Thin layers with high barrier to oxygen and other gases are a key component to many packaging applications, such as flexible electronics, food, and pharmaceuticals. Vapor deposited thin films provide significant gas barrier, but are prone to cracking when flexed, require special, non-ambient processing environments, and can involve complex fabrication when layered with polymers. The addition of clay into polymers can enhance barrier properties relative to the neat polymer; however, these composites are subject to clay aggregation at high loadings, which leads to increased opacity and random platelet alignment that ultimately reduce barrier improvement. Layer-by-layer (LbL) assembly is capable of producing thin films that exhibit super gas barrier properties, while remaining flexible and completely transparent. Montmorillonite (MMT) clay and branched polyethylenimine (PEI) were deposited via LbL assembly to create gas barrier films that can be tailored by altering the pH of the PEI deposition solution or the concentration of the MMT suspension. Films grow linearly as a function of layers deposited, where increasing PEI pH increases spacing between clay layers and increasing MMT concentration increases thin film clay content. An oxygen transmission rate (OTR) below the detection limit of commercial instrumentation (< 0.005 cm3/m2•day•atm) is observed after 70 layers of 0.2 wt % MMT or 24 layers of 2 wt % MMT are deposited with pH 10 PEI onto 179 µm thick poly(ethylene terephthalate) (PET) film. Three-component films of PEI, poly(acrylic acid) (PAA), and MMT grow exponentially as a function of PEI/PAA/PEI/MMT quadlayers deposited. A transparent, ultrathin film of only four quadlayers deposited onto PET exhibits the lowest oxygen permeability ever reported for any thin film material, at only 51 nm thick. Finally, the first example of LbL assembly using large aspect ratio vermiculite (VMT) clay was performed. PEI/VMT films grow linearly as a function of layers deposited and exhibit 95 % light transmission with 97 wt % VMT. The barrier of these films is due to the highly aligned nanobrick wall structure that creates a tortuous path for permeating molecules. Coupling high flexibility, transparency, and barrier, these coatings are good candidates for a variety of packaging applications.

With growing environmental concerns, efforts are made to replace petroleum based products with renewable alternatives. This is particularly evident in the packaging industry, where replacing synthetic polymers with renewable materials is of considerable interest. Materials for food packaging need to give protection, acting as a barrier against substances that can adversely affect the food quality such as water and oxygen. In this work, barrier dispersion coatings based on starch were used to produce coated papers which act as barrier against water and oxygen. However, since starch is both a hydrophilic and hygroscopic material, this barrier material becomes problematic to use at high relative humidity. In order to reduce this problem and improve the barrier properties enabling starch based barrier materials to be used in food packaging applications, two approaches were studied. Citric acid was utilized as a cross-linker of the starch and it was found to reduce the moisture sorption, the molecular movement and swelling at high relative humidity. It was seen that cross-linking and hydrolysis due to the low pH both affected the barrier properties significantly, but in opposing directions. By controlling these two reactions it was seen that this could lead to reduced gas permeability. It was also seen that cross-linking of starch by citric acid occurs at low temperatures, 70 °C at pH as high as 6.5. Starch nano-composites were produced by incorporating montmorillonite, to the barrier dispersion to improve the barrier properties. It was seen that the suspension viscosity was reduced by poly(ethylene glycol) and citric acid adsorption on the montmorillonite particles. Also, a tendency for improved barrier properties with reduced aggregate volume fraction and reduced swelling was observed. It was also seen that up scaling this formulation to pilot scale was possible and that promising results were achieved. / Baksidestext With growing environmental concerns, efforts are made to replace petroleum based materials with renewable alternatives such as starch. In this work, dispersions based on starch were used to produce coated papers which act as barrier against substances that can adversely affect the food quality such as water and oxygen. However, since starch is both a hydrophilic and hygroscopic material, this barrier material becomes problematic to use at high relative humidity. Citric acid was utilized as cross-linker for starch and it was found to reduce the moisture sorption, diffusion and swelling at high relative humidity. Both cross-linking and hydrolysis due to the low pH affected the barrier properties significantly, but in opposing directions. By controlling these two reactions it was possible to achieve reduced gas permeability. Starch nano-composites were produced by incorporating montmorillonite clay, to the barrier dispersion. It was seen that the suspension viscosity was reduced by poly(ethylene glycol) and citric acid adsorption on the clay. Also, a tendency for improved barrier properties with reduced aggregate volume fraction and reduced swelling was observed. It was also seen that up scaling this formulation to pilot scale was possible and promising results were achieved. / Renewable Functional Barriers

The aim of this thesis is to investigate the effects of additives, reactive elements and impurities, on the lifetime of thermal barrier coatings. The thesis consists of a number of studies on interface adhesion, impurity diffusion, grain boundary sliding and cleavage processes and their impact on the mechanical behaviour of grain boundaries. The effects of additives and impurity on interface adhesion were elaborated by using total energy calculations, electron localization and density of states, and by looking into the atomic separations. The results of these calculations allow the assessment of atomic level contributions to changes in the adhesive trend. Formation of new bonds across the interface is determined to improve the adhesion in reactive element(RE)-doped structures. Breaking of the cross interface bonds and sulfur(S)-oxygen(O) repulsion is found responsible for the decreased adhesion after S segregation. Interstitial and vacancy mediated S diffusion and the effects of Hf and Pt on the diffusion rate of S in bulk NiAl are studied. Hf is shown to reduce the diffusion rate, and the preferred diffusion mechanism of S and the influence of Pt are revealed to be temperature dependent. Finally, the effects of reactive elements on alumina grain boundary strength are studied. Reactive elements are shown to improve both the sliding and cleavage resistance, and the analysis of atomic separations suggest an increased ductility after the addition of quadrivalent Hf and Zr to the alumina grain boundaries.

Cronobacter species cause serious infections such as meningitis and enteritis in newborns and neonates, with the major vehicle being contaminated powdered infant formula. The main objectives of this study were i) to identify potential virulence factors, such as enterotoxin production; ii) characterize the gene(s) involved in adhesion and invasion of the human brain microvascular endothelial cells (HBMEC); and iii) determine whether strains from clinical, food, and environmental sources differ in their ability to produce surface-attached bacterial aggregates, known as biofilms. Random transposon mutagenesis was used on strains demonstrating the best adherence and invasion to blood- brain barrier cell lines (BBB). Isogenic mutants were then screened for increased or decreased adherence and invasion. Screening of the transposon library identified one isogenic mutant of a clinical strain which lost the ability to adhere to BBB cells. The transposon rescue revealed the insertion site to be within a diguanylate cyclase (DGC) gene. The major function of DGC in many Gram-negative bacteria is to synthesize cyclic diguanylate (c-di-GMP), a secondary bacterial metabolite known for regulating biofilm formation, motility, and virulence or aspects of microbial pathogenicity. Based on the findings of this study, DGC appears to play an important role in Cronobacter species’ ability to produce biofilms and may also have a role of the pathogenicity in the microorganism.

Voltage-gated ion channels play fundamental roles in neural excitability, they are for instance responsible for every single heart beat in our bodies, and dysfunctional channels cause disease that can be even lethal. Understanding how the voltage sensor of these channels function is critical for drug design of compounds targeting neuronal excitability. The opening and closing of the pore in voltage-gated potassium (Kv) channels is caused by the arginine-rich S4 helix of the voltage sensor domain (VSD) moving in response to an external potential. In fact, VSDs are remarkably efficient at turning membrane potential into conformational changes, which likely makes them the smallest existing biological engines. Exactly how this is accomplished is not yet fully known and an area of hot debate, especially due to the lack of structures of the resting and intermediate states along the activation pathway. In this thesis I study how the VSD activation works and show how toxic compounds modulate channel gating through direct interaction with these quite unexplored drug targets. First, I show that a secondary structure transition from alpha- to 3(10)-helix in the S4 helix is an important part of the gating as this helix type is significantly more favorable compared to the -helix in terms of a lower free energy barrier. Second, I present new models for intermediate states along the whole voltage sensor cycle from closed to open and suggest a new gating model for S4, where it moves as a sliding 3(10)-helix. Interestingly, this 3(10)-helix is formed in the region of the single most conserved residue in Kv channels, the phenylalanine F233. Located in the hydrophobic core, it directly faces S4 and creates a structural barrier for the gating charges. Substituting this residue alters the deactivation free energy barrier and can either facilitate the relaxation of the voltage sensor or increase the free energy barrier, depending on the size of the mutant. These results are confirmed by new experimental data that supports that a rigid ring at the phenylalanine position is the rate-limiting factor for the deactivation gating process, while the activation is unaffected. Finally, we study how the activation can be modulated for pharmaceutical reasons. Neurotoxins such as hanatoxin and stromatoxin push S3b towards S4 helix limiting S4's flexibility. This makes it harder for the VSD to activate and might explain the stronger binding affinities in resting state. All these results are highly important both for the general topic of biological macromolecules undergoing functionally critical conformational transitions, as well as the particular case of voltage-gated ion channels where understanding of the gating process is probably the key step to explain the effects of mutations or drug interactions. / <p>QC 20121115</p>

Herein, we report the first solution-processed broadband photodetectors to break the past compromise between sensitivity and speed of response. Specifically, we report photodiodes having normalized detectivity (D*) > 1012 Jones and a 3dB bandwidth of > 2.9 MHz. This finding represents a 170,000 fold improvement in response speed over the most sensitive colloidal quantum dot (CQD) photodetector reported1 and a 100,000 fold improvement in sensitivity over the fastest CQD photodetector reported2. At the outset of this study, sensitive, solution-processed IR photodetectors were severely limited by low response speeds1. Much faster response speeds had been demonstrated by solution-processed photodetectors operating in the visible3, but these devices offered no benefits for extending the spectral sensitivity of silicon. No available solution-processed photodetector combined high sensitivity, high operating speed, and response to illumination across the UV, visible and IR. We developed a fast, sensitive, solution-processed photodetector based on a photodiode formed by a Schottky barrier to a CQD film. Previous attempts to form sensitive photodetectors based on CQD photodiodes had demonstrated low quantum efficiencies that limited sensitivity4,5. Efficient, sensitive semiconductor photodiodes are based on two fundamental characteristics: a large built-in potential that separates photogenerated charge carriers and minimizes internal noise generation, and high semiconductor conductivity for efficient collection of photogenerated charge. Schottky barriers to CQD films were developed to provide high, uniform built-in potentials. A multi-step CQD ligand exchange procedure was developed to allow deposition of tightly packed films of CQDs with high mobility and sufficiently well-passivated surfaces to form high-quality metallurgical junctions. The temporal response of the CQD photodiodes showed separate drift and diffusion components. Combined with detailed measurements of the Schottky barrier, these characteristics provided the physical basis for a numerical model of device operation. Based on this understanding, devices that excluded the slow diffusive component were fabricated, exploiting only the sub-microsecond field-driven transient to achieve MHz response bandwidth. These devices are the first to combine megahertz-bandwidth, high sensitivity, and spectral-tunability in photodetectors based on semiconducting CQDs. Record performance is achieved through advances in materials and device architecture based on a detailed understanding the physical mechanisms underlying the operation of CQD photodiodes.

Yttria Partially Stabilized Zirconia (Y-PSZ) plasma-sprayed coatings are widely used in turbine engines as thermal barrier coatings. However, in diesel engines Y-PSZ TBCs have not met with wide success. To reach the desirable temperature of 850-900˚C in the combustion chamber from the current temperature of 400-600˚C, a coating with a thickness of approximately 1mm is required. This introduces different considerations than in the case of turbine blade coatings, which are on the order of 100µm thick. Of the many factors affecting the durability and failure mechanism of TBCs, in service and residual stresses play an especially important role as the thickness of the coating increases. For decreasing the residual stress in the system, a multi-layer coating is helpful. The design of a multilayer coating employing relatively low cost materials with complementary thermal properties is described. Numerical models were used to describe the residual stress after deposition and under operating conditions for a multilayer coating that exhibited the desired temperature gradient. Results showed that the multilayer coating had a lower maximum stress under service conditions than a conventional Y-PSZ coating. Model validation with experiments showed a good match between the two.

In vivo real-time data of ultrasound and microbubble assisted blood-brain barrier disruption is centrally based on low-resolution magnetic resonance images. Additional information can be gained using online microscopic monitoring. This study presents the first ever in vivo two-photon microscopy, four-dimensional data sets of ultrasound and microbubble assisted blood-brain barrier disruption. It characterized the threshold pressures and mechanical index needed to disrupt the vasculature with 800 kHz ultrasound, and found three different leakage constants from the compromised vasculature. Furthermore, using numerical models, an ultrasound array was designed and optimized to perform specifically with our two-photon microscope. It was fabricated, fully characterized, and its performance met both the required pressure field profile and the pressure values needed for our in vivo two-photon microscopy experiments. This array is an important step in microscopically characterizing ultrasound and microbubble assisted blood-brain barrier disruption.

The effects on heat transfer of piston crown surface finish and use of a metal based thermal barrier coating (TBC) on the piston crown were studied in an SI engine. Measured engine parameters such as power, fuel consumption, emissions and cylinder pressure were used to identify the effects of the coating and its surface finish. Two piston coatings were tested: a baseline copper coating and a metal TBC. Reducing surface roughness of both coatings increased in-cylinder temperature and pressure as a result of reduced heat transfer through the piston crown. These increases resulted in small improvements in both power and fuel consumption, while also having measurable effect on emissions. Oxides of nitrogen emissions were increased while total hydrocarbon emissions were decreased. Improvements attributed to the TBC were found to be small, but statistically significant. At an equivalent surface finish, the TBC performed better than the baseline copper finish.

In vivo real-time data of ultrasound and microbubble assisted blood-brain barrier disruption is centrally based on low-resolution magnetic resonance images. Additional information can be gained using online microscopic monitoring. This study presents the first ever in vivo two-photon microscopy, four-dimensional data sets of ultrasound and microbubble assisted blood-brain barrier disruption. It characterized the threshold pressures and mechanical index needed to disrupt the vasculature with 800 kHz ultrasound, and found three different leakage constants from the compromised vasculature. Furthermore, using numerical models, an ultrasound array was designed and optimized to perform specifically with our two-photon microscope. It was fabricated, fully characterized, and its performance met both the required pressure field profile and the pressure values needed for our in vivo two-photon microscopy experiments. This array is an important step in microscopically characterizing ultrasound and microbubble assisted blood-brain barrier disruption.