterns in plant secondary-metabolite inheritance may have implications for a range of plant-insect interactions.

Photograph of oil painting portrait by Olaf Segerfeldt of Rudolf Simonis Portraits Men

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A lifespan perspective on emotion regulation, stress, and well-being in the workplace

Researchers in the field of occupational stress and well-being are increasingly interested in the role of emotion regulation in the work context. Emotion regulation has also been widely investigated in the area of lifespan developmental psychology, with findings indicating that the ability to modify one's emotions represents a domain in which age-related growth is possible. In this chapter, we integrate the literatures on aging, emotion regulation, and occupational stress and well-being. To this end, we review key theories and empirical findings in each of these areas, summarize existing research on age, emotion regulation, and stress and well-being at work, and develop a conceptual model on how aging affects emotion regulation and the stress process in work settings to guide future research. According to the model, age will affect: (1) what kinds of affective work events are encountered and how often; (2) the appraisal of and initial emotional response to affective work events (emotion generation), and; (3) the management of emotions and coping with affective work events (emotion regulation). The model has implications for researchers and practitioners who want to understand and facilitate successful emotion regulation and stress reduction in the workplace among different age groups.

Reproduction of oil painting portrait of Liepmann Seligmann Danziger Portraits Men

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Reproduction of oil painting portrait of Judith Danziger nee Nathan Portraits Women

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Reproduction of oil painting portrait of Sara Pesche Polack nee Ruben Hirsch Portraits Women

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Reproduction of oil painting portrait of Ernestine Salomonsen nee Philip Portraits Women

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The buffering effect of selection, optimization, and compensation strategy use on the relationship between problem solving demands and occupational well-being: A daily diary study

This study investigated within-person relationships between daily problem solving demands, selection, optimization, and compensation (SOC) strategy use, job satisfaction, and fatigue at work. Based on conservation of resources theory, it was hypothesized that high SOC strategy use boosts the positive relationship between problem solving demands and job satisfaction, and buffers the positive relationship between problem solving demands and fatigue. Using a daily diary study design, data were collected from 64 administrative employees who completed a general questionnaire and two daily online questionnaires over four work days. Multilevel analyses showed that problem solving demands were positively related to fatigue, but unrelated to job satisfaction. SOC strategy use was positively related to job satisfaction, but unrelated to fatigue. A buffering effect of high SOC strategy use on the demands-fatigue relationship was found, but no booster effect on the demands-satisfaction relationship. The results suggest that high SOC strategy use is a resource that protects employees from the negative effects of high problem solving demands.