VictorJuiz/thesis huggingface dataset:
A Unified, [2+2+n] Cycloaddition Platform for Synthesis of Diverse Conjugated Nanocarbons

Future developments in molecular carbon nanoscience will hinge on the availability of versatile synthetic strategies that enable rational control of properties. Since the majority of nanocarbons are comprised of fused rings, polycyclic aromatic hydrocarbons (PAHs) can be viewed both as the smallest nanocarbons and as building blocks for their macromolecular congeners (e.g. graphene nanoribbons and carbon nanotubes). The major synthetic challenge is the fusion of many rings, which requires regioselective formation of many C–C bonds. Very few methods have found general use in this regard, and most provide unfunctionalized products or cannot easily produce analogues. This thesis develops an efficient and versatile ring-fusion platform, based on a final-step [2+2+n] cycloaddition, which also enables divergent production of functionalized analogues. The work presented herein not only puts the large number of known [2+2+n] cycloadditions into a unified conceptual framework for strategic application to conjugated nanocarbons, but also contributes new reactions to the toolbox./nChapter 1 introduces the general features of the synthetic platform, which can be conceptually broken up into three steps: 1) modular synthesis of an oligo-diyne or -dinitrile precursor; 2) ring-fusion via metal-mediated cyclization; and 3) divergent, “post-fusion” functionalization. Steps 2 and 3, which together make up a formal [2+2+n] reaction, can usually be performed in the one pot or make up part of a catalytic cycle. Chapters 2–7 chronicle the development of the synthetic strategy via its target-driven application to synthetically challenging nanocarbons. Some targets have a storied history (e.g. arylene ethynylene macrocycles and cycloarenes) and others are previously unknown (e.g. expanded helicenes and their macrocyclic derivatives), but all are inaccessible using previous approaches.

Advisor: Tilley, T. Don
States of Disunion: American Marriage and Divorce, 1867–1906

This dissertation comprises three essays on the historical relationship between capitalist development, state formation and marriage and divorce patterns in the United States./nThe first examines the effects of liberalizing women’s property rights on divorce. In the late nineteenth century, most American states gave married women new rights to own and control assets and earnings. Using administrative data on most U.S. divorces between 1867 and 1906, I show that rights transfers gave women financial independence from husbands that enabled them to exit undesirable unions at greater rates. However, husbands also filed for more divorces following women’s economic gains, suggesting that the violation of traditional gender norms of household governance also destabilized unions./nThe second essay explores the legal behavior of men and women who faced significant restrictions on divorce. Before the 1970s, U.S. states allowed legal divorces only for specified causes. Examining data on the causes cited by divorce seekers, I document the routinization of divorce procedure over historical time. I also exploit legal changes to demonstrate that individuals adapted to divorce regulations by changing the causes they cited. Strategic legal behavior was widespread but differed by gender, with men being more prone toward routinization and women being more likely to adapt to new rules./nThe third essay reflects critically on the quality of available data on nineteenth-century marriages. I compare vital records of marriages to census microdata on marital duration, showing that the latter exhibit significant measurement error. Despite growing interest by elite state actors in measuring marriage and divorce at the population level, vital recording, which had administrative origins in the clarification of individual legal statuses, seems to have elicited more reliable participation in official knowledge projects. I analyze the extent and distribution of mismeasurement, which has consequences for both the study of American political development and the validity of quantitative historical research on the family.

Advisor: Fligstein, Neil
Towards More Scalable and Robust Machine Learning

For many data-intensive real-world applications, such as recognizing objects from images, detecting spam emails, and recommending items on retail websites, the most successful current approaches involve learning rich prediction rules from large datasets. There are many challenges in these machine learning tasks. For example, as the size of the datasets and the complexity of these prediction rules increase, there is a significant challenge in designing scalable methods that can effectively exploit the availability of distributed computing units. As another example, in many machine learning applications, there can be data corruptions, communication errors, and even adversarial attacks during training and test. Therefore, to build reliable machine learning models, we also have to tackle the challenge of robustness in machine learning./nIn this dissertation, we study several topics on the scalability and robustness in large-scale learning, with a focus of establishing solid theoretical foundations for these problems, and demonstrate recent progress towards the ambitious goal of building more scalable and robust machine learning models. We start with the speedup saturation problem in distributed stochastic gradient descent (SGD) algorithms with large mini-batches. We introduce the notion of gradient diversity, a metric of the dissimilarity between concurrent gradient updates, and show its key role in the convergence and generalization performance of mini-batch SGD. We then move forward to Byzantine distributed learning, a topic that involves both scalability and robustness in distributed learning. In the Byzantine setting that we consider, a fraction of distributed worker machines can have arbitrary or even adversarial behavior. We design statistically and computationally efficient algorithms to defend against Byzantine failures in distributed optimization with convex and non-convex objectives. Lastly, we discuss the adversarial example phenomenon. We provide theoretical analysis of the adversarially robust generalization properties of machine learning models through the lens of Radamacher complexity.

Advisor: Ramchandran, Kannan
Effects of Isotretinoin on Meibomian Glands

Population-based studies found that approximately 60% of symptomatic dry eye patients presented with visible signs of Meibomian gland dysfunction (MGD), which is considered the most common cause of dry eye symptoms.1,2 The prevalence of MGD varies widely between 3.5%-70%.1–6 An estimated 85% of adolescents and young adults between 12-24 years old suffer from acne and over 13 million people, including children, have been treated with isotretinoin since its availability in 1982.8 Isotretinoin is a vitamin A analogue used to treat severe inflammatory, nodular acne, and has been linked to MGD.7 Lipid mediators, which are biomarkers for normal physiology or pathophysiology in many tissues including ocular surface and lacrimal gland, are among the earliest inflammatory/immune regulators released in response to stress, but their role in MGD has not been investigated./nThe research aimed to elucidate the short- and long-term effects of isotretinoin therapy on Meibomian gland structure and function and meibum lipid mediator profiles via (1) a single-visit cohort study to compare past- and non-users of isotretinoin, and (2) a 12-month longitudinal study to compare changes from baseline during and after therapy among isotretinoin and control cohorts./nAmong many commonly reported Meibomian gland (MG) characteristics, MG contrast was found to be a repeatable and reliable measure for MG function. Specifcally, low MG contrast was found to be a risk factor for lipid-deficient dry eye. During isotretinoin therapy, MG contrast decreased significantly but returned to baseline by 6-months post treatment. In general, there were significant differences in many meibum-related clinical measures and symptoms between study groups during treatment, and some of those differences persisted six months post-therapy, including number of expressed glands and meibum quality score. Past-users had worse symptoms, worse MG function, and lower levels of prostaglandin D2, a potential biomarker for meibocyte function. Furthermore, elevated docosahexaenoic acid (DHA) levels were significantly correlated with worse symptoms, suggesting that its detection in meibum represents active inflammation and/or a metabolic deficiency preventing the effective and/or efficient conversion of DHA to specialized pro-resolving lipid mediators. In summary, isotretinoin patients develop signs of MGD during isotretinoin therapy that persist long after treatment. Lipidomic results provide potential biomarkers for detecting inflammation, DHA metabolic deficiency, and/or PGD2-related MGD.

Advisor: Lin, Meng C
Figures of Speech: Texts, Bodies, and Performance in Lucian

This dissertation examines four texts of Lucian of Samosata (Fisherman, Apology, On Dancing, and Herakles), with a focus on the representation of bodies and embodiment and their relation to speech, writing and performance. I argue that the representation of bodies is an important metaphor for how Lucian’s texts imagine their own reception, and for how they imagine the possibilities and limitations of reading, writing, performing, and spectating. The first two chapters each discuss a text in which the author uses the control and punishment of bodies as a framework for engaging with the reception and criticism of his own texts. Chapter One shows how the comic dialogue Fisherman imagines the interpretation of texts as a contentious process of securing control in which authors, readers, and texts seem to be able to influence one another in an almost physical or material way. Chapter Two examines how the Apology confronts a lack of alignment between the author and views expressed in an earlier text. I argue that this misalignment is characterized as a disruption to the connection between the author and his text that has caused him to lose control over its interpretation. Like Fisherman, the Apology imagines a kind of material connection among texts, authors, and readers, but suggests that securing physical and interpretive control over them is not always possible. Chapter Three discusses the dialogue On Dancing, demonstrating how it depicts pantomime as a space in which bodies transform and where the fluidity of a body is one of its more significant attributes. I argue that a central concern of this text is how dancer and audience interact and the influence that one can have upon the other. This emphasis on fluidity and transformation complicates the standard model of interpretation as the province of an individual interpreter who asserts control over a performer or particular text, and problematizes the concept of a body as an object or agent that can be interpreted in isolation from other bodies to which it is connected. Chapter Four explores the intersection of language, bodies, interpretation, and control through the figure of Herakles in Lucian. I argue that this image of Herakles is used to represent both the possibility of multiple interpretative viewpoints, and also the power of language to constrain and control bodies, up to and including the speaker himself. These paradoxical threads are never fully resolved, but remain in unsettling tension, even in later reception and re-imaginings of this text.

Advisor: Telò, Mario
Kuwaiti Modernity: The Development of Institutions and Their Architecture in a City-State

Architectural historians dated the project of modernity in Kuwait in 1948. This dissertation questioned the start date and proved that Kuwait presents alternative modernity shaped by a continuous process of change that relies on the political, economic, and social changes happening within the city or nearby cities. Kuwait’s modernity was visible through its architecture four decades earlier, starting from the early twentieth century. The project investigates nation-building and modernity in Kuwait during the early twentieth century under the leadership of Sheikh Mubarak Al-Sabah. Looking at the architecture and spatial formation of four newly developed institutions: Seif Palace, the British Political Agency (BPA), al-Mubarakia school, and the American Mission Hospital. Architecture was used as a primary factor in constructing an independent city-state that emphasized the political powers through the building of institutions. Each building prototype added a layer to the process of constructing a national identity to the newly developing independent city. The struggle between Sheikh Mubarak al-Sabah and foreign powers created a platform for Kuwait’s modernity that sparked but did not take it further. Kuwaiti governmental buildings continue to produce the same solo national identity: Muslim, Sunni, Bedouin, and Arab. The one selected national identity ignores the complex social and cultural backgrounds of Kuwait’s residents.

Advisor: AlSayyad, Nezar
Crysler, Grieg
Circuits and Systems for Decentralized Power Conversion

This dissertation explores circuit, control, and optimization techniques for power electronics with the objective of enabling high performance electric networks for a variety of important applications. The motivation for this work is driven in part by societal-scale trends towards systems that are increasingly dominated by power electronics, including applications such as renewable energy integration, vehicle electrification, power management for mobile devices, and data center power delivery. A key approach demonstrated in this dissertation is the design of switching power converter circuits that naturally coordinate with larger networks in order to achieve system-level benefits, whether with respect to efficiency, power quality, or reliability. A central goal of this work is to have this coordination realized in a decentralized or autonomous fashion, such that scalability, modularity, and resiliency can be achieved inherently. In the first part of this dissertation, we explore techniques for improving the power quality of electric networks with high penetrations of switching power converters, in particular, techniques that can minimize aggregate power converter harmonics in an optimal sense while also eliminating the need for communication between distributed converters. In the second part of this dissertation, we explore methods for improving the reliability and fault tolerance of such networks, in particular, model- and estimation-based strategies that transform power converters into active probes that can detect, identify, and diagnose faults in real-time. Together, these contributions demonstrate how power electronics can be designed and collectively controlled and optimized to enable highly efficient, robust, and resilient electric networks.

Advisor: Sanders, Seth R.
Study of Laser Melted Liquids and of Interfacial Ions by Nonlinear Spectroscopy

The content of this thesis can be broken into two distinct parts. The first summarizes experimental efforts to develop a better understanding of the structure and properties of liquid carbon and silicon after melting appropriate targets with an intense femtosecond laser pulse. Further research into the properties and structure of liquid carbon, particularly that focused on understanding the relationship between the thermodynamic state of the liquid and the material properties, is critical for resolving the many current controversies. Moreover, as laser synthesis grows in popularity as a tool for the production of nanomaterials, it has become increasingly critical to characterize the liquid melt which serves as an intermediate in the synthesis process, as well as the ensuing nucleation of nanostructures in the melt. To address these issues, we have carried out experiments on laser melted graphite and silicon substrates using a wide array of techniques including linear and non-linear laser spectroscopy as well as x-ray scattering to study the properties of the liquids on ultrafast timescales. The results of these studies provided new insights both into the structure and properties of the non-thermally melted liquid as well as the subsequent dynamics of the ablation plume that forms after laser melting./nThe second half of the text discusses nonlinear spectroscopy experiments studying the thermodynamics of ion solvation at the water surface in solutions containing surfactants or mixed salts. Only recently has it been recognized that certain specific anions exhibit enhanced interfacial populations relative to the solution bulk. The interfacial affinity for these ions that accumulate at the interface follows the inverse of the well-known Hoffmeister series. The physics that drive these ions to accumulate at the water surface, contradicting predictions from older theories of ion solvation, remain incompletely understood. The presence of these ions, however, has profound implications for biology and atmospheric chemistry. As such, it is critical to further advance our understanding of the mechanisms that result in selected ions localizing to the interface. The nonlinear optics experiments detailed in the second half of this thesis expand the understanding of the interfacial solvation physics of ions by extending beyond the simple single salt systems studied in previous work. Measurement of the thermodynamics of ion adsorption in these more complex solutions permits the validity of different thermodynamics models of ion adsorption to be assessed and so facilitates the development of a universal model for ion solvation physics at the interface between media. Additionally, the systems studied in the experiments detailed in this thesis are relevant to real-world atmospheric and biological systems and may lead advances in these areas.

Advisor: Saykally, Rich
Towards Interpretability and Robustness of Machine Learning Models

Modern machine learning models can be difficult to probe and understand after they have been trained. This is a major problem for the field, with consequences for trustworthiness, diagnostics, debugging, robustness, and a range of other engineering and human interaction issues surrounding the deployment of a model. Another problem of modern machine learning models is their vulnerability to small adversarial perturbations to the input, which incurs a security risk when they are applied to critical areas./nIn this thesis, we develop systematic and efficient tools for interpreting machine learning models and evaluating their adversarial robustness. Part I focuses on model interpretation. We derive an efficient feature scoring method by exploiting the graph structure in data. We also develop a learning-based method under an information-based framework. As an attempt to leverage prior knowledge about what constitutes a satisfying interpretation in a given domain, we propose a systematic approach to exploiting syntactic constituency structure by leveraging a parse tree for interpretation of models in the setting of linguistic data. Part II focuses on the evaluation of adversarial robustness. We first propose a probabilistic framework for generating adversarial examples on discrete data, and develop two algorithms to implement it. We also introduce a novel attack method in the setting where the attacker has access to model decisions alone. We investigate the robustness of various machine learning models and existing defense mechanisms under the proposed attack method. In Part III, we build a connection between the two fields by developing a method for detecting adversarial examples via tools in model interpretation.

Advisor: Jordan, Michael I
Wainwright, Martin J
The Politics of Prison Privatization: Political Strategies of Business and Labor

What is the political impact of prison privatization? Does prison privatization introduce a new political interest group into the criminal justice sphere? Do private prison firms have an incentive to push for increased incarceration and do they have the power to succeed? How similar, or different, are the political goals and strategies of private prison firms from other groups interested in the operation of prisons, such as corrections officer unions?/nI argue that the structure of firms sets them apart from other interest groups. The benefits of growth flow to all shareholders in a firm, and all shareholders have a stake in the increasing profitability of the firm they own. This aligns the concerns of shareholders and reduces conflict. In contrast, other groups often have constituents and stakeholders with conflicting interests. Labor unions, another politically influential type of interest group, have a fraught relationship with growth. If a labor union grows in size, many of the benefits flow not to the incumbent union members, but rather to new union members. I argue that this distinction between firms and labor unions should manifest in different political strategies where firms are more likely to adopt pro- active political strategies aimed at increasing market share and profit, whereas labor unions will adopt defensive political strategies aimed at safeguarding the position of their current members. This implies that private prison firms have much more to gain from increased incarceration than do corrections officer unions. I compare the political activities of private prison firms and corrections officer unions and show that private prison firms do appear to value increased incarceration more than corrections officer unions. Drawing on a time series cross-sectional model, I show that privatization appears to drive increased incarceration in states within the United States. These results are robust to a variety of model specifications. These results are not driven by political shifts, crime rates, or cost savings./nThis dissertation also describes the results of a series of interviews with state legislators and lobbyists. Across states, these subject matter experts believe private prison firms are more politically proactive, more politically sophisticated, and more supportive of increased incarceration than are corrections officer unions.

Advisor: Van Houweling, Robert