Photogenerated o-Azaxylylenes: Mechanistic Studies and Synthetic Applications

This research sets out to build upon excited state o-azaxylylene cycloaddition. The mechanism behind the excitation and cycloaddition process of photogenerated o-azaxylylenes was determined experimentally. Time-correlated single-photon counting, steady-state spectroscopy, triplet quenching experiments, and quantum yield studies provided evidence suggesting that excited state intramolecular proton transfer is followed by intersystem crossing and stepwise addition to the tethered unsaturated pendant. In keeping with the principles of diversity oriented synthesis, a modular approach was taken to gain access to a diverse array of N,O,S-Polyheterocycles which were modified postphotochemically via Suzuki coupling to yield fused biaryls. Cycloaddition products, outfitted with halogens in the aromatic ring of the o-azaxylylene, proved to be reactive with a variety of boronic acids resulting in a rapid growth in structural complexity. A novel procedure was developed that utilized multiple o-azaxylylene cores in a photochemical cascade transformation yielding complex scaffolds of unprecedented topology. The photoprecursors were produced in a one-pot two-step sequence from commercially available starting materials, and upon irradiation yield structures containing up to five fused hetrocyclic rings, and showed complete diastereoselectivity.

Exponential decay of spin-spin correlation between distant defect states produced by contour hydrogenation of polycyclic aromatic hydrocarbon molecules

The first few low-lying spin states of alternant polycyclic aromatic hydrocarbon (PAH) molecules of several shapes showing defect states induced by contour hydrogenation have been studied both by ab initio methods and by a precise numerical solution of Pariser-Parr-Pople (PPP) interacting model. In accordance with Lieb's theorem, the ground state shows a spin multiplicity equal to one for balanced molecules, and it gets larger values for imbalanced molecules (that is, when the number of π electrons on both subsets is not equal). Furthermore, we find a systematic decrease of the singlet-triplet splitting as a function of the distance between defects, regardless of whether the ground state is singlet or triplet. For example, a splitting smaller than 0.001 eV is obtained for a medium size C46H28 PAH molecule (di-hydrogenated [11]phenacene) showing a singlet ground state. We conclude that π electrons unbound by lattice defects tend to remain localized and unpaired even when long-range Coulomb interaction is taken into account. Therefore they show a biradical character (polyradical character for more than two defects) and should be studied as two or more local doublets. The implications for electron transport are potentially important since these unpaired electrons can trap traveling electrons or simply flip their spin at a very small energy cost.

Cyclobutadiene automerization and rotation of ethylene: Energetics of the barriers by using Spin-polarized wave functions

Spin-projected spin polarized Møller–Plesset and spin polarized coupled clusters calculations have been made to estimate the cyclobutadiene automerization, the ethylene torsion barriers in their ground state, and the gap between the singlet and triplet states of ethylene. The results have been obtained optimizing the geometries at MP4 and/or CCSD levels, by an extensive Gaussian basis set. A comparative analysis with more complex calculations, up to MP5 and CCSDTQP, together with others from the literature, have also been made, showing the efficacy of using spin-polarized wave functions as a reference wave function for Møller–Plesset and coupled clusters calculations, in such problems.

The rearrangements of naphthyinitrenes: UV/Vis and IR spectra of azirines, cyclic ketenimines, and cyclic nitrile ylides

Ar matrix photolysis of 1- and 2-naphthyl azides 3 and 4 at 313 nm initially affords the singlet naphthyl nitrenes, (1)1 and (1)2. Relaxation to the corresponding lower energy, persistent triplet nitrenes (3)1 and (3)2 competes with cyclization to the azirines 15 and 18, which can also be formed photochemically from the triplet nitrenes. On prolonged irradiation, the azirines can be converted to the seven-membered cyclic ketenimines 10 and 13, respectively, as described earlier by Dunkin and Thomson. However, instead of the o-quinoid ketenimines 16 and 19, which are the expected primary ring-opening products of azirines 15 and 18, respectively, we observed their novel bond-shift isomers 17 and 20, which may be formally regarded as cyclic nitrile ylides. The existence of such ylidic heterocumulenes has been predicted previously, but this work provides the first experimental observation of such species. The factors which are responsible for the special stability of the ylidic species 17 and 20 are discussed.

Seronegative spondyloarthropathies: To lump or split?

The advent of novel biological therapies for the treatment of rheumatic disease has renewed interest in the seronegative spondyloarthropathies (SpAs). International efforts are redefining disease classification and measures of disease activity, outcome, metrology, and imaging. However, opinion is divided between those who propose that the SpA group represents the same disease with variable expression (the lumpers) and those who consider these to be separate diseases with shared clinical features (the splitters). This review presents the evidence for both approaches.

Towards effective indexing for very large video sequence database

With rapid advances in video processing technologies and ever fast increments in network bandwidth, the popularity of video content publishing and sharing has made similarity search an indispensable operation to retrieve videos of user interests. The video similarity is usually measured by the percentage of similar frames shared by two video sequences, and each frame is typically represented as a high-dimensional feature vector. Unfortunately, high complexity of video content has posed the following major challenges for fast retrieval: (a) effective and compact video representations, (b) efficient similarity measurements, and (c) efficient indexing on the compact representations. In this paper, we propose a number of methods to achieve fast similarity search for very large video database. First, each video sequence is summarized into a small number of clusters, each of which contains similar frames and is represented by a novel compact model called Video Triplet (ViTri). ViTri models a cluster as a tightly bounded hypersphere described by its position, radius, and density. The ViTri similarity is measured by the volume of intersection between two hyperspheres multiplying the minimal density, i.e., the estimated number of similar frames shared by two clusters. The total number of similar frames is then estimated to derive the overall similarity between two video sequences. Hence the time complexity of video similarity measure can be reduced greatly. To further reduce the number of similarity computations on ViTris, we introduce a new one dimensional transformation technique which rotates and shifts the original axis system using PCA in such a way that the original inter-distance between two high-dimensional vectors can be maximally retained after mapping. An efficient B+-tree is then built on the transformed one dimensional values of ViTris' positions. Such a transformation enables B+-tree to achieve its optimal performance by quickly filtering a large portion of non-similar ViTris. Our extensive experiments on real large video datasets prove the effectiveness of our proposals that outperform existing methods significantly.

Auditory stream segregation in cochlear implant listeners:measures based on temporal discrimination and interleaved melody recognition

The evidence that cochlear implant listeners routinely experience stream segregation is limited and equivocal. Streaming in these listeners was explored using tone sequences matched to the center frequencies of the implant’s 22 electrodes. Experiment 1 measured temporal discrimination for short (ABA triplet) and longer (12 AB cycles) sequences (tone/silence durations = 60/40 ms). Tone A stimulated electrode 11; tone B stimulated one of 14 electrodes. On each trial, one sequence remained isochronous, and tone B was delayed in the other; listeners had to identify the anisochronous interval. The delay was introduced in the second half of the longer sequences. Prior build-up of streaming should cause thresholds to rise more steeply with increasing electrode separation, but no interaction with sequence length was found. Experiment 2 required listeners to identify which of two target sequences was present when interleaved with distractors (tone/silence durations = 120/80 ms). Accuracy was high for isolated targets, but most listeners performed near chance when loudness-matched distractors were added, even when remote from the target. Only a substantial reduction in distractor level improved performance, and this effect did not interact with target-distractor separation. These results indicate that implantees often do not achieve stream segregation, even in relatively unchallenging tasks.

Pryolytic and kinetic study of Chlorella Vulgaris under isothermal and non-isothermal conditions

Algae are a new potential biomass for energy production but there is limited information on their pyrolysis and kinetics. The main aim of this thesis is to investigate the pyrolytic behaviour and kinetics of Chlorella vulgaris, a green microalga. Under pyrolysis conditions, these microalgae show their comparable capabilities to terrestrial biomass for energy and chemicals production. Also, the evidence from a preliminary pyrolysis by the intermediate pilot-scale reactor supports the applicability of these microalgae in the existing pyrolysis reactor. Thermal decomposition of Chlorella vulgaris occurs in a wide range of temperature (200-550°C) with multi-step reactions. To evaluate the kinetic parameters of their pyrolysis process, two approaches which are isothermal and non-isothermal experiments are applied in this work. New developed Pyrolysis-Mass Spectrometry (Py-MS) technique has the potential for isothermal measurements with a short run time and small sample size requirement. The equipment and procedure are assessed by the kinetic evaluation of thermal decomposition of polyethylene and lignocellulosic derived materials (cellulose, hemicellulose, and lignin). In the case of non-isothermal experiment, Thermogravimetry- Mass Spectrometry (TG-MS) technique is used in this work. Evolved gas analysis provides the information on the evolution of volatiles and these data lead to a multi-component model. Triplet kinetic values (apparent activation energy, pre-exponential factor, and apparent reaction order) from isothermal experiment are 57 (kJ/mol), 5.32 (logA, min-1), 1.21-1.45; 9 (kJ/mol), 1.75 (logA, min-1), 1.45 and 40 (kJ/mol), 3.88 (logA, min-1), 1.45- 1.15 for low, middle and high temperature region, respectively. The kinetic parameters from non-isothermal experiment are varied depending on the different fractions in algal biomass when the range of apparent activation energies are 73-207 (kJ/mol); pre-exponential factor are 5-16 (logA, min-1); and apparent reaction orders are 1.32–2.00. The kinetic procedures reported in this thesis are able to be applied to other kinds of biomass and algae for future works.

Holonic supply chain:a study from family-based manufacturing perspective

In the contemporary business environment, to adhere to the need of the customers, caused the shift from mass production to mass-customization. This necessitates the supply chain (SC) to be effective flexible. The purpose of this paper is to seek flexibility through adoption of family-based dispatching rules under the influence of inventory system implemented at downstream echelons of an industrial supply chain network. We compared the family-based dispatching rules in existing literature under the purview of inventory system and information sharing within a supply chain network. The dispatching rules are compared for Average Flow Time performance, which is averaged over the three product families. The performance is measured using extensive discrete event simulation process. Given the various inventory related operational factors at downstream echelons, the present paper highlights the importance of strategically adopting appropriate family-based dispatching rule at the manufacturing end. In the environment of mass customization, it becomes imperative to adopt the family-based dispatching rule from the system wide SC perspective. This warrants the application of intra as well as inter-echelon information coordination. The holonic paradigm emerges in this research stream, amidst the holistic approach and the vital systemic approach. The present research shows its novelty in triplet. Firstly, it provides leverage to manager to strategically adopting a dispatching rule from the inventory system perspective. Secondly, the findings provide direction for the attenuation of adverse impact accruing from demand amplification (bullwhip effect) in the form of inventory levels by appropriately adopting family-based dispatching rule. Thirdly, the information environment is conceptualized under the paradigm of Koestler's holonic theory.

Photo-Reactivity of Natural Dissolved Organic Matter from Fresh to Marine Waters in the Florida Everglades, USA

Natural dissolved organic matter (DOM) is the major absorber of sunlight in most natural waters and a critical component of carbon cycling in aquatic systems. The combined effect of light absorbance properties and related photo-production of reactive species are essential in determining the reactivity of DOM. Optical properties and in particular excitation–emission matrix fluorescence spectroscopy combined with parallel factor analysis (EEM-PARAFAC) have been used increasingly to track sources and fate of DOM. Here we describe studies conducted in water from two estuarine systems in the Florida Everglades, with a salinity gradient of 2 to 37 and dissolved organic carbon concentrations from 19.3 to 5.74 mg C L−1, aimed at assessing how the quantity and quality of DOM is coupled to the formation rates and steady-state concentrations of reactive species including singlet oxygen, hydroxyl radical, and the triplet excited state of DOM. These species were related to optical properties and PARAFAC components of the DOM. The formation rate and steady-state concentration of the carbonate radical was calculated in all samples. The data suggests that formation rates, particularly for singlet oxygen and hydroxyl radicals, are strongly coupled to the abundance of terrestrial humic-like substances. A decrease in singlet oxygen, hydroxyl radical, and carbonate radical formation rates and steady-state concentration along the estuarine salinity gradient was observed as the relative concentration of terrestrial humic-like DOM decreased due to mixing with microbial humic-like and protein-like DOM components, while the formation rate of triplet excited-state DOM did not change. Fluorescent DOM was also found to be more tightly coupled to reactive species generation than chromophoric DOM.

The role of frameshifting and transcriptional dysregulation in spinocerebellar ataxia type-3

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Atomic layer structure of vanadium oxide nanotubes grown on nanourchin structures

We report the detailed characterization of high quality vanadium oxide (VOx) nanotubes (NTs) and highlight the zipping of adjacent vanadate layers in such NTs formed on remarkable nanourchin structures. These nanostructures consist of high-density spherical radial arrays of NTs. The results evidence vanadate NTs with unprecedented uniformity and evidences the first report of vanadate atomic layer zipping. The NTs are ∼2 μm in length with inner diameters of 20-30 nm. The tube walls comprise scrolled triplet-layers of vanadate intercalated with organic surfactant. Such high-volume structures might be useful as open-access electrolyte scaffolds for lithium insertion-based charge storage devices.

Phase Locked Loop and Modulo Games, The Dogma Loops; and “Finding Ibrida”

This dissertation consists of two independent musical compositions and an article detailing the process of the design and assembly of an electric guitar with particular emphasis on the carefully curated suite of embedded effects.

The first piece, 'Phase Locked Loop and Modulo Games' is scored for electric guitar and a single echo of equal volume less than a beat away. One could think of the piece as a 15 minute canon at the unison at the dotted eighth note (or at times the quarter or triplet-quarter), however the compositional motivation is more about weaving a composite texture between the guitar and its echo that is, while in theory extremely contrapuntal, in actuality is simply a single [superhuman] melodic line.

The second piece, 'The Dogma Loops' picks up a few compositional threads left by ‘Phase Locked Loop’ and weaves them into an entirely new tapestry. 'Phase Locked Loop' is motivated by the creation of a complex musical composite that is for the most part electronically transparent. 'The Dogma Loops' questions that same notion of composite electronic complexity by essentially asking a question: "what are the inputs to an interactive electronic system that create the most complex outputs via the simplest musical means possible?"

'The Dogma Loops' is scored for Electric Guitar (doubling on Ukulele), Violin and Violoncello. All of the principal instruments require an electronic pickup (except the Uke). The work is in three sections played attacca; [Automation Games], [Point of Origin] and [Cloning Vectors].

The third and final component of the document is the article 'Finding Ibrida.' This article details the process of the design and assembly of an electric guitar with integrated effects, while also providing the deeper context (conceptual and technical) which motivated the efforts and informed the challenges to hybridize the various technologies (tubes, transistors, digital effects and a microcontroller subsystem). The project was motivated by a desire for rigorous technical and hands-on engagement with analog signal processing as applied to the electric guitar. ‘Finding Ibrida’ explores sound, some myths and lore of guitar tech and the history of electric guitar distortion and its culture of sonic exploration.

A Search for a New Particle Decaying to Pairs of Weak Gauge Bosons with the ATLAS Detector

A search for new heavy resonances decaying to boson pairs (WZ, WW or ZZ) using 20.3 inverse femtobarns of proton-proton collision data at a center of mass energy of 8 TeV is presented. The data were recorded by the ATLAS detector at the Large Hadron Collider (LHC) in 2012. The analysis combines several search channels with the leptonic, semi-leptonic and fully hadronic final states. The diboson invariant mass spectrum is studied for local excesses above the Standard Model background prediction, and no significant excess is observed for the combined analysis. 95$\%$ confidence limits are set on the cross section times branching ratios for three signal models: an extended gauge model with a heavy W boson, a bulk Randall-Sundrum model with a spin-2 graviton, and a simplified model with a heavy vector triplet. Among the individual search channels, the fully-hadronic channel is predominantly presented where boson tagging technique and jet substructure cuts are used. Local excesses are found in the dijet mass distribution around 2 TeV, leading to a global significance of 2.5 standard deviations. This deviation from the Standard Model prediction results in many theory explanations, and the possibilities could be further explored using the LHC Run 2 data.

Experimental and Theoretical Models to Probe Mechanisms of Biological Charge Flow

Nature is challenged to move charge efficiently over many length scales. From sub-nm to μm distances, electron-transfer proteins orchestrate energy conversion, storage, and release both inside and outside the cell. Uncovering the detailed mechanisms of biological electron-transfer reactions, which are often coupled to bond-breaking and bond-making events, is essential to designing durable, artificial energy conversion systems that mimic the specificity and efficiency of their natural counterparts. Here, we use theoretical modeling of long-distance charge hopping (Chapter 3), synthetic donor-bridge-acceptor molecules (Chapters 4, 5, and 6), and de novo protein design (Chapters 5 and 6) to investigate general principles that govern light-driven and electrochemically driven electron-transfer reactions in biology. We show that fast, μm-distance charge hopping along bacterial nanowires requires closely packed charge carriers with low reorganization energies (Chapter 3); singlet excited-state electronic polarization of supermolecular electron donors can attenuate intersystem crossing yields to lower-energy, oppositely polarized, donor triplet states (Chapter 4); the effective static dielectric constant of a small (~100 residue) de novo designed 4-helical protein bundle can change upon phototriggering an electron transfer event in the protein interior, providing a means to slow the charge-recombination reaction (Chapter 5); and a tightly-packed de novo designed 4-helix protein bundle can drastically alter charge-transfer driving forces of photo-induced amino acid radical formation in the bundle interior, effectively turning off a light-driven oxidation reaction that occurs in organic solvent (Chapter 6). This work leverages unique insights gleaned from proteins designed from scratch that bind synthetic donor-bridge-acceptor molecules that can also be studied in organic solvents, opening new avenues of exploration into the factors critical for protein control of charge flow in biology.