Removal of organic content from diesel exhaust particles alters cellular responses of primary human bronchial epithelial cells cultured at an air-liquid interface

Background Exposure to air pollutants, including diesel particulate matter, has been linked to adverse respiratory health effects. Inhaled diesel particulate matter contains adsorbed organic compounds. It is not clear whether the adsorbed organics or the residual components are more deleterious to airway cells. Using a physiologically relevant model, we investigated the role of diesel organic content on mediating cellular responses of primary human bronchial epithelial cells (HBECs) cultured at an air-liquid interface (ALI). Methods Primary HBECs were cultured and differentiated at ALI for at least 28 days. To determine which component is most harmful, we compared primary HBEC responses elicited by residual (with organics removed) diesel emissions (DE) to those elicited by neat (unmodified) DE for 30 and 60 minutes at ALI, with cigarette smoke condensate (CSC) as the positive control, and filtered air as negative control. Cell viability (WST-1 cell proliferation assay), inflammation (TNF-α, IL-6 and IL-8 ELISA) and changes in gene expression (qRT-PCR for HO-1, CYP1A1, TNF-α and IL-8 mRNA) were measured. Results Immunofluorescence and cytological staining confirmed the mucociliary phenotype of primary HBECs differentiated at ALI. Neat DE caused a comparable reduction in cell viability at 30 or 60 min exposures, whereas residual DE caused a greater reduction at 60 min. When corrected for cell viability, cytokine protein secretion for TNF-α, IL-6 and IL-8 were maximal with residual DE at 60 min. mRNA expression for HO-1, CYP1A1, TNF-α and IL-8 was not significantly different between exposures. Conclusion This study provides new insights into epithelial cell responses to diesel emissions using a physiologically relevant aerosol exposure model. Both the organic content and residual components of diesel emissions play an important role in determining bronchial epithelial cell response in vitro. Future studies should be directed at testing potentially useful interventions against the adverse health effects of air pollution exposure.

Osteoclast formation from circulating precursors in osteoporosis

Objective: An imbalance between bone formation and bone resorption is thought to underlie the pathogenesis of reduced bone mass in osteoporosis. Bone resorption is carried out by osteoclasts, which are formed from marrow-derived cells that circulate in the monocyte fraction. Ihe aim of this study was to determine the role of osteoclast formation in the pathogenesis of bone loss in osteoporosis. Methods: The proportion of circulating osteoclast precursors and their relative sensitivity to the osteoclastogenic effects of M-CSF, 1,25(OH)2D3 and RANKL were assessed in primary osteoporosis patients and normal controls. Results: Although there was no difference in the number of circulating osteoclast precursors in osteoporosis patients and normal controls, osteoclasts formed from osteoporosis patients exhibited substantially increased resorptive activity relative to normal controls. Although no increased sensitivity to the osteoclastogenic effects of 1,25(OH)2D3 or M-CSF was noted, increased bone resorption was found in osteoporosis peripheral blood mononuclear cell (PBMC) cultures to which these factors were added. Conclusion: Our findings suggest that osteoclast functional activity rather than formation is increased in primary involutional osteoporosis and that dexamethasone acts to increase osteoclast formation.

Halogen bonds in 2D supramolecular self-assembly of organic semiconductors

Weak interactions between bromine, sulphur, and hydrogen are shown to stabilize 2D supramolecular monolayers at the liquid–solid interface. Three different thiophene-based semiconducting organic molecules assemble into close-packed ultrathin ordered layers. A combination of scanning tunneling microscopy (STM) and density functional theory (DFT) elucidates the interactions within the monolayer. Electrostatic interactions are identified as the driving force for intermolecular Br⋯Br and Br⋯H bonding. We find that the S⋯S interactions of the 2D supramolecular layers correlate with the hole mobilities of thin film transistors of the same materials.

Unprecedented transformation of tetrathienoanthracene into pentacene on Ni(111)

The imaging and characterization of single-molecule reaction events is essential to both extending our basic understanding of chemistry and applying this understanding to challenges at the frontiers of technology, for example, in nanoelectronics. Specifically, understanding the behavior of individual molecules can elucidate processes critical to the controlled synthesis of materials for applications in multiple nanoscale technologies. Here, we report the synthesis of an important semiconducting organic molecule through an unprecedented reaction observed with submolecular resolution by scanning tunneling microscopy (STM) under ultrahigh vacuum (UHV) conditions. Our images reveal a sulfur abstraction and cyclization reaction that converts tetrathienoanthracene precursors into pentacene on the Ni(111) surface. The identity of the final reaction product was confirmed by time-of-flight secondary ion mass spectrometry (TOF-SIMS). This reaction has no known literature analogue, and highlights the power of local-probe techniques for exploring new chemical pathways.

Synthesis, characterization, and electronic structure studies of cubic Bi1.5ZnTa1.5O7 for photocatalytic applications

Bi1.5ZnTa1.5O7 (BZT) has been synthesized using an alkoxide based sol-gel reaction route. The evolution of the phases produced from the alkoxide precursors and their properties have been characterized as function of temperature using a combination of thermogravimetric analysis (TGA) coupled with mass spectrometry (MS), infrared emission spectrometry (IES), X-ray diffraction (XRD), ultraviolet and visible (UV-Vis) spectroscopy, Raman spectroscopy, and N2 adsorption/desorption isotherms. The lowest sintering temperature (600∘C) to obtain phase pure BZT powders with high surface area (14.5m2/g) has been determined from the thermal decomposition and phase analyses.The photocatalytic activity of the BZT powders has been tested for the decolorization of organic azo-dye and found to be photoactive under UV irradiation.The electronic band structure of the BZT has been investigated using density functional theory (DFT) calculations to determine the band gap energy (3.12 eV) and to compare it with experimental band gap (3.02 eV at 800∘C) from optical absorptionmeasurements. An excellent match is obtained for an assumption of Zn cation substitutions at specifically ordered sites in the BZT structure.

Characterisation, toxicity and source apportionment of atmospheric organic pollutants in urban schools

Airborne organic pollutants have significant impacts on health; however their sources, atmospheric characteristics and resulting human exposures are poorly understood. This research characterized chemical composition of atmospheric volatile organic compounds, polycyclic aromatic hydrocarbons and carbonyls in representative number of primary schools in Brisbane Metropolitan Area, quantified their concentrations, assessed their toxicity and apportioned them to their sources. The findings expand scientific knowledge of these pollutants, and will contribute towards science based management of risks associated with pollution emissions and air quality in schools and other urban and indoor environments.

Biorefineries – creating economic opportunities from biofuels and bio-products

Biorefineries, producing fuels, green chemicals and bio-products, offer great potential for improving the profitability and sustainability of tropical agricultural industries. Biomass from tropical crops like sugarcane, sweet sorghum, palm and cassava offer great potential because of the high biomass growth potential under favourable climatic conditions. Biorefineries aim to convert waste residues through biochemical and enzymatic processes to low cost fermentable sugars which are a platform for value-adding. Through subsequent fermentation utilising microbial biotechnologies or chemical synthesis, the sugars can be converted to fuels including ethanol and butanol, oils, organic acids such as lactic and levulinic acid and polymer precursors. Other biorefinery products can include food and animal feeds, plastics, fibre products and resins. Pretreatment technologies are a key to unlocking this potential and new technologies are emerging. This paper will address the opportunities available for tropical biorefineries to contribute to the future profitability of tropical agricultural industries. The importance of pretreatment technologies will be discussed.

The economic value of new tropical biorefinery industries in Australia

Biorefineries, co-producing fuels, green chemicals and bio-products, offer great potential for enhancing agricultural value, and developing new industries in the bioeconomy. Biomass biorefineries aim to convert agricultural crops and wastes through biochemical and enzymatic processes to low cost fermentable sugars and other products which are platforms for value-adding. Through subsequent fermentation or chemical synthesis, the bio-based platforms can be converted to fuels including ethanol and butanol, oils, organic acids such as lactic and levulinic acid and polymer precursors. Other biorefinery products can include food and animal feeds, plastics, fibre products and resins. In 2014, QUT commissioned a study from Deloitte Access Economics and Correlli Consulting to assess the potential future economic value of tropical biorefineries to Queensland. This paper will report on the outcomes of this study and address the opportunities available for tropical biorefineries to contribute to the future profitability and sustainability of tropical agricultural industries in Queensland and more broadly across northern Australia.

Influence of organic amendments on greenhouse gas emissions and N use efficiency in sub-tropical cropping systems

This thesis investigated the impact of organic sources of nutrients on greenhouse gas emissions (carbon dioxide, nitrous oxide and methane), nitrogen use efficiency and biomass production in subtropical cropping soils. The study was conducted in two main soil types in subtropical ecosystems, sandy loam soil and clay soil, with a variety of organic materials from agro-industrial residues and crop residues. It is important for recycling of agro-industrial residues and agricultural residues and the mitigation of greenhouse gas emissions and nitrogen use efficiency.

Plasma assisted surface modification of organic biopolymers to prevent bacterial attachment

Despite many synthetic biomaterials having physical properties that are comparable or even superior to those of natural body tissues, they frequently fail due to the adverse physiological reactions they cause within the human body, such as infection and inflammation. The surface modification of biomaterials is an economical and effective method by which biocompatibility and biofunctionality can be achieved while preserving the favorable bulk characteristics of the biomaterial, such as strength and inertness. Amongst the numerous surface modification techniques available, plasma surface modification affords device manufacturers a flexible and environmentally friendly process that enables tailoring of the surface morphology, structure, composition, and properties of the material to a specific need. There are a vast range of possible applications of plasma modification in biomaterial applications, however, the focus of this review paper is on processes that can be used to develop surface morphologies and chemical structures for the prevention of adhesion and proliferation of pathogenic bacteria on the surfaces of in-dwelling medical devices. As such, the fundamental principles of bacterial cell attachment and biofilm formation are also discussed. Functional organic plasma polymerised coatings are also discussed for their potential as biosensitive interfaces, connecting inorganic/metallic electronic devices with their physiological environments.

Complex permittivity measurements of RF plasma polymerized polyterpenol organic thin films employing split post dielectric resonator

In the fields of organic electronics and biotechnology, applications for organic polymer thin films fabricated using low-temperature non-equilibrium plasma techniques are gaining significant attention because of the physical and chemical stability of thin films and the low cost of production. Polymer thin films were fabricated from non-synthetic terpinen-4-ol using radiofrequency polymerization (13.56 MHz) on low loss dielectric substrates and their permittivity properties were ascertained to determine potential applications for these organic films. Real and imaginary parts of permittivity as a function of frequency were measured using the variable angle spectroscopic ellipsometer. The real part of permittivity (k) was found to be between 2.34 and 2.65 in the wavelength region of 400–1100 nm, indicating a potential low-k material. These permittivity values were confirmed at microwave frequencies. Dielectric properties of polyterpenol films were measured by means of split post dielectric resonators (SPDRs) operating at frequencies of 10 GHz and 20 GHz. Permittivity increased for samples deposited at higher RF energy – from 2.65 (25 W) to 2.83 (75 W) measured by a 20-GHz SPDR and from 2.32 (25 W) to 2.53 (100 W) obtained using a 10-GHz SPDR. The error in permittivity measurement was predominantly attributed to the uncertainty in film thickness measurement.

Effect of organic gate dielectric material properties on interfacial charging and discharging of pentacene MIM device

The effect of material properties of an environmentally friendly, optically transparent dielectric material, polyterpenol, on the carrier transients within the pentacene-based double-layer MTM device was investigated. Polyterpenol films were RF plasma polymerised under varied process conditions, with resultant films differing in surface chemistry and morphology. Independent of type of polyterpenol, time-resolved EFISHG study of IZO/polyterpenol/pentacene/Au structures showed similar transient behaviour with carriers injected into pentacene from Au electrode only, confirming polyterpenol to be a suitable blocking layer for visualisation of single-species carrier transportation during charging and discharging under different bias conditions. Polyterpenol fabricated under higher input power show better promise due to higher chemical and thermal stability, improved uniformity, and absence of defects.

Fabrication and characterization of polyterpenol as an insulating layer and incorporated organic field effect transistor

A non-synthetic polymer material, polyterpenol, was fabricated using a dry polymerization process namely RF plasma polymerization from an environmentally friendly monomer and its surface, optical and electrical properties investigated. Polyterpenol films were found to be transparent over the visible wavelength range, with a smooth surface with an average roughness of less than 0.4 nm and hardness of 0.4 GPa. The dielectric constant of 3.4 for polyterpenol was higher than that of the conventional polymer materials used in the organic electronic devices. The non-synthetic polymer material was then implemented as a surface modification of the gate insulator in field effect transistor (OFET) and the properties of the device were examined. In comparison to the similar device without the polymer insulating layer, the polyterpenol based OFET device showed significant improvements. The addition of the polyterpenol interlayer in the OFET shifted the threshold voltage significantly; + 20 V to -3 V. The presence of trapped charge was not observed in the polyterpenol interlayer. This assisted in the improvement of effective mobility from 0.012 to 0.021 cm 2/Vs. The switching property of the polyterpenol based OFET was also improved; 107 compared to 104. The results showed that the non-synthetic polyterpenol polymer film is a promising candidate of insulators in electronic devices.

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.

Assessing infant exposure to persistent organic pollutants via dietary intake in Australia

Persistent organic pollutants (POPs) including polybrominated diphenyl ethers (PBDEs); organochlorine pesticides (OCPs); and polychlorinated biphenyls (PCBs) persist in the environment, bioaccumulate, and pose a risk of causing adverse human health effects. Typically, exposure assessments undertaken by modeling existing intake data underestimate the concentrations of these chemicals in infants. This study aimed to determine concentrations of POPs in infant foods, assess exposure via dietary intake and compare this to historical exposure. Fruit purees, meat and vegetables, dairy desserts, cereals and jelly foods (n = 33) purchased in 2013 in Brisbane, Australia were analyzed. For OCPs and PCBs, concentrations ranged up to 95 pg/g fw and for PBDEs up to 32 pg/g fw with most analytes below the limit of detection. Daily intake is dependent on type and quantity of foods consumed. Consumption of a 140 g meal would result in intake ranging from 0 to 4.2 ng/day, 4.4 ng/day and 13.3 ng/day, for OCPs, PBDEs and PCBs, respectively. PBDEs were detected in 3/33 samples, OCPs in 9/33 samples and PCBs in 13/33 samples. Results from this study indicate exposure for infants via dietary (in contrast to dust and breast milk) intake in Australia contribute only a minor component to total exposure.