Kunskap om olika utvecklingsmetoder vid start av ett nytt mjukvaruutvecklingsprojekt äravgörande för utvecklarna, styrorganen och slutprodukten. Därför prioriteras ofta nya ochokända metoder ned för att säkerställa att arbetet blir gjort och att lösningen kommer attlevereras i tid och med hög kvalitet. Detta beteende gör på lång sikt att mjukvaruutvecklingsprojektgår miste om nya och bättre utvecklingsmetoder.För belysa nya utvecklingsmetoder och upplysa de som behöver, valde vi att undersökaskillnaderna i krav framställning inom området Open Source Software(OSS)1-utveckling.I vårt arbete ställer tre forskningsfrågor som ska belysa ämnet dessa bevarar vi genom attutföra en fallstudie. I fallstudien undersöker vi hur och av vilka som krav framställts i ettföretagsstyrt projekt jämfört med ett projekt drivet av en frivilligorganisation.Fallstudien visade att externa användare i frivilligorganisation OSS-projekt har lägredelaktighet, det vill säga bidrag till projektartefakter, jämfört med företagsdrivna projektdär deltagandet av externa användare är högre. Slutligen diskuterar vi implikationerna avresultaten för både OSS-projekt drivna av företag och frivilligorganisationer. Vi kan förbåda styrorganen dra slutsatsen att det är möjligt att öka både utvecklingshastighet ochproduktens värde för kunden. / Knowledge about different development methods when starting up a new software developmentproject is crucial for the developers, the governing bodies and the end product.Therefore new and unfamiliar options are taken out of the equation to make sure that thework gets done and that the solution will be delivered on time and with high quality. Thisbehaviour in the long term does, however, exclude new and better ways of executing thework in the process.To shine light upon new development methods and enlighten those who are in needof insight into a new viable option we chose to investigate the differences in requirementelicitation within the area of Open Source Software development. By examining how andby who requirements are elicited in a firm-driven project compared to a community drivenproject, we framed a total of three research questions to base our case study on.The case study showed that in community driven Open Source Software projects externalusers have low participation, in other words contributions to project artefacts, comparedto firm-driven projects where the participation of external users is high. Finally, wediscuss the potential implications of the findings for both community- and firm-driven OSSprojects. We could conclude for both types that it’s possible to increase both developmentspeed and customer product value.

<p>Ytterbium-doped optical fibers have extensive applications in high-power fiber lasers, optical amplifiers, and amplified spontaneous emission light sources. In this thesis two sub-projects associated with ytterbium doped fibers are discussed.</p> <p>Numerical simulations have been used to model high-repetition rate ultrafast ytterbium-doped fiber amplifier systems assuming continuous-wave input signals under variable situations, such as one-sided and two-sided pumping. Different system configurations are also developed, such as a single-stage amplification system, a two-stage amplification system and a separated amplification system, providing alternative choices for experiments and applications. The simulation results are compared with experimental data and the simulation results from some other software. The influence of nonlinear effects in the fiber is also very briefly discussed in this thesis.</p> <p>In a second research activity, the distribution of ytterbium atoms is being investigated in a range of double-clad ytterbium-doped fibers. Using aberration-corrected electron microscopy, ytterbium atoms are directly observed from the wedge-shaped specimen, which was prepared from ytterbium-doped optical fibers by tripod polishing combined with ion milling. Challenges related to sample preparation and the interpretations of images are discussed, but the approach shows great potential to investigate the doping behaviors down to atomic scale in the fibers. The work is expected to help reveal mechanisms affecting the performance for the doped fibers, such as photodarkening which is potentially associated with clustering effects.</p> / Master of Applied Science (MASc)

<p> Poly(N-isopropylacrylamide) (PNIPAM) has attracted much attention as a thermo-responsive polymer. However, the molecular weight (MW) dependence of its phase transition temperature is still controversial. This situation is largely due to the difficulty in synthesizing narrow-disperse PNIPAM. We have addressed the challenge and developed an atom transfer radical polymerization (ATRP) method to prepare narrow-disperse PNIPAM with moderate to high conversions, using branched alcohols as solvents. Aqueous solutions of these narrow-disperse PNIPAMs showed a dramatic decrease of the phase transition temperature with increasing molecular weight, as measured by turbidimetry and differential scanning calorimetry. Four other series of narrow-disperse PNIPAM with well-controlled molecular weights and with end groups of varying hydrophobicity were also synthesized by ATRP using the corresponding initiators, which enabled us to resolve the MW and end group effects. All the four series of samples showed an inverse molecular weight (MW) dependence of their phase transition temperature. The magnitude of the MW dependence decreased when using more hydrophobic end groups. The end groups were observed to have effects on the cloud point temperature, on the shape of the cloud point curves, and on the enthalpy of the phase transition.</p> / Thesis / Master of Science (MSc)

When a biomaterial is inserted into the body, the interaction of the surface with the surrounding biological environment is crucial. Given the importance of the surface, the ability to alter the surface properties to support a compatible environment is therefore desirable. Silicone hydrogel contact lenses (CL) allow for improved oxygen permeability through the incorporation of siloxane functional groups. These groups however are extremely surface active and upon rotation, can impart hydrophobicity to the lens surface, decreasing lens wettability and increasing protein and lipid deposition. Lens biofouling may be problematic and therefore surface modification of these materials to increase compatibility is exceedingly recognized for importance in both industry and research. The current work focuses on the creation of a novel anti-fouling polymer surface by the incorporation of 2-methacryoyloxyethyl phosphorylcholine (MPC), well known for its biomimetic and anti-fouling properties. A controlled polymerization method was used to generate a unique double-grafted architecture to explore the effect of increasing surface density of polyMPC chains on corresponding anti-fouling properties. The novel free polymer was synthesized by a 3-step atom transfer radical polymerization (ATRP). First, poly(2-hydroxyethyl methacrylate) (polyHEMA) was polymerized by ATRP, where the hydroxyl (OH) groups of the polymer then underwent an esterification to create macroinitiating sites. From these sites, a second ATRP of poly(MPC) varying in length occurred, yielding the double-grafted polymer poly(2(2-bromoisobutyryloxy-ethyl methacrylate)-graft-poly(2-methacryloyloxyethyl phosphorylcholine (pBIBEM-g-pMPC). The polymer was designed for resistance to protein adsorption through a possible synergistic effect between the surface induced hydration layer by surrounding PC groups coupled with steric repulsion of the densely grafted chains. To test its potential as a surface modifier, the polymer was grafted from model silicone hydrogel CL through a 4-step surface initiated ATRP (SI-ATRP) in a similar manner to the free polymer. First, the ATRP initiator was immobilized from the HEMA OH groups of the unmodified CL, generating Intermedate-1. A polyHEMA brush was grafted from the initiating sites yielding pHEMA-50, followed by the generation of a second initiator layer (Intermediate- 2). A sequential ATRP of poly(MPC) then generated the target pMPC-50/pMPC-100 surfaces. For the free pBIBEM-g-pMPC polymer analysis, 1H-NMR and GPC determined polymers formed with a predictable MW and low polydispersity (PDI). For surface grafting, using a sacrificial initiator, 1H-NMR and GPC indicated that the pHEMA-50 and pMPC-50/pMPC-100 polymers were well-controlled, with a MW close to the theoretical and a low PDI. For surface chemical composition, ATR-FTIR showed the presence of the ATRP initiator (Intermediate-1 and 2) by the appearance of a C-Br peak and disappearance of the OH peak. XPS confirmed the chemical composition of the 4-step synthesis by a change in the fraction of expected surface elements. Both the surface wettability and EWC of the materials increased upon pMPC modification, further improving upon increasing pMPC chain length. The contact angle was as low as 16.04 ± 2.37º for pMPC-50 surfaces and complete wetting for pMPC-100. Finally, the single protein adsorption using lysozyme and bovine serum albumin (BSA) showed significantly decreased protein levels for pMPC-50/100 lenses, as much as 83% (p 0.00036) for lysozyme and 73% (p 0.0076) for BSA, with no significant difference upon chain length variation. The aforementioned data demonstrates that the novel polymer has potential in providing an anti-fouling and extremely wettable surface, specifically regarding silicone hydrogel CL surfaces. / Thesis / Master of Applied Science (MASc)

Metallic bone implant devices are commonly used to tackle a wide array of bone failures in human patients. The success of such implants relies on the biomechanical and functional bonding between the living bone tissue and implant, a process defined as osseointegration. However, the mechanism of osseointegration is still under debate in the scientific community. One efficient method to help understand this complex process is to characterize the interface between human bones and implant devices after the osseointegration has been established, while another approach is to visualize mineralization in real-time under simulated body conditions. Both of these approaches to understand mineralization have been explored in this thesis. Firstly, due to the inhomogeneous nature of bone and complex topography of implant surfaces, a suitable sample geometry for three-dimensional (3D) characterization was required to fully understand osseointegration. Electron tomography has been proven as an efficient technique to visualize the nanoscale topography of bone-implant interface in 3D. However, resulting from the thickness and shadowing effects of conventional transmission electron microscope (TEM) lamellae at high tilt angles and the limited tilt-range of TEM holders, “missing wedge” artifacts limit the resolution of final reconstructions. In Chapter 3, the exploration of a novel sample geometry to explore osseointegration is reported. Here, on-axis electron tomography based on a needle-shaped sample was applied to solve the problem of the “missing wedge”. This resulted in a near artifact-free 3D visualization of the structure of human bone and laser-modified titanium implant, showing bone growth into the nanotopographies of the implant surface and contributing to the evolution of the definition of osseointegration towards nano-osseointegration. One of the key issues regarding the mechanism of osseointegration that remains is that of the chemical structure at the implant interface, namely distribution of calcium-based and carbon-based components at the interface and their origins. Thus, the second objective of this thesis aimed to push characterization techniques further to four dimensions (4D), by incorporating chemical information as the fourth dimension after the spatial X,Y,Z coordinates. In Chapter 4, correlative 4D characterization techniques including electron energy-loss spectroscopy (EELS) tomography and atom probe tomography (APT) and other spectroscopy techniques were used to probe the nanoscale chemical structure of the bone-implant interface. This work uncovered a transitional biointerphase at the bone-implant interface, consisting of morphological and chemical differences compared to bone away from the interface. Also, a TiN layer between the surface oxide and bulk metal was identified in the laser-modified commercial dental implant. Both findings have implications for the immediate and long-term osseointegration. Since bone formation at the implant interface is a dynamic process, which includes calcium phosphates (CaP) biomineralization as a basis of these reactions, the third objective of this work focused on exploring real-time mineralization processes. Liquid-phase transmission electron microscopy (LP-TEM) is a promising technique to enable real-time imaging with nanoscale spatial resolution and sufficient temporal resolution. In Chapter 5, by using this technique, we present the first real-time imaging of CaP nucleation and growth, which is a direct evidence to demonstrate that CaP mineralization occurs by particle attachment. Overall, this thesis has applied state-of-the-art advanced microscopy techniques to enhance the knowledge and understanding of osseointegration mechanisms by investigating established biointerfaces and real-time mineralization. The developed correlative 4D tomography workflow is transferable to study other interfacial applications in materials science and biological systems, while the LP-TEM work forms a basis for further mineralization research. / Thesis / Doctor of Philosophy (PhD)

Graphene and its functionalized derivatives, such as nitrogen-doped graphene, have recently become a popular substrate material for the proton exchange membrane fuel cell (PEMFC) due to its enhanced electrical conductivity, electrochemical stability, and increased surface area when compared to the conventional, carbon black. In order to further develop the alternative fuel industry, the Pt catalyst within the PEMFC must also be considered. Single Pt atoms have a higher surface area to volume ratio when compared to nanoparticles, thus offering the potential to create a more affordable and efficient PEMFC. In this thesis, electrode materials comprising single Pt atoms and clusters, produced using atomic layer deposition (ALD) on various C derivatives, including graphene, N-doped graphene, carbon nanotubes (CNTs), and N-doped CNTs (NCNTs) are investigated through the utilization of aberration corrected transmission electron microscopy. Structural and chemical analysis was performed on thermally exfoliated N-doped graphene and CVD-produced graphene that was exposed to N+ ion sources. It was determined that the thermally exfoliated N-doped graphene maintained the short-range order of the graphene lattice; however, local inhomogeneities existed for the total N concentration, and the specific N-dopants within and between graphene sheets. More importantly, Pt atoms and clusters were observed and determined to be primarily stabilized at the edge of the N-doped graphene sheets. The stabilization of the Pt atoms and clusters resulted in a significantly higher mass and specific activity for the hydrogen evolution reaction, when compared to the use of a graphene substrate and Pt nanoparticles on C black. The N+ ion implantation in the CVD graphene showed the incorporation of N-dopants; however, electron energy loss spectroscopy revealed structural damage to thin sheets. NCNTs were also characterized in this thesis as possible gas containers, and as a substrate material to examine the effects of varying ALD conditions. It was determined that the NCNTs were an effective N2 gas conduit, wherein a decreasing pressure was observed with an increase to the inner diameter of the nanotubes. Using similar NCNTs, the effect of dosing time, temperature, and substrate on the Pt size were analyzed using ALD. While no singular condition resulted in the sole production of single Pt atoms, modifying both the substrate and dosing time were shown to provide the greatest potential for producing individual Pt atom catalysts. / Thesis / Doctor of Philosophy (PhD)

The recent upsurge of degenerative diseases believed to be the result of oxidative stress has sparked an increased interest in utilizing the fundamental principles of physical organic chemistry to understand biological problems. Enzyme pathways can pose several experimental complications due to their complexity, therefore the small molecule probe approach can be utilized in an attempt understand the more complex enzyme mechanisms. The work described in this dissertation focuses on the use of N-cyclopropyl amines that have been used as probes to study the mechanism of monoamine oxidase (MAO) and cytochrome P-450 (cP-450). A photochemical model study of benzophenone triplet (3BP) with the MAO-B substrate 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP) and two of its derivatives, 1-cyclopropyl-4-phenyl-1,2,3,6-tetrahydropyridine and (+/-)-[trans-2-phenylcyclopropyl-4-phenyl-1,2,3,6-tetrahydropyridine is presented in Chapter 2. The barrier for ring opening of aminyl radical cations derived from N-cyclopropyl derivatives of tertiary amines (such as MPTP) is expected to be low. Reactions of 3BP with all three compounds are very similar. The results suggest that the reaction between benzophenone triplet and tertiary aliphatic amines proceed via a simple hydrogen atom transfer reaction. Additionally these model examinations provide evidence that oxidations of N-cyclopropyl derivatives of MPTP catalyzed by MAO-B may not be consistent with a pure SET pathway. The chemistry of N-cyclopropyl amines has been used to study the mechanism of amine oxidations by cP-450. Until recently, the rate constant for these ring opening reactions has not been reported. Direct electrochemical examinations of N-cyclopropyl-N-methylaniline showed that the radical cation undergoes a unimolecular rearrangement consistent with a cyclopropyl ring opening reaction. Examination of both the direct and indirect electrochemical data showed that the oxidation potential N-cyclopropyl-N-methylaniline to be +0.528 V (0.1 M Ag⁺/Ag), and rate constant for ring opening of 4.1 x 10⁴ s⁻¹. These results are best explained by two phenomena: (i) a resonance effect in which the spin and charge of the radical cation in the ring closed form is delocalized into the benzene ring hindering the overall rate of the ring opening reaction, and/or (ii) the lowest energy conformation of the molecule does not meet the stereoelectronic requirements for a ring opening pathway. Therefore a new series of spiro cyclopropanes were designed to lock the cyclopropyl group into the appropriate bisected conformation. The electrochemical results reported herein show that the rate constant for ring opening of 1'-methyl-3',4'-dihydro-1'H-spiro[cyclopropane-1,2'-quinoline] and 6'-chloro-1'-methyl-3',4'-dihydro-1'H-spiro[cyclopropane-1,2'-quinoline] are 3.5 x 10² s⁻¹ and 4.1 x 10² s⁻¹ with redox potentials of 0.3 V and 0.366 V respectively. In order to examine a potential resonance effect a derivative of N-methyl-N-cyclopropylaniline was synthesized to provide a driving force for the ring opening reaction thereby accelerating the overall rate of the ring opening pathway. The electrochemical results show that the rate constant for ring opening of 4-chloro-N-methyl-N-(2-phenylcyclopropyl)aniline to be 1.7 x 10⁸ s⁻¹ . The formal oxidation potential (E°OX) of this substrate was determined to be 0.53 V. The lowered redox potentials of 1'-methyl-3',4'-dihydro-1'H-spiro[cyclopropane-1,2'-quinoline] and 6'-chloro-1'-methyl-3',4'-dihydro-1'H-spiro[cyclopropane-1,2'-quinoline] can be directly attributed to the electron donating character of the ortho alkyl group of the quinoline base structure of these spiro derivatives, and therefore the relative energy of the ring closed radical cations directly affects the rate of ring opening reactions. The relief of ring strain coupled with the formation of the highly resonance stabilized benzylic radical explains the rate increase for the ring opening reaction of 4-chloro-N-methyl-N-(2-phenylcyclopropyl)aniline. / Ph. D.

Oxidative processes are linked to a number of major disease states as well as the breakdown of many materials. Of particular importance are reactive oxygen species (ROS), as they are known to be endogenously produced in biological systems as well as exogenously produced through a variety of different means. In hopes of better understanding what controls the behavior of ROS, researchers have studied radical chemistry on a fundamental level. Fundamental knowledge of what contributes to oxidative processes can be extrapolated to more complex biological or macromolecular systems. Fundamental concepts and applied data (i.e. interaction of ROS with polymers, biomolecules, etc.) are critical to understanding the reactivity of ROS. A detailed review of the literature, focusing primarily on the hydroxyl radical (HO•) and hydrogen atom (H•) abstraction reactions, is presented in Chapter 1. Also reviewed herein is the literature concerning high density polyethylene (HDPE) degradation. Exposure to treated water systems is known to greatly reduce the lifetime of HDPE pipe. While there is no consensus on what leads to HDPE breakdown, evidence suggests oxidative processes are at play. The research which follows in Chapter 2 focuses on the reactivity of the hydroxyl radical and how it is controlled by its environment. The HO• has been thought to react instantaneously, approaching the diffusion controlled rate and showing little to no selectivity. Both experimental and calculational evidence suggest that some of the previous assumptions regarding hydroxyl radical reactivity are wrong and that it is decidedly less reactive in an aprotic polar solvent than in aqueous solution. These findings are explained on the basis of a polarized transition state that can be stabilized via the hydrogen bonding afforded by water. Experimental and calculational evidence also suggest that the degree of polarization in the transition state will determine the magnitude of this solvent effect. Chapter 3 discusses the results of HDPE degradation studies. While HDPE is an extremely stable polymer, exposure to chlorinated aqueous conditions severely reduces the lifetime of HDPE pipes. While much research exists detailing the mechanical breakdown and failure of these pipes under said conditions, a gap still exists in defining the species responsible or mechanism for this degradation. Experimental evidence put forth in this dissertation suggests that this is due to an auto-oxidative process initiated by free radicals in the chlorinated aqueous solution and propagated through singlet oxygen from the environment. A mechanism for HDPE degradation is proposed and discussed. Additionally two small molecules, 2,3-dichloro-2-methylbutane and 3-chloro-1,1-di-methylpropanol, have been suggested as HDPE byproducts. While the mechanism of formation for these products is still elusive, evidence concerning their identification and production in HDPE and PE oligomers is discussed. Finally, Chapter 4 deals with concluding remarks of the aforementioned work. Future work needed to enhance and further the results published herein is also addressed. / Ph. D.

No / The 70 eV electron impact mass spectra of a wide range of 2-substituted benzazoles are reported and discussed. Particular attention is paid to the mechanistic significance and analytical utility of [M–H]+ and [M–X]+ signals in the spectra of benzazoles in which the 2-substituent contains a terminal aryl group with one or more substituents, X. Loss of H or X occurs preferentially from an ortho-position from ionized 2-benzylbenzimidazoles, 2-phenethylbenzimidazoles, 2-styrylbenzimidazoles, 2-styrylbenzoxazoles and 2-styrylbenzothiazoles. In the three styrylbenzazole series, the [M–H]+ and/or [M–X]+ signals dominate the spectra. This unusually facile loss of H or X may be attributed to a proximity effect, in which cyclization of the ionized molecule is followed by elimination of an ortho-substituent to give an exceptionally stable polycyclic ion. Formation of a new five- or six-membered ring by the proximity effect occurs rapidly; cyclization to a seven-membered ring takes place rather less readily; but formation of a ring with only four atoms or more than seven atoms is not observed to a significant extent. The proximity effect competes effectively with loss of a methyl radical by simple cleavage of an ethyl, isopropyl and even a t-butyl group in the pendant aromatic ring of ionized 2-(4-alkylstyryl) benzazoles.

No / Several series of styrylbenzoxazoles of general formula XC6H3(NCO)CH=CHC6H4Y [X= F, Cl or Br; Y = H, F, Cl, Br, CH3 or CH3O] have been investigated by positive ion electrospray and electron ionization mass spectrometry. These compounds, many of which are biologically active or have pharmaceutical potential, show in their electrospray spectra strong peaks for MH+ ions, which undergo relatively little fragmentation. The electron ionization spectra are extremely clean, being dominated by the loss of an atom or radical, Y*, from the ortho position of the pendant ring, by a rearrangement that may be interpreted as a proximity effect. The resultant [M-Y](+) ions are exceptionally stable and rarely undergo further fragmentation. The analytical value of this proximity effect, which is analogous to intramolecular aromatic substitution, in revealing the presence of a substituent in the pendant ring and determining its position, is emphasized. Elimination of a species (including H* or F*) derived from an ortho substituent in the pendant ring occurs even when apparently more favourable alternative fragmentation is possible by direct cleavage of the C-X bond (X = Cl or Br) in the benzoxazole ring.