VictorJuiz/thesis huggingface dataset:
Selenophene- and Thiophene-based π-Conjugated Polymer Gels

In this thesis, I describe my effort in the synthesis of selenophene- and thiophene-based conjugated polymers and the development of organogels and hydrogels from them. In Chapter 1, I provide a general introduction on what are conjugated polymers and their applications. Then, a brief overview of programmable self-assembly of conjugated polymers including covalent programming and solid-state programming is introduced. It provides the background, importance, and recent works on the development of conjugated polymer gels. In Chapter 2, I describe the formation and characterization of selenophene- and thiophene-based conjugated homopolymer organogels. I demonstrate the first reported polyselenophene organogels and the result shows they are promising for the development of stretchable electronics. I have also developed a cycle-doping method to successfully dope the bulk gel films and offer the merit of being able to monitor the change in the film conductivity as the doping cycle increases at the same time. And this method can be applied to dope bulk films in general. In Chapter 3, I further expand the types of conjugated polymer organogels to selenophene- and thiophene-based statistical copolymers. I investigate the influence of molecular weight on the electrical performance of those statistical copolymers. I report the self-assembly behaviour of both the statistical copolymer thin films and their gels at low, medium, and high degrees of polymerization. And the doping mechanism of statistical copolymer gels is also determined. In Chapter 4, I examine the concept of forming hydrogels from full conjugated block copolymers. I demonstrate the synthesis of an amphiphilic block copolymer and the successful development of hydrogel from it. In Chapter 5, I summarize the main conclusions and offer outlooks for my thesis work. Future directions in the development of conjugated polymer organogels and hydrogels are described, and they could offer a better understanding and higher impact in the field of conjugated polymer gels.

Advisor: Seferos, Dwight
Ultralight Axions and the Cosmic Web

The $\Lambda$CDM model suggests that most of the mass in our Universe is composed of dark matter of unknown origin. Among the most promising dark matter candidates are the axions which are light bosons which were initially theorized to solve the Strong CP problem of quantum chromodynamics. Axions also arise in string theory where they can form in large numbers on a spectrum of masses. At the lower end of this spectrum, we find the ultralight axions (ULAs) which are the topic of this dissertation. ULAs' very low mass make them challenging to detect directly. However it also makes their de Broglie wavelength sufficiently large for them to alter the formation of cosmic structures such as halos and filaments. Given the enduring mystery surrounding dark matter, detecting traces of these particles in the cosmic web would constitute a major advance in in the field. To this end, we formulate three research goals: (1) identify the signatures of ULAs on the cosmic web and how they can be observed, (2) differentiate between axions and other particles and dark matter candidates, and (3) reduce the significant computational cost associated with ULA simulations. The chapters of this work describe the steps we have taken to tackle these questions. First, we developed fast modelling techniques based on perturbation theory to study the impact of these axions on the formation and evolution of cosmic filaments. Then, we considered a population of thermal axions at the epoch of Big Bang nucleosynthesis, and identified cosmic microwave background observatories as the best probes of the effect of ULAs in the early Universe. At lower redshifts, we also looked for traces of ULAs in galaxy clustering statistics by adapting a model based on the effective field theory of large-scale structure. To validate our improved model, we generated our own set of simulated galaxy catalogs and reached the strongest constraints on their contribution to the dark matter content of the Universe for axion masses $10^{-32}\;\mathrm{eV}\leq m\leq 10^{-25}\;\mathrm{eV}$. Finally, we identified new observational signatures for axions with masses above $10^{-25}$ eV by creating the first cosmological mixed ultralight dark matter simulations.

Advisor: Bond, Richard
Hložek, Renée
Unaccompanied Violin Music of Mid-twentieth-century Israeli Composers: Paul Ben-Haim’s Three Studies and Ben-Zion Orgad’s Ballade

The primary goal of this dissertation is to explore the stylistic elements of the unaccompanied violin works of two Israeli composers of the mid-twentieth century, Paul Ben-Haim (1897-1984) and Ben-Zion Orgad (1926-2006). These elements are representative of an Israeli national style that dominated the music of the period in the Israel-Palestine region.The incorporation of these stylistic elements resulted in the development of violinistic idioms, both technical and motivic, which can be seen in the works of these composers. These techniques may also be found in the works of other Israeli composers participating in the writing of this genre, despite their differences in personal styles. My aim is to establish some of these key identifiers that contributed to this distinct trend. The dissertation begins with a brief historical overview of the early twentieth-century Israeli musical style which was developed by immigrant composers of British Mandated Palestine. The life and musical style of Ben-Haim, considered to be one of the founding fathers of this early period is discussed next, specifically his contributions to the early Israeli style and how they manifested in his solo violin works. Special attention is placed on the manipulation of metric impulses and combinations of Western and non-Western elements. A detailed analysis of his late work, the Three Studies for Solo Violin (1981) shows examples of these compositional techniques.The following chapter focuses on the music of Ben-Zion Orgad. A student of Ben-Haim, Orgad represents the second generation of Israeli composers, showing a more developed usage of Israeli idioms that were presented in the works of the founders, in combination with diverse influences from inside and outside of the state. Of particular interest is Orgad’s manipulation of metric impulses which stem from his studies of the Hebrew language. An analysis of his Ballade for solo violin (1947), a work written shortly after his tutelage with Ben-Haim, illustrates these characteristics. The concluding chapter briefly situates these works in the context of unaccompanied violin works by other prominent Israeli composers of the mid-twentieth century. This study reveals an Israeli style of writing for the unaccompanied violin that carries distinctive stylistic elements.

Keywords: Ben-Haim
Israeli
Orgad
Solo
Unaccompanied
Violin
Advisor: McClelland, Ryan
Doctors, Drugs, and Death: Separating Supply and Demand Factors in the Opioid Crisis

Dramatic reversals in mortality trends have been identified in the United States and Canada since 1997, in part driven by rising opioid-related deaths. Two schools of thought have emerged to explain these statistics: demand and supply side forces. The supply-side channel argues that these deaths are a product of the increasing availability of legally prescribed opioids. The demand-side channel argues that growing income inequality creates a mental health burden, which can manifest in individuals as suicidality and substance abuse. This thesis investigates precisely the role of these two channels on health consequences and mortality in the United States and Canada. The first chapter focuses on supply-side forces in the opioid epidemic, particularly through the role of pharmaceutical firm promotion and physician prescribing in the United States. In order to disentangle the supply behaviour of doctors from the demand behaviour of patients, it leverages the staggered introduction of Medicaid expansion across states to exogenously shift opioid supply. The results suggest that pharmaceutical firms respond strategically to this policy by increasing their promotional targeting of physicians. These promotions appear to be effective in changing physicians prescribing behaviour, even during a period of increased awareness of the dangers of these drugs. While not persistent, this is associated with a small increase in opioid-related mortality. The second chapter focuses on the role of absolute and relative income effects on hospitalizations in Canada. To identify the effect of a change of one's position in the income distribution, it exploits the heterogeneous effects of exogenous movements in the price of oil on the distribution of local income. Using hospitalization records linked to census data, it demonstrates that non-oil workers who have many neighbors in the oil industry are more likely to be hospitalized after oil prices rise (and their relative income falls). These results shed new light on mechanisms through which income inequality might affect people's well-being. Overall, these two chapters highlight the complex interrelationships between supply and demand side forces in the opioid epidemic.

Advisor: Benjamin, Dwayne
Eli, Shari
Cultivating Whole Persons through Liberal Arts Education: A Case Study of Three Universities in Mainland China, Hong Kong, and Taiwan

This study explores Liberal Arts Education (LAE) in three institutions in Chinese contexts to see how their LAE is designed and implemented toward whole person cultivation by nurturing students as responsible citizens with capabilities needed in the uncertain future of the 21st century. In contrast to human capital theory, the study takes the lens of the capabilities approach to examine liberal arts models and their innovative practices for nurturing the all-around development of critical thinking, civic engagement, and intercultural competence. The study adopts a mixed-methods design, using data such as curriculum documents, interviews with administrators and faculty members, and surveys with students and alumni. I examined how universities design and adapt LAE models into their social and cultural contexts. I found that the three universities integrated cultural tradition and social factors into their LAE, so as to form an ideal higher education with a focus on the value of person-making or whole person development rooted in a Chinese cultural tradition. There are also differences in LAE in the three societies with Yuanpei influenced by the socialist context in Mainland China, Lingnan situated in the practically oriented international city of Hong Kong, and greater emphasis on traditional Chinese culture and the influence of Christian tradition in Tunghai, situated in Taiwan. Following the common model of broad knowledge, residential learning, close student-faculty relationships, small-class teaching, and extra-curricular activities, the LAE in the three institutions constitutes an educational philosophy and mode of learning focusing on mentorship experience, participation, and an experiential process, which prepares students for future uncertainties with a sense of responsibility and capabilities both for personal flourishing and sustainable development. This educational philosophy and mode of learning can find its roots in both Western and Confucian learning approaches. Given the massification of higher education, findings from the three institutions indicated that LAE in these Chinese contexts has moved away from the elite status it often held in the past and is offered to the majority of students for the cultivation of abilities needed for the future. It thus contributes to inclusion and social equity in the 21st century.

Keywords: capabilities
Confucian
East Asia
general education
liberal arts education
whole person
Advisor: Hayhoe, Ruth
The Legal Regulation of Holy Sites Through the Constitutional Guarantee of Freedom of Religion

This comparative analysis is a study of the legal regulation of holy sites through the constitutional guarantee of freedom of religion. I investigate how the holy site is produced within the co-constitutive relationship between law and space and argue that in remaining in the realm of the abstract theory, the law fails to capture the material aspects of freedom of religion. After summarizing the theoretical foundations of legal geography and investigating the workings of the secular in space, I study holy sites in India, Israel and Canada. Each chapter traces the historical development of regulations, with particular attention on the impact of colonialism, and how secularism influenced the legal construction of the space. In the comparative analysis, I excavate common moves within the three jurisdictions and argue that we can only start to capture these dynamics by paying attention to the complex interaction between law, religion, and space.

Keywords: critical legal studies
freedom of religion
holy sites
law and post-colonialism
legal geography
sacred space
Advisor: Shachar, Ayelet
Engineered SH2 Domains for Targeted Phosphoproteomics

The Src Homology 2 (SH2) domain is a small modular pTyr-peptide/protein binding domain that mediates important signal transduction pathways in human cells. SH2 domains bind ligands in a pTyr and sequence dependent manner, albeit with low micromolar affinity. As the canonical modular post-translational modification (PTM) binding domain, the SH2 domain has been studied extensively and engineered into a biotechnology for affinity-purification coupled to mass spectrometry (AP-MS) workflows.The SH2 domain of the Src tyrosine kinase protein has been previously engineered (superSrc, sSrc1) to increase its affinity for pTyr-peptides and used to probe the phosphoproteome of cancer cell lines. This SH2 superbinder could recover greater numbers of pTyr-peptides than conventional technologies like IMAC or anti-pTyr antibodies and can be inexpensively produced in large quantities. However, sSrc1 can only recover a certain subset of pTyr-peptides from the phosphoproteome due to its intrinsic specificity preferences. This limits coverage of the pTyr-phosphoproteome and therefore the use of sSrc1 use in AP-MS workflows. Here, I developed a general method to engineer the affinity of human SH2 domains with different specificity profiles and used these new SH2 superbinders for AP-MS based phosphoproteomics. A new Fes-SH2 domain phage-display library was constructed and used to select a variant (superFes, sFes1) with high affinity for Fes specific pTyr-peptides. To understand the molecular mechanisms of sFes1 high affinity binding, the structure of sFes1 bound to a pTyr-peptide was solved using x-ray crystallography. Systematic structure-function analysis of the sFes1 and sSrc1 superbinders showed a common mechanism of pTyr coordination between different SH2 superbinders. This data was then used to graft essential pTyr-coordinating residues into seventeen additional human SH2 domains that had different specificity profiles. SH2 superbinders could enrich far greater numbers of unique pTyr-peptides than their wild-type (wt) counterparts or IMAC controls in AP-MS experiments. This work also demonstrated that SH2 superbinders maintain most of their intrinsic specificity profiles, enabling comprehensive phosphoproteome coverage. Finally, SH2 superbinders with unique specificity classes capable of enriching large numbers of pTyr-peptides were combined and used to probe the phosphoproteome of a cancer cell line with unparalleled depth and coverage.

Keywords: Diagnostics
Phage Display
Phosphotyrosine
Protein Engineering
Proteomics
Structural Biology
Advisor: Sidhu, Sachdev S
Essays in the Macroeconomics of the Labour Market

In this thesis, I combine three essays that examine earnings consequences of labour market transitions, using detailed data and search-theoretical frameworks. In the first chapter, I use German employer-employee data to explore long-run earnings consequences of mass layoffs. I find that workers who return to the employer that laid them off experience larger earnings losses, both in the short and in the long run. These larger earnings losses for these so-called recalled workers are driven by employment in the short run and by wages in the long run. Furthermore, recalled workers are more likely to lose their job again compared to workers who were re-employed at different employers. In the second chapter, I propose a job search model that explains these findings. In the model, I distinguish between workers who may be recalled soon and regularly unemployed workers. The model replicates the larger earnings losses experienced by recalled workers, despite these workers optimally choosing for this recall, thus suggesting that the recall was not a bad outcome. Indeed, decomposing the difference in earnings loss between recalled and non-recalled workers shows that the short-run difference is largely explained by selection, whereas the long-run effect is driven by recalled workers being more likely to lose their job again. The third chapter investigates the cyclicality of occupational mobility and its consequences for subsequent earnings and wages, distinguishing between workers who switch occupations through unemployment and workers who switch during a job-to-job transition. Using data from the Survey of Income and Program Participation, I find that the fraction of occupational switchers switching through unemployment is countercyclical, and while these workers generally do worse in terms of earnings than workers who make a job-to-job transition, their earnings and wage patterns may slightly improve in recessions. I then propose a job search model of occupational mobility in which I incorporate both types of occupational switches and show that the overall deterioration of earnings outcomes for occupational switchers in recessions is driven by a composition change towards switching through unemployment, dampened by the outcomes experienced by workers who switch occupations without switching employers.

Keywords: Displacement
Labor Market Transitions
Occupational Mobility
Recall
Advisor: Kambourov, Gueorgui
Wolthoff, Ronald
Efficiency Automation in Aerodynamic Shape Optimization: Multimodal Dynamic Search Spaces

This work addresses two topics of relevance to efficiency and automation in aerodynamic shape optimization: multimodality and dynamic geometry control. Multimodality presents a challenge to efficiency and automation by introducing the risk of poor optimizer performance or inferior final geometries if not adequately addressed, necessitating careful selection of an optimization algorithm and considerable user insight. To shed light on this risk, a previously developed gradient-based multistart algorithm is leveraged to perform a large-scale parametric study of multimodality in aerodynamic shape optimization. This study reveals that multimodality is much more common in aerodynamic shape optimization than previously believed, that it is endemic in exploratory optimization problems, and that such multimodality is robust in the face of common optimization constraints. Traditional static geometry control methods offer a similar impediment to efficiency and automation by introducing performance trade-offs at various stages of optimization, enforcing arbitrary constraints on open-ended optimization, and necessitating foreknowledge of problem behaviour to design an effective control scheme. These shortcomings can be mitigated through dynamic geometry control, which partly automates the geometry control design process by refining the geometry control topology throughout optimization; such refinement can occur in a pre-determined fashion (as in progressive control) or more automatically using sensitivity information to guide refinement (as in adaptive control). Both methods are implemented in the context of axial and free-form deformation geometry control, and several novel contributions are made to the adaptive algorithm including several novel ``potential indicators" to rank candidate refinements, a new approach to the treatment of active constraints, and the application of these methods to a wider suite of problems than previously attempted. This work demonstrates that dynamic geometry control is effective, reducing required iterations to convergence by 50% or more, realizing reductions in final drag of up to 2% while using as little as 10% as many design variables as a well-designed static control scheme, all while reducing labour requirements on the user. These gains are demonstrated across a wide variety of problems, representative of detailed, preliminary, and exploratory problems often encountered in both academia and industry.

Keywords: Aerodynamic Shape Optimization
Computational Fluid Dynamics
Dynamic Geometry Control
Multimodality
Optimization
Advisor: Zingg, David W
Functional Transcendence in Mixed Hodge Theory

The Ax-Schanuel theorem is a function field analogue of the Schanuel’s conjecture in transcendental number theory. Building on the works of Bakker, Gao, Klingler, Mok, Pila, Tsimerman, Ullmo and Yafaev, we extend the Ax-Schanuel theorem to mixed period mappings. Using this together with the Ax-Schanuel theorem for foliated principal bundles by Blázquez-Sanz, Casale, Freitag, and Nagloo, we furthur extend the Ax-Schanuel theorem to the derivatives of mixed period mappings. Linear subspaces in the Ax-Schanuel theorem are replaced by weak Mumford-Tate domains, which are certain group orbits of mixed Hodge structures. Likewise, algebraic subtori are replaced by a notion called weakly special subvarieties. We prove that if an irreducible analytic subset of the jet space of germs of local liftings of a mixed period mapping satisfies a certain property about the dimensions of this subset and its Zariski closure, then the projection of it lies in a proper weakly special subvariety. The proof uses o-minimal geometry, namely the definable Chow theorem and the Pila-Wilkie counting theorem. Preliminarily, we prove that the weak Mumford-Tate domains have complex structures, and that their real-split retractions can be decomposed into semisimple and unipotent parts. We also prove that the image of a mixed period mapping is contained in the weak Mumford-Tate domain that arises from the monodromy group of the variation.

Keywords: Ax-Schanuel
functional transcendence
mixed Hodge
Advisor: Tsimerman, Jacob