Optical and microscopic study of a polymer-nanotube mixture for organic photovoltaic applications

Organic solar cells based on bulk heterojunction between a conductive polymer and a carbon nanostructure offer potential advantages compared to conventional inorganic cells. Low cost, light weight, flexibility and high peak power per unit weight are all features that can be considered a reality for organic photovoltaics. Although polymer/carbon nanotubes solar cells have been proposed, only low power conversion efficiencies have been reached without addressing the mechanisms responsible for this poor performance. The purpose of this work is therefore to investigate the basic interaction between carbon nanotubes and poly(3-hexylthiophene) in order to demonstrate how this interaction affects the performance of photovoltaic devices. The outcomes of this study are the contributions made to the knowledge of the phenomena explaining the behaviour of electronic devices based on carbon nanotubes and poly(3-hexylthiophene). In this PhD, polymer thin films with the inclusion of uniformly distributed carbon nanotubes were deposited from solution and characterised. The bulk properties of the composites were studied with microscopy and spectroscopy techniques to provide evidence of higher degrees of polymer order when interacting with carbon nanotubes. Although bulk investigation techniques provided useful information about the interaction between the polymer and the nanotubes, clear evidence of the phenomena affecting the heterojunction formed between the two species was investigated at nanoscale. Identifying chirality-driven polymer assisted assembly on the carbon nanotube surface was one of the major achievements of this study. Moreover, the analysis of the electrical behaviour of the heterojunction between the polymer and the nanotube highlighted the charge transfer responsible for the low performance of photovoltaic devices. Polymer and carbon nanotube composite-based devices were fabricated and characterised in order to study their electronic properties. The carbon nanotube introduction in the polymer matrix evidenced a strong electrical conductivity enhancement but also a lower photoconductivity response. Moreover, the extension of pristine polymer device characterisation models to composites based devices evidenced the conduction mechanisms related to nanotubes. Finally, the introduction of carbon nanotubes in the polymer matrix was demonstrated to improve the pristine polymer solar cell performance and the spectral response even though the power conversion efficiency is still too low.

Static and dynamic strain sensing using a polymer : carbon nanotube film strain sensor

The search for new multipoint, multidirectional strain sensing devices has received a new impetus since the discovery of carbon nanotubes. The excellent electrical, mechanical, and electromechanical properties of carbon nanotubes make them ideal candidates as primary materials in the design of this new generation of sensing devices. Carbon nanotube based strain sensors proposed so far include those based on individual carbon nanotubes for integration in nano or micro elecromechanical systems (NEMS/MEMS) [1], or carbon nanotube films consisting of spatially connected carbon nanotubes [2], carbon nanotube - polymer composites [3,4] for macroscale strain sensing. Carbon nanotube films have good strain sensing response and offer the possibility of multidirectional and multipoint strain sensing, but have poor performance due to weak interaction between carbon nanotubes. In addition, the carbon nanotube film sensor is extremely fragile and difficult to handle and install. We report here the static and dynamic strain sensing characteristics as well as temperature effects of a sandwich carbon nanotube - polymer sensor fabricated by infiltrating carbon nanotube films with polymer.

Ultraviolet photodetection of flexible ZnO nanowire sheets in polydimethylsiloxane polymer

ZnO nanowires are normally exposed to an oxygen atmosphere to achieve high performance in UV photodetection. In this work we present results on a UV photodetector fabricated using a flexible ZnO nanowire sheet embedded in polydimethylsiloxane (PDMS), a gas-permeable polymer, showing reproducible UV photoresponse and enhanced photoconduction. PDMS coating results in a reduced response speed compared to that of a ZnO nanowire film in air. The rising speed is slightly reduced, while the decay time is prolonged by about a factor of four. We conclude that oxygen molecules diffusing in PDMS are responsible for the UV photoresponse

Photoclickable surfaces for profluorescent covalent polymer coatings

The nitrile imine-mediated tetrazole-ene cycloaddition reaction (NITEC) is introduced as a powerful and versatile conjugation tool to covalently ligate macromolecules onto variable (bio)surfaces. The NITEC approach is initiated by UV irradiation and proceeds rapidly at ambient temperature yielding a highly fluorescent linkage. Initially, the formation of block copolymers by the NITEC methodology is studied to evidence its efficacy as a macromolecular conjugation tool. The grafting of polymers onto inorganic (silicon) and bioorganic (cellulose) surfaces is subsequently carried out employing the optimized reaction conditions obtained from the macromolecular ligation experiments and evidenced by surface characterization techniques, including X-ray photoelectron spectroscopy and FT-IR microscopy. In addition, the patterned immobilization of variable polymer chains onto profluorescent cellulose is achieved through a simple masking process during the irradiation. Photoinduced nitrile imine-alkene 1,3-dipolar cycloaddition (NITEC) is employed to covalently bind well-defined polymers onto silicon oxide or cellulose. A diaryl tetrazole-functionalized molecule is grafted via silanization or amidification, respectively. Under UV light, a reactive nitrile imine rapidly forms and reacts with maleimide-functionalized polymers yielding a fluorescent linkage. Via a masking method, polymeric fluorescent patterns are achieved.

Molecular phylogeny supports the paraphyletic nature of the genus Trogoderma (Coleoptera: Dermestidae) collected in the Australasian ecozone

To date, a molecular phylogenetic approach has not been used to investigate the evolutionary structure of Trogoderma and closely related genera. Using two mitochondrial genes, Cytochrome Oxidase I and Cytochrome B, and the nuclear gene, 18S, the reported polyphyletic positioning of Trogoderma was examined. Paraphyly in Trogoderma was observed, with one Australian Trogoderma species reconciled as sister to all Dermestidae and the Anthrenocerus genus deeply nested within the Australian Trogoderma clade. In addition, time to most recent common ancestor for a number of Dermestidae was calculated. Based on these estimations, the Dermestidae origin exceeded 175 million years, placing the origins of this family in Pangaea.

Studies on the surface properties of biodegradable polymer carriers in respiratory delivery of drug from Dry Powder Inhaler formulations

Dry Powder Inhaler (DPI) technology has a significant impact in the treatment of various respiratory disorders. DPI formulations consist of a micronized drug (<5ìm) blended with an inert coarse carrier, for which lactose is widely used to date. DPIs are one of the inhalation devices which are used to target the delivery of drugs to the lungs. Drug delivery via DPI formulations is influenced by the physico-chemical characteristics of lactose particles such as size, shape, surface roughness and adhesional forces. Commercially available DPI formulations, which utilise lactose as the carrier, are not efficient in delivering drug to the lungs. The reasons for this are the surface morphology, adhesional properties and surface roughness of lactose. Despite several attempts to modify lactose, the maximum efficient drug delivery to the lungs remains limited; hence, exploring suitable alternative carriers for DPIs is of paramount importance. Therefore, the objective of the project was to study the performance of spherical polymer microparticles as drug carriers and the factors controlling their performance. This study aimed to use biodegradable polymer microspheres as alternative carriers to lactose in DPIs for achieving efficient drug delivery into the lungs. This project focused on fabricating biodegradable polymer microparticles with reproducible surface morphology and particle shape. The surface characteristics of polymeric carriers and the adhesional forces between the drug and carrier particles were investigated in order to gain a better understanding of their influence on drug dispersion. For this purpose, two biodegradable polymers- polycaprolactone (PCL) and poly (DL-lactide-co-glycolide) (PLGA) were used as the carriers to deliver the anti-asthmatic drug - Salbutamol Sulphate (SS). The first study conducted for this dissertation was the aerosolization of SS from mixtures of SS and PCL or PLGA microparticles. The microparticles were fabricated using an emulsion technique and were characterized by laser diffraction for particle size analysis, Scanning Electron Microscopy (SEM) for surface morphology and X-ray Photoelectron Spectroscopy (XPS) to obtain surface elemental composition. The dispersion of the drug from the DPI formulations was determined by using a Twin Stage Impinger (TSI). The Fine particle Fraction (FPF) of SS from powder mixtures was analyzed by High Performance Liquid Chromatography (HPLC). It was found that the drug did not detach from the surface of PCL microspheres. To overcome this, the microspheres were coated with anti-adherent agents such as magnesium stearate and leucine to improve the dispersion of the drug from the carrier surfaces. It was found that coating the PCL microspheres helped in significantly improving the FPF of SS from the PCL surface. These results were in contrast to the PLGA microspheres which readily allowed detachment of the SS from their surface. However, coating PLGA microspheres with antiadherent agents did not further improve the detachment of the drug from the surface. Thus, the first part of the study demonstrated that the surface-coated PCL microspheres and PLGA microspheres can be potential alternatives to lactose as carriers in DPI formulations; however, there was no significant improvement in the FPF of the drug. The second part of the research studied the influence of the size of the microspheres on the FPF of the drug. For this purpose, four different sizes (25 ìm, 48 ìm, 100 ìm and 150 ìm) of the PCL and PLGA microspheres were fabricated and characterized. The dispersion of the drug from microspheres of different sizes was determined. It was found that as the size of the carrier increased there was a significant increase in the FPF of SS. This study suggested that the size of the carrier plays an important role in the dispersion of the drug from the carrier surface. Subsequent experiments in the third part of the dissertation studied the surface properties of the polymeric carrier. The adhesion forces existing between the drug particle and the polymer surfaces, and the surface roughness of the carriers were quantified using Atomic Force Microscopy (AFM). A direct correlation between adhesion forces and dispersion of the drug from the carrier surface was observed suggesting that adhesion forces play an important role in determining the detachment potential of the drug from the carrier surface. However, no direct relationship between the surface roughness of the PCL or PLGA carrier and the FPF of the drug was observed. In conclusion, the body of work presented in this dissertation demonstrated the potential of coated PCL microspheres and PLGA microspheres to be used in DPI formulations as an alternative carrier to sugar based carriers. The study also emphasized the role of the size of the carrier particles and the forces of interaction prevailing between the drug and the carrier particle surface on the aerosolization performances of the drug.

Self-assembled hyperbranched polymer - gold nanoparticle hybrids : understanding the effect of polymer coverage on assembly size and SERS performance

In the past few years, remarkable progress has been made in unveiling novel and unique optical properties of strongly coupled plasmonic nanostructures. However, application of such plasmonic nanostructures in biomedicine remains challenging due to the lack of facile and robust assembly methods for producing stable nanostructures. Previous attempts to achieve plasmonic nano-assemblies using molecular ligands were limited due to the lack of flexibility that could be exercised in forming them. Here, we report the utilization of tailor-made hyperbranched polymers (HBP) as linkers to assemble gold nanoparticles (NPs) into nano-assemblies. The ease and flexibility in tuning the particle size and number of branch ends of a HBP makes it an ideal candidate as a linker, as opposed to DNA, small organic molecules and linear or dendrimeric polymers. We report a strong correlation of polymer (HBP) concentration with the size of the hybrid nano-assemblies and “hot-spot” density. We have shown that such solutions of stable HBP-gold nano-assemblies can be barcoded with various Raman tags to provide improved surface-enhanced Raman scattering (SERS) compared with non-aggregated NP systems. These Raman barcoded hybrid nano-assemblies, with further optimization of NP shape, size and “hot-spot” density, may find application as diagnostic tools in nanomedicine.

Self-regulation and mastery motivation in individuals with developmental disabilities : barriers, supports, and strategies

The development of the capacity for self-regulation represents an important achievement of childhood and is associated with social, behavioral, and academic competence (Bronson, 2001; Cleary & Zimmerman, 2004). Self-regulation evolves as individuals mature, with its final form integrating emotional, cognitive, and behavioral elements working together to achieve self-selected goals. This evolution is closely intertwined with the innate press to master the environment, labeled mastery motivation (Morgan, Harmon, & Maslin-Cole, 1990), as competence is the aim that underpins mastery motivation.

Recent advances in fabrication and characterization of graphene-polymer nanocomposites

Graphene has attracted considerable interest over recent years due to its intrinsic mechanical, thermal and electrical properties. Incorporation of small quantity of graphene fillers into polymer can create novel nanocomposites with improved structural and functional properties. This review introduced the recent progress in fabrication, properties and potential applications of graphene-polymer composites. Recent research clearly confirmed that graphene-polymer nanocomposites are promising materials with applications ranging from transportation, biomedical systems, sensors, electrodes for solar cells and electromagnetic interference. In addition to graphene-polymer nanocomposites, this article also introduced the synergistic effects of hybrid graphene-carbon nanotubes (CNTs) on the properties of composites. Finally, some technical problems associated with the development of these nanocomposites are discussed.

An influenza virus inspired polymer system for the timed release of siRNA

Small interfering RNA silences specific genes by interfering with mRNA translation, and acts to modulate or inhibit specific biological pathways; a therapy that holds great promise in the cure of many diseases. However, the naked small interfering RNA is susceptible to degradation by plasma and tissue nucleases and due to its negative charge unable to cross the cell membrane. Here we report a new polymer carrier designed to mimic the influenza virus escape mechanism from the endosome, followed by a timed release of the small interfering RNA in the cytosol through a self-catalyzed polymer degradation process. Our polymer changes to a negatively charged and non-toxic polymer after the release of small interfering RNA, presenting potential for multiple repeat doses and long-term treatment of diseases.

How collaborative technology supports cognitive processes in collaborative process modeling : a capabilities-gains-outcome model

We examine which capabilities technologies provide to support collaborative process modeling. We develop a model that explains how technology capabilities impact cognitive group processes, and how they lead to improved modeling outcomes and positive technology beliefs. We test this model through a free simulation experiment of collaborative process modelers structured around a set of modeling tasks. With our study, we provide an understanding of the process of collaborative process modeling, and detail implications for research and guidelines for the practical design of collaborative process modeling.