<p>Multifunctional drug delivery systems incorporated with stimuli-sensitive drug release, magnetic nanoparticles and magnetic resonance (MR) <em>T</em>₂ contrast agents is attracting increasing attention recently. In this thesis, works on polymer nanospheres response to temperature change, superparamagnetic iron oxide nanoparticles (SPION)/polymeric composite materials for MR imaging contrast agents are summarized.</p><p>A “shell-in-shell” polymeric structure has been constructed through a “modified double-emulsion method”. Thermosensitive inner shell is comprised of poly(<em>N</em>-isopropylacrylamide) which undergoes phase transition at body temperature. Such a feature could facilitate drug release at an elevated temperature upon administration. Furthermore, the dual-shell structure is covered by a layer of gold nanoparticles. According to the cytotoxicity tests, the biocompatibility is shown to be enhanced due to the layer of gold.</p><p>SPION have been prepared using a high temperature decomposition method. Particle growth of SPION is monitored by transmission electron microscope and synchrotron X-ray diffraction. Poly(L,L-lactide)@SPION (PLLA@SPION) composite particles have been prepared through surface-initiated ring-opening polymerization which has been developed in our lab. For biomedical applications, it is essential to transfer the particles to physiological solutions from organic solutions. Phase transfer of SPION has been carried out by utilizing small molecules. Stability at the neutral pH is of large concern for such transfer systems. A novel phase transfer agent, Pluronic F127 (PF127), a triblock copolymer has been applied and the stability of the aqueous PF127@oleic acid (OA)@SPION solution has been greatly enhanced over a broad pH range. Most interestingly, PF127@OA@SPION show remarkable efficacy as T2 contrast agents as indicated by relaxometric measurements compared with commercially available products.</p>

This research project is concentrated on tuning the properties of small organic molecules, namely polyacenes, tropones and thiepins, by incorporating redox-active transition metal centers π-bonded to terminal cyclopentadienyl ligands. Organometallic-fused acenequinones, tropones, thiepins and cyclopentadiene-capped polyacenes were synthesized and characterized. This work was divided into three parts: first, the synthesis of ferrocene-fused acenequinones, cyclopentadiene-capped acenequinones and their subsequent aromatization to polyacenes; second, the synthesis of ferrocene-fused tropones, thiotropones and tropone oxime; and third, the synthesis of ferrocene-fused thiepins. Ferrocene-fused quinones are the precursors to our target complexes. Our synthetic route to ferrocenequinones involved two-fold aldol condensation between 1,2-diformylferrocene and naphthalene-1,4-diol or anthracene-1,4-diol, and four-fold condensation between 1,2-diformylferrocene and 1,4-cyclohexanedione. Reduction of ferrocene-fused quinones with borane in THF resulted in ferrocene-fused dihydroacenes. Attempts to reduce ferrocene-fused acenequinones with sodium dithionite led to metal-free cyclopentadiene- (Cp-) capped acenequinones. Cp-capped acenequinones were aromatized to bis(triisopropylsilyl)ethynyl polyacenes by using lithium (triisopropylsilyl)acetylide (TIPSC≡CLi) with subsequent dehydroxylation by stannous chloride. The compounds were characterized by using spectroscopic methods and X-ray crystallography. Further, the electronic properties of these compounds were studied by using cyclic voltammetry and UV-visible spectroscopy. Cyclic voltammetry showed oxidation potentials of Cp-capped TIPS-tetracene and bis-Cp-capped TIPS-anthracene as 0.49 V and 0.61 V, respectively (vs. ferrocene/ferrocenium). The electrochemical band gaps were 2.15 eV and 2.58 eV, respectively. Organic thin-film transistor device performance of Cp-capped polyacenes was studied using solution deposition bottom-contact, bottom-gate (BCBG) device architecture and the resulting performance parameters are described herein. Similarly, we are also interested in potential applications of metallocene-fused tropones and derivatives as organic electronic materials. Condensation of 1,2-diformylferrocene with acetone or 1,3-diphenylacetone in the presence of KOH resulted in the ferrocene-fused tropone (η5-2,4-cyclopentadien-1-yl)[(1,2,3,3a,8a-η)-1,6-dihydro-6-oxo-1-azulenyl]iron (1, R = H, E = O) and its 5,7-diphenyl derivative (1, R = Ph, E = O) as previously reported by Tirouflet. The use of piperidine as base resulted in Michael addition of piperidine to one of the carbon-carbon double bonds of the tropones. Lawesson’s reagent converted the ferrocene-fused tropones to either a thiotropone (1, R = H, E = S) or a detached 5,7-diphenylazulenethiol (2). Reaction of the ferrocene-fused thiotropone with hydroxylamine gave the corresponding oxime (1, R = H, E = NOH). Products were characterized by using spectroscopic methods and X-ray crystallography. Their electronic properties were studied by using cyclic voltammetry and UV-visible spectroscopy. The third project involved the two-fold aldol condensation of 1,2-diformylferrocene with dimethylthioglycolate S-oxide in the presence of freshly distilled triethylamine, which gave mono- and di-dehydrated products. Deoxygenation of the ferrocene-fused thiepin S-oxide with 2-chloro-1,3,2-benzodioxaphosphole in the presence of pyridine resulted in the corresponding thiepin. The ester groups of the thiepin and thiepin S-oxide were hydrolyzed under basic conditions to give carboxylic acids, which were converted into acid chlorides using oxalyl chloride. Attempts to decarboxylate the thiepin and thiepin S-oxide diacids resulted in decomposition.

The interactive wireless sensor detects many hazardous gases such as Hexane, Propane, Carbon monoxide and Hydrogen. These gases are highly toxic and used in different kinds of manufacturing industries, domestic purpose and so on. So, building a sensor that can detect this kind of gases can save the environment; prevent the potential for explosion, and endangering human life. In long term, interactive wireless sensor can also prevent the financial losses that might occur due to the hazardous incident that might occur due to these toxic gases. Hexane is a colorless, strong gas which inhaled in significant amounts by a person then he may suffer with hexane poisoning and suffocation. It also causes skin burns when exposed in high concentrations. Propane, carbon monoxide and hydrogen can easily freeze in room temperature, if in contact with eye, it could permanently damage eye or cause blindness. The advantage of this wireless sensor is the use of artificial olfactory system (electronic nose) that can be taught to detect these hazardous gases. This sensor has a unique molecular combination of analysts, impurities and background that corresponds to a gas leak. It consists of a chemiresistor, such as an array of conductometric sensors, and a mechanism analyzing the data in real time. A smell-print is composed of many molecules which reaches receptor in the human nose. When a specific receptor receives a molecule, it sends a signal to the brain where the smell is identified and associated with that particular molecule. Similar manner, albeit substituting sensors for the receptors, and transmitting the signal to a machine learning algorithm for processing, rather than to the brain. This wireless gas leak sensing consists of microchip Pic 32, integrated electronic nose, automated data analysis unit, power supply, and communications. The communication channel will use the ZigBee link, or the cellular links, or other specific frequency wireless link. The time-stamped and position-stamped sensor measurement data are transmitted to the central computer in predetermined periods of time. The data will be stored in the computer database for possible future analysis of the gas leak development process.

Mesoporous silicates are excellent materials for supported catalysis due to their ease of functionalization, tunable pore size and high surface areas. Mesoporous silicates have been utilized in a variety of applications such as drug delivery scaffolds and catalyst supports. Functionalization of the surface can be achieved by either grafting of alkoxy silanes or co-condensation of the organosilane with the inorganic silica source. My research in this area can be divided into two components. In the first, we address the significant issue of metal contamination after reactions that are catalyzed by transition metals. In the second, we examine the design of new catalysts based on organic/inorganic composites. Ruthenium catalyzed processes such as olefin metathesis or asymmetric hydrogenation, are often underutilized due to the difficulty of removing the ruthenium by-products. Attempts to remove ruthenium involve treating the solution with a scavenging reagent followed by silica chromatography. Often these scavenging agents are expensive phosphines or toxic agents like lead tetra-acetate. SBA-15 functionalized with aminopropyl triethoxysilane displays a high affinity for ruthenium. Furthermore, it can be utilized to remove ruthenium by-products from olefin metathesis or hydrogenation reactions without the need for silica chromatography. We have also prepared sulfur-functionalized mesoporous silicates that have a high affinity for palladium. The materials after loading prove to be active catalysts for a variety of palladium catalyzed processes such as Suzuki-Miyaura and Sonogashira couplings. The catalysts are recyclable with moderate loss of activity and structure, depending on the method of incorporation of the thiol. We have characterized the as-synthesized and used catalysts by nitrogen sorption, TEM, X-ray photoelectron spectroscopy (XPS) and a variety of homogeneity tests were performed on the catalysts. Periodic mesoporous organosilicates (PMOs) are a well known class of inorganic-organic hybrid materials. The majority of PMOs prepared utilize simple organic bridges such as ethyl, phenyl or biphenyl. The use of a chiral organic bridging group, such as BINAP, allows the synthesis of chiral PMOs with possible applications in catalysis and separation science. The synthesis of a triethoxysilyl functionalized BINAP as well as its incorporation into PMO materials with 4,4’-bistriethoxysilyl biphenyl or tetraethylorthosilicate as co-silica sources are described. / Thesis (Ph.D, Chemistry) -- Queen's University, 2009-04-20 10:49:13.443

Lithium-ion batteries (LIBs) are the most commonly used type of rechargeable batteries with a global market estimated at $11 billion, which is predicted to grow to $60 billion by 2020. The global commercialization of Li-ion batteries is impeded by issues such as poor cycle life (5000 cycles achieved in some LIBs) in high energy and power density applications because of the rising internal resistance due to aging and safety concerns such as overcharge which ultimately leads to thermal runaway and explosions. A battery’s performance mainly depends on external factors such as electrode thickness and degree of compacting, and the type of conductive additive and electrolyte mixture used, and internal factors such as its internal temperature and state of charge. The performance suffers due to aging or erroneous mechanisms such as decomposition of the electrode or electrolyte material affecting the lifetime. In this thesis, an attempt is made to improve the lifetimes of the Li-ion batteries by incorporating suitable electrolyte additives, which were incorporated in the battery electrolyte to prevent overcharge. Also, several conductive electrode additives were incorporated as filler materials in an anode to explore the effects on its discharge capacities.

The brittleness of concrete has always been a safety and economic issue of great concern. The low tensile strength of concrete is the cause of its intrinsic brittle nature. This is critical considering the amount of concrete used for the construction of highways, buildings, and other facilities. The mechanical properties of concrete must be improved to provide upgraded construction. Crack resistant and durable concrete has always been a major goal for engineers. Many approaches have been tried to make concrete a better construction material. Fiber reinforcement is an approach which has been shown to improve the quality and durability of concrete. The focus of this research is to develop a mix design of fiber reinforced concrete and then test these materials for both compressive and tensile strength after casting into cubes. The effect of polyvinyl alcohol fibers on the mechanical properties of concrete was also studied. The impacts of moisture and the stress applied on the fibers were determined using Raman spectroscopy.

In the past few years, the solution-processed organic based solar cells gained more importance by meeting the demands for cost effective photovoltaic devices. To date, the focus of the organic photovoltaic devices has been on the optimization of the processing the materials to improve photo conversion efficiency and also by modifying the active components of the organic materials. Recently, it has been recognized that the deposition techniques also plays a major role in enhancing the power conversion efficiencies. Currently, though the most common deposition technique for organic solar cells is spin coating, which does not allow scaling up of the large device area. As an alternative method, a simple airbrush spray deposition technique has been developed to fabricate the test devices. The film thickness of the layers was characterized under scanning electron microscope. Devices with different thickness (1000 nm, 500 nm, 240 nm) of poly(3,4-ethylenedioxythipohene) polystyrene sulfonate (PEDOT.PSS) and active layers are prepared and their photovoltaic performances have been evaluated and compared by plotting the IV curves with respect to each thickness. Maintaining the distance between the substrate and the airbrush nozzle the thickness of the layers was controlled. From the results, we found that the test devices with 500 nm thickness of PEDOT.PSS and active layers shows the best device performance with highest current density of 3.97 mA/cm2, open circuit voltage of 1.3 V and power conversion efficiency of 2.34%. As a control experiment, devices were also developed using the standard poly(3- hexylthiophene-2,5-diyl):phenyl-C61-butyric acid methyl ester (P3HT:PCBM) system, but the power conversion efficiencies of these devices were not promising with respect to the literature results. Future studies of this project will focus on improving the power conversion efficiency of poly(3-hexylthiophene-2,5-diyl)/perylenediimide bridged system (P3HT/PDIB) by developing a new device architecture called “tandem solar cells” which consists of multiple layers of different donor and acceptor blends with inorganic transition metal oxides such as zinc oxide and molybdenum oxides.

This study are based on the premise that the incorporation of metal ions into nano titania-PHEMA [poly (2-hydroxyethyl methacrylate)] hydrogels would enhance the desirable properties in the photodecomposition of pollutants. The investigation are centered in the use of Cu(II) as metal ion of interest. The development of TiO2-PHEMA-Cu hydrogels was conducted, and the characterization of the materials by FT-IR, XRD and fluorescence was performed. The absorption of copper(II) from the solution was monitored by UV-Vis. The FT-IR are found too, be the most effective tool too, analyze the interaction of Cu(II) with PHEMA in the nanocomposite hydrogels. The free carbonyl group has the IR band at 1715 cm-1 in the TiO2-PHEMA. Upon uptaking Cu(II), the hydrogels showed a new band at 1595 cm-1. Further examination establishes the relationship between the two bands. The time-dependent study revealed that the intensity of band at 1595 cm-1 would increase while that at 1715 cm-1 would decrease as the time for uptaking Cu(II) increased. A concentration-dependent study also demonstrated the same trend that showed the intensities of the two bands moved in the opposite directions.

Boric acid based fuel and oil additives were investigated in this study, with the aims to gain a deeper understanding of how the boric acid fuel additive behaves, to investigate the effect of low rates of fuel additive addition and tribofilm longevity, and to investigate how boric acid behaves as a hydraulic oil additive. Fuel additive experiments were performed in a reciprocating sliding rig with a cylinder on flat contact geometry with fuel additive sprayed on the contact repeatedly, whereas the hydraulic oil experiments were performed in a reciprocating sliding rig with a ball on flat contact with the oil and additive present from the start. Analysis was performed using vertical scanning interferometry (VSI), scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDS). The tribofilms created by the fuel additive provided excellent friction reduction capabilities, even with low or no rate of replenishment. As more additive was sprayed, wear resistance seemed to increase as the surface became increasingly covered. Film coverage need to be less than 20% of the surface in order to gain full friction reducing effects. The hydraulic oil additive had little effect on friction or wear resistance under the used parameters and no tribofilm was found.

Cu(In,Ga)Se2 (CIGS) is a semiconductor material and the basis of the promising thin-film photovoltaic technology with the same name. The CIGS film has a typical thickness of 1-2 mm, and solar cells based on CIGS technology has recently reached efficiencies of 23.3%. Ultra-thin CIGS solar cells use sub-micrometer thick films that require significantly less material and can be manufactured in a shorter amount oftime than films with typical thicknesses. With decreasing thickness, both electrical and optical losses get more significant and lower the overall performance. Electrical losses can be decreased by increasing the overall film quality and by utilising a graded bandgap throughout the CIGS layer. The band gap can be changed by varying the[Ga]/([Ga]+[In]) (GGI) ratio. Higher overall film quality and a higher band-gap towards the back of the absorber are expected to increase the performance. In this work, sputtered CIGS solar cells were made with different CIGS layer thicknesses, that ranged between 550-950 nm. Increased heat during deposition was examined and shown to increase the film quality and performance for all thicknesses. Two different ways of doping CIGS with Na was examined and it was found that higher Na content lead to an increasing predominance of the (112) plane. The bandgap was graded by varying the GGI composition throughout the CIGS layer and depth profiles were made with Glow-Discharge Optical Emission Spectroscopy (GDOES). It was found that a sputtered CuGaSe2 (CGS)layer below the CIGS-layer lead to a steep increase of the GGI near the back contact. When CGS made up 10% of the total CIGS layer thickness, a significant increase in performance was observed for all thicknesses. CIGS-absorbers with a less graded region with low GGI, making up 30% or 60% of the total CIGS layer thickness were made. A decrease in GGI in that region, was shown to increase the current but lower the voltage. No substantial increase in total performance compared to a fully graded CIGS layer was seen regardless of layer thickness. For further work the optical losses needs to be addressed and work on increasing the optical path in the CIGS layer needs to be done.