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Optical Sensing of Small Molecules through Click-Like Chemistry or Metal Coordination
No full textPh.D.Chiroptical sensing has gained increasing interest in the last decades as an alternative to traditional enantioselective analysis, such as NMR spectroscopy and chiral chromatography. However, chiroptical sensing has been limited to opportune compound classes, in particular amines, amino alcohols, amino acids, and -hydroxy acids. Furthermore, sensing methods have typically been limited to binary mixtures of enantiomers, while stereoisomeric and regioisomeric mixtures have been largely neglected. In this thesis, the development and evaluation of several chiroptical sensing strategies that address these gaps is presented. The inherent chromophoric and redox properties of halogenated benzoquinones were exploited for operationally simple sensing of amines, amino alcohols and amino acids. Rapid chiroptical redox switching was demonstrated using NaBH4 and air as external stimuli for up to three consecutive cycles with no chiroptical signal decay. The oxidized quinone and reduced hydroquinone states have distinctive CD/UV spectra, which for the first time allows er analysis of constitutional isomers at constant concentration. This protocol was then extended to high throughput sensing of stereoisomeric mixtures of vicinal amino alcohols. Optimization with a naphthoquinone probe generated characteristic UV and CD spectra that were intentionally altered via NaBH4 reduction to provide a second complementary chiroptical data set. Chemometric analysis using partial least squares enabled spectral deconvolution of the two data sets and accurately predicts individual concentrations of binary, ternary and quaternary mixtures.
To this day, chiral alcohols remain one of the most challenging sensing substrates due to their inherently weak nucleophilicity. As a result, most covalent bond formations with alcohols require harsh conditions and unstable reagents or involve dynamic equilibria prone to side reactions. It was shown that the Mitsunobu reaction overcomes these shortcomings, as it achieves high-yielding stereospecific conversion of a chiral alcohol to a new functional group with a variety of chromophoric pronucleophiles. Extensive screening revealed an achiral sulfonamide probe that quickly reacts and generates strong red-shifted CD spectra suitable for an optical relay assay with a commercially available quinone which enables er and concentration sensing of alcohols. With this approach, the space between chirality center and CD reporter unit is minimized, allowing sensing of remote stereocenters at the alpha-,beta-,delta-, and even gamma-position and by virtue of isotopic substitution.
Mono-carboxylic acids are yet another functional group that has been underexplored. A simple CD protocol based on stoichiometric metal coordination to a commercially available Pd sensor was developed. This method was successfully applied to sensing of mono-carboxylic acids, N-protected amino acids, and hydroxy acids. Using a recently introduced unified CD sensing approach, accurate concentration and er determination of a variety of mono-carboxylic acids is now possible using only CD measurements.
Finally, an optical method for accurate concentration and er determination of chiral nitriles via hydroziroconation and subsequent transmetalation to a commercially available Pd probe was developed. Chiral nitriles have remained one of the most challenging analytes due to the weak binding affinity of the CN moiety. This sensing methodology overcomes this limitation by functionalizing the CN bond with the well-established Schwartz reagent. The in-situ generated Zr-imine functionality is then transmetalated generating a CD-active Pd species
VASUDHAIVA KUTUMBAKAM & INDIA’S PARADOX: HOW INDIAN PHARMA BOTH ENABLES AND UNDERMINES STATE POWER
No full textGlobal health related issues have become critical forums for states to pursue their
foreign policy goals. In India, where the pharmaceutical sector (pharma) is key to global
health discourse, this industry’s contribution to the state’s geopolitical positioning is
undeniable, though understudied. Through interviews with experts in Indian
pharmaceutical policy and global health engagement, this work asks how Indian
pharma’s contributions to the generic therapeutics market factor into the state’s use of
health as a means to global power. It finds that the Indian pharmaceutical sector’s
strength produces two competing effects on the state’s use of health for foreign policy.
Firstly, Indian pharma provides substantive backing to support the state’s positioning as
a leader and “protector” of the Global South. Subsequently, the state, deriving political
standing from the industry’s contributions, acts to protect the industry where it can. In
doing so, India occasionally acts counter to the Global South’s interests. However,
protecting pharma, which in some cases harms consumers in LMICs, allows India the
geopolitical power necessary to continue advocating for LMIC interests more broadly.
The resulting dynamic provides interesting insights into the future of the LMIC pharma
market, pharmaceutical trade negotiations, and India’s geopolitical positioning.Science, Technology, and International Affair
Impact of Implementing Routine Depression Screening for Employees on the Utilization of Workplace Well-Being Resources
No full textD.N.P.Depression affects an estimated 8% of the population in the U.S. and is a common cause of disability and absenteeism in the workplace. Recommendations to improve employees’ mental health include depression screening in the occupational setting and educating employees about workplace well-being resources. A quality improvement project using a pre/post design was offered to manufacturing plant employees. The primary aim of this project was to assess the impact of implementing a depression screening program and introducing workplace well-being resources on employees’ utilization of those resources. The secondary aim was to evaluate how utilizing workplace well-being resources impacted PHQ-9 scores and the outcomes based on demographic data. Participants completed a pre-survey assessing their knowledge of workplace well-being resources and a PHQ-9 depression screening. Additionally, they received a handout about workplace well-being resources. Thirty days later, employees completed a post-survey about using those resources and a second PHQ-9. A total of fourteen (N=14) participants completed the project. In the pre-survey, 50% indicated they knew of at least one resource, while 21% said they utilized resources post-survey. Being too busy was the most prevalent reason for not using the resources. There was no statistically significant change in PHQ-9 scores pre-and-post survey. Implementing depression screening in the occupational setting and ensuring employees are aware of workplace well-being resources could be helpful tools for workers to improve their mental health
China's Engagement in the International Order: Through Human Rights Norms, Currency Adoption, and Security Rhetoric
No full textPh.D.My dissertation advances our understanding of how China engages in the liberal international order in various aspects: human rights norms, currency adoption, and security rhetoric. The first article examines whether China is contesting the international normative order. While China and the US mention “rights” exactly the same number of times in their Universal Periodic Review (UPR) recommendations, I argue that the two countries understand and use the norm differently, reflecting their divergent value systems and political views. Moreover, I posit that the varying contextualization of norms is further affected by the audience as states have distinct semantic objectives to friends and adversaries. Using text embeddings on UPR recommendations, I identify the contexts in which core human rights norms are used by different countries. I find that China deviates from the “liberal script” that prioritizes individual rights and freedom, particularly when addressing non-democracies. The findings also suggest non-democracies tend to share China’s understanding of the norms than democracies do. The second article studies why China has loaned less in Renminbi (RMB) and more in US dollar (USD) even after announcing to internationalize RMB in 2009. Using data on Chinese lending from 2000 to 2021, I find that while relational factors that determine recipient’s bargaining leverage are influential, the driving force behind the currency denomination of Chinese loans is structural. Specifically, the global dominance of the USD and the excessive foreign reserves in China constrain China’s decision. This demonstrates China has limited ability to compete with the US in the financial order, at least in the short-term. The third article explores how states’ security rhetorics are positioned relative to China and the US. It develops a two-step measurement model to estimate dynamic ideal points from the UN Security Council Debates. The first step uses the Fighting Words method to distinguish terms used significantly more by China than the US and vice versa. These estimates are then imposed as a structure on a WordFish ideal point model. Results indicate while China’s rhetoric has become more distinct since the mid-2000s, it remains isolated with only a few non-permanent members adopting positions close to China
Investigating the Global Data on Climate Migration
No full textM.P.P.This report is part of the field of study of climate migration, whereby an individual relocates elsewhere as a direct result of a climate-induced event. While researchers have conducted several studies into the broad motivations of individuals to migrate, few empirical studies exist at present which specifically test climate change as a driving factor. This report aims to determine whether a correlation between temperature increases from human-caused climate change and rates of human migration across international borders exists. This report tests its hypothesis through a series of ordinary least squares (OLS) regression models, controlling for additional contributory migration factors such as poverty, corruption, and population. While none of the report’s regressions found a statistically significant correlation between temperature increase and net migration, limiting factors such as inconsistent results from multiple transnational surveys, the transcendence of the effects of climate change beyond national boundaries, and the earliness of the tangible effects of climate change on human behavior likely contribute to this lack of correlation. The contributions of this report ought to aid policymakers in developing evidence-based solutions to address the needs of these communities in crisis in a timely, safe, and humane manner
Annual Statistical Transparency Report Regarding the Intelligence Community’s Use of National Security Surveillance Authorities: Calendar Year 2023 (2024)
No full textFirst page of documen
Examining Food as a Cultural Artifact in Narratives of Immigration and Displacement
No full textM.A.As people read, they often overlook scenes of food or cooking. Those anxious to arrive at the plot's climax or the conclusion may gloss over food scenes, deeming them unimportant to the storyline. My thesis aims to prove that overlooking the importance of food is not only a mistake, but that food is also essential to understanding cultural values, shifts, and adaptations. My thesis will examine the intersection between food studies and cultural studies in four narratives of immigration and displacement by exploring how food scenes are used as a vehicle for understanding how characters connect with their home regions or countries, mediate their relationships with their host country, and cope with the trauma of relocation. To focus the scope of my project, I have selected narratives that derive from Northern California or share the experiences of immigrants in transit to California because of the state’s historical significance as a destination for immigrants since the California Gold Rush in the mid-19th century. I begin in San Francisco in 1904 with The California Immigrant by Barbara Anne King, my second chapter moves to an analysis of The Joy Luck Club by Amy Tan, my third chapter shifts to Oakland with Tommy Orange’s There There, and my final chapter concludes with roots in Berkeley with Micheline Aharonian Marcom’s The New American. Employing frameworks such as Kyla Wazana Tompkins’ critical eating studies approach, I argue for a revaluing of what she names “embodied existence” within literature, grounding literary analysis in the physicality of food while simultaneously acknowledging the context in which characters interact with food.Furthermore, I structure my analysis of the material through scholars such as Elaine Freedgood and Michel Rolph Trouillot as their work urges for a deeper understanding of the historical importance of physical artifacts and their complex connections to history. Ultimately, food becomes a prism in which to view the complex mosaic of immigration and displacement through. Its ubiquitous presence has led many scholars to deny its importance, however, my thesis aims to prove that food and recipes are as valid of historical traces as buildings or other physical markers because of their deep ties to cultural values and intrinsic connection to home
The Sectoral Composition of Employment and Female Labor Force Participation: A Cross-Country Analysis
No full textM.P.P.Female labor force participation (FLFP) is a critical indicator of gender equality and economic development. This study proposes to investigate the relationship between the sectoral composition of employment and FLFP across countries, using data from the World Bank Open Data, International Labour Organization (ILOSTAT), and World Values Survey (WVS) datasets. The analysis employs an ordinary least squares (OLS) regression model to estimate the associations between the shares of employment in agriculture, manufacturing, services, and the public sector on FLFP, while controlling for macro-level factors, institutional variables, and gender norms. The research aims to test the hypothesis that a higher share of service sector and public sector employment is associated with higher FLFP, while a higher share of agricultural and informal employment is correlated with lower FLFP. By examining the role of sectoral composition in shaping women's employment opportunities and outcomes, the study seeks to contribute to the growing body of evidence on the structural determinants of FLFP and inform policy debates on promoting gender equality and inclusive growth in the context of economic development. The study draws on insights from the literature on economic development, structural change, globalization, and feminist economics to develop a comprehensive conceptual framework for analyzing the complex relationships between sectoral composition, institutional factors, social norms, and FLFP
Investing in Hearts and Minds: An Analysis of the Effects of US and Chinese FDI on Political Attitudes in Host Nations
No full textM.P.P.Debate surrounding the impact of foreign direct investment (FDI) often grapples with the dualistic nature of its effects. FDI has the potential to invigorate economic growth and can introduce complex challenges, like debt dependency and poor working conditions. These dimensions of FDI not only impact the economic fabric of nations but also resonate deeply with citizens, shaping their perception of foreign nations. As such, this paper analyzes and compares the effects of Chinese and US FDI on perceptions of China and the US in Asian and African countries. It uses data regarding outward FDI from the International Monetary Fund Coordinated Direct Investment survey and cross-sectional data about sentiment from the Afrobarometer and Asian Barometer. It estimates fixed effects models using national and individual-level data spanning from 2018-2021. US FDI has a statistically significant relationship with negative sentiment towards the US across Asia and Africa. Meanwhile, Chinese FDI demonstrates a statistically significant relationship with positive sentiment towards China in Asia and the reverse in Africa. However, this study in limited in its robustness and carries risks of multicollinearity. As such additional studies that aim to juxtapose the effects of Chinese and US FDI in terms of political attitudes should incorporate panel data to enable a more comprehensive analysis
Violating the Body Politic: The Politic of Suffering, Gender, and Royal Authority during the French Wars of Religion (1560-1589)
No full textPh.D.This dissertation is a study of gender, suffering, and authority in the political language and culture of the French Wars of Religion. I argue that from 1560 to 1589, the metaphor of the family replaced the metaphor of the body as the primary framework used by members of French political society, with the king represented as the common father of his subjects rather than the head of the collective body of the realm. Although both the metaphor of the body politic and the metaphor of the family politic originated in political philosophies favorable to strong royal authority, I argue that in practice members of French political society used both metaphors flexibly and adaptively to pursue a variety of interests throughout the Wars of Religion, including objecting to royal policies or decisions. The family politic, far more than the body politic, relied on power dynamics related to gender and sexuality in order to represent hierarchy and authority within French political society. The study focuses on the political language of the Estates Generals of 1560, 1561, 1576, and 1588, demonstrating how the shift from body politic to family politic reshaped the narratives of violence that emerged out of the assemblies’ debates and discussions about the ongoing war. Although sexual violence was often taboo in the sixteenth century, even during times of war, the deputies at the Estates Generals elevated local complaints about soldiers’ acts of rape and sexual violence into metaphors of France’s collective suffering because rape represented a violation of the family. This dissertation examines complaints about sexual violence in local grievances produced during the Wars of Religion and in the records of the Estates General assemblies for the first time, demonstrating how the shift from body politic to family politic entailed a politicization of gender-based patterns of violence that extended beyond the Estates General into the broader political culture of the Wars of Religion