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Time-Resolved Crystallographic Analysis of the Mechanism of Formation of the MOF HKUST-1
No full textMetal-organic frameworks (MOFs) are a class of inorganic porous coordination compounds of interest for technically relevant applications including gas storage & sequestration, catalysis, and drug delivery (Chapter 2). The last decade has seen significant development in this field of coordination chemistry, and an extensive array of MOFs have been reported despite the lack of a comprehensive scheme for how these materials form. The development of novel MOFs is not a trivial task, as the synthesis of target MOFs is notably unpredictable, and experiments require extensive trial-and-error reactions with systematic manipulation of the synthetic variables. Ideally, a toolbox method based on a mechanism of formation for these materials, such as those available to organic chemists, could simplify this process and present a more accessible pathway to novel MOFs. Efforts towards understanding the mechanism of formation of MOFs have provided insights into specific MOF systems (such as MOF-5) that follow the reticular chemistry model (Chapter 3): whereby a specific set of reaction conditions will produce a target MOF while only varying ligand substituents which vary the resulting MOF’s pore size. While this model has produced a significant number of complexes from a relatively minor number of base MOFs, this scheme does not explain how the synthetic variables influence MOF formation, nor does it experimentally identify reaction intermediates. This thesis seeks to contribute to the greater understanding of how synthetic variables influence MOF formation and to determine a mechanism of formation of MOFs. This work focuses on the copper-based MOF, HKUST-1 which was studied by time-resolved small-/wide-angle X-ray scattering techniques (S/WAXS) at the Elettra Synchrotron in Trieste, Italy (Chapter 4). SAXS analyses provide structural insights into the solid aggregation and nucleation growth processes while WAXS studies the growth of the larger crystalline MOF framework. Different series of reactions were performed to analyze the effect of a different synthetic variable (Chapter 5). The results have indicated that water has an inhibitive effect on MOF growth while solvent systems containing alcohol rapidly accelerate MOF growth. While water is desirable for greener MOF syntheses, our work also shows that when using high amounts of water (low reagent concentrations) MOF formation will not occur. Reagent addition is also an important factor related to the influence of water on MOF formation. Slow combination of the reagents is required to prevent significant amounts of water being introduced at any point in the reaction. When the reagents are rapidly combined, MOF growth is poor although it may still occur after a significant period. This thesis also identifies that solvent plays a structure-determining role in HKUST-1. This work has also identified the presence and formation of a reaction intermediate. Once the synthesis of HKUST-1 starts, the intermediate begins forming within seconds and grows for a brief period. This species then begins to convert to a di-copper paddlewheel crystalline complex identified as the secondary building unit (SBU) of HKUST-1. The SBU is considered in the reticular model to be the base unit of MOF which oligomerizes to form the greater MOF network. This work also attempted to elucidate a pattern regarding the effect of the anion of the different copper salts used to form HKUST-1
Race, Space, Taste in the Postwar U.S.: Three Independent Studies on Urban Restaurants in Syracuse, New York
No full textThis dissertation examines how racial inequality shapes the survival, visibility, and strategic adaptation of restaurants in postwar Syracuse, New York. It investigates how commercial food spaces reflect, reinforce, and negotiate racialized patterns of urban development, consumer taste, and economic opportunity. Drawing on longitudinal business and demographic data, a computational content analysis of online restaurant reviews, and original interviews with immigrant restaurateurs, the study integrates quantitative, computational, and qualitative methods to illuminate how race and space co-produce outcomes in the urban food economy. The first empirical chapter shows that Black-majority neighborhoods face higher commercial volatility and shorter restaurant survival, while white-majority areas benefit from durable clustering, suggesting race conditions the protective effects of density. The second chapter reveals how consumer discourse around immigrant cuisines is framed by authenticity and exoticism, while mainstream foods evoke familiarity and comfort. The third chapter draws on interviews to show how immigrant restaurateurs navigate pressures to balance cultural expression with market appeal, often tailoring offerings to meet the expectations of a broader, often white, audience. Together, these chapters demonstrate that the restaurant economy in Syracuse is not simply a reflection of entrepreneurial initiative or consumer preference but a racialized field structured by spatial inequality, discursive framing, and institutional power. By tracing the consumption of food across time, place, and discourse, this dissertation offers a sociological account of how symbolic multiculturalism coexists with material exclusion, and how race continues to shape who gets to represent culture, and who is allowed to thrive, in the urban marketplace
Technological Revolutions and Advertising: Historical Innovation Cycles, AI, and the Future of Platform Power
No full textThis study explores the future of advertising amidst a digital landscape increasingly shaped by artificial intelligence (AI). Leveraging Carlota Perez’s Technological Revolutions and Financial Capital framework, it examines how AI is poised to further disrupt the advertising ecosystem through the key elements of automation, user data, and inventory. Collectively, these dynamics have become key drivers of platform power, with implications for user behavior, competitive strategy, and the societal diffusion of AI technology more broadly. Employing a thematic analysis across historical and contemporary cases of advertising technology, the research identifies five themes worthy of strategic and scholarly consideration. Two primary themes—Dependency and Differentiation, alongside sub-themes of Concentration, Resilience, and Transparency/Openness—illustrate advertisers’ and publishers’ increasing reliance on the differentiated capabilities of a small set of dominant platforms, reinforcing market concentration and challenging platform resilience in the face of regulatory, technological, and competitive friction. This study makes three contributions to innovation theory and techno-economic paradigm scholarship. First, it extends Perez’s framework by showing how financial and production capital increasingly converge within dominant platforms, rather than being deployed by disparate parties across distinct phases. Second, it further develops the Technological Revolutions and Financial Capital framework by positioning elements of modern production capital as self-optimizing and appreciating in value, rather than depreciating or depleting over time like the physical assets of prior eras. Third, it advances Zuboff’s concept of behavioral surplus by reframing user data not as excess extraction but as an operational necessity in AI-powered contexts. Collectively, these contributions offer a framework for understanding AI-era platform power with societal implications well beyond advertising. By leveraging historical and contemporary events to establish plausible trajectories—including agentic advertising, decentralized data ecosystems, and physical-world data capture—this research highlights both the enduring dominance of major platforms and the strategic options available to other stakeholders, calling for informed, collaborative, and proactive engagement from academics, industry professionals, policymakers, and users to shape AI’s future across industries
Here We Rio Again: The 2016 Olympic Games and the Reproduction of Spatial Struggles by Mega-events in Rio de Janeiro
No full textThis paper analyzes the unequal nature of urban development projects associated with international megaevents in Rio de Janeiro, Brazil, through the lenses of race and social class. By doing this, I seek to demonstrate how spatial struggles associated with such urban development projects are part of a longstanding pattern of socio-cultural conflict between the Brazilian elite and the urban poor. This paper specifically examines the spatial struggles embodied by the destruction of Morro do Castelo during the early 1920s, and the removal of favelas, including Vila Autódromo, between 2009 and 2016. This research is based on information from primary documents such as news coverage of resistance to development projects leading up to the 2016 Olympics, and planning documents including Rio de Janeiro’s Olympic bid and the Games’ transportation development plan. In addition to these sources, I have also drawn on the scholarship of Lorraine Leu, Theresa Williamson, and Christopher Gaffney
A Framework for Advancing and Strengthening the Veteran Entrepreneur Ecosystem
No full textThis brief is designed for funders, program leaders, and policymakers working to build stronger veteran entrepreneurship ecosystems. This paper brings together insights about veteran entrepreneurial ecosystems from Military Entrepreneurship Forum (MEF) roundtable conversations, the National Survey of Military-Affiliated Entrepreneurs (NSMAE), and other entrepreneurship research. Rather than offering a one-size-fits-all solution, this paper lays out a set of components that communities can use to strengthen their own ecosystems. Veteran entrepreneurship is a lens into broader questions of economic mobility, local resilience, and civic leadership. But systems matter. With veteran-serving organizations facing revenue declines and donor fatigue, coordinated entrepreneurial ecosystems are a necessity. Veteran entrepreneurship is not just a matter of personal success; it’s a strategy for national resilience, economic revitalization, and civic strength. While each community is different, these recommendations offer adaptable building blocks rooted in research and veteran experience
The Politics, Policy, and International Relations Section Companion Document to the Framework: Process and Outcomes
No full textThe Politics, Policy, and International Relations (PPIRS) section of ACRL is a forum for librarians to exchange information and ideas relevant to disciplines such as political science, law, international relations, security studies, public policy, and related fields. From 2018-2021, an ad hoc committee of section members worked to develop an addition to the ACRL Framework for Information Literacy for Higher Education focused on the Framework’s applications to PPIRS disciplines, now known as the Companion Document to the ACRL Framework for Information Literacy for Higher Education: Politics, Policy, and International Relations (the PPIRS Companion Document).1 In this chapter, we provide an overview of the process by which we developed this document
The Employment Situation of Veterans: August 2025
No full textVeteran employment trends and statistics among various demographics during August 2025
Rain, Rain, Go Away: Geoengineering and the Illusion of Control
No full text“Geoengineering” is increasingly seen as the best, perhaps even last, hope in the fight against global warming. Calls for such practices as Solar Radiation Management are becoming urgent as the effects of the climate crisis make themselves visible. This essay uses California’s Salton Sea, a geo-engineered palimpsest of once natural terrain turned toxic and inhospitable through human intervention, as a case study against the illusion of control. Through the critical lens of Magical Realism and the visual language of the architecture studio, this essay calls into question the desire to exert human control over natural systems, illustrating that the unintended consequences of such efforts will only serve to compound the problems they were initially meant to resolve
Artificial Intelligence in English Language Programs: From Planning to Policy
Get PDFThis report summarizes a presentation on artificial intelligence in English language programs given at the EnglishUSA Annual Conference in September, 2024. It includes a discussion of use cases in materials design and development and classroom application, as well as recommendations on AI policy for English language programs
