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    Electronic Supporting Data: Tetrachloroanthracene Walled Glycoluril Dimer Undergoes Self-Association and 1:1, 2:2, and 1:3 Host•Guest Binding

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    We report the design, synthesis and characterization of a tetrachloroanthracene walled methylene bridged glycoluril dimer (H1). According to 1H NMR spectroscopy and symmetry considerations we formulate H1 as a C2v-symmetric monomer in DMSO but it exists as a C2h-symmetric dimer (H1•H1) in water. The H1•H1 dimer persists below 25 uM in water and displays high thermodynamic stability (Ks ≥ 1.8 x 106 M-1). H1•H1 is also stable up to 70 ˚C in water. We investigated the binding of H1 with a panel of five dyes by isothermal titration calorimetry and 1H NMR spectroscopy and found that H1 engages with dyes with several different stoichiometries of binding. For example, NMeAc and Berb are capable of causing the dissociation of H1•H1 resulting in the formation of the 1:1 intracavity dye complexes H1•NMeAc and H1•Berb. In contrast, Rh6G and ThT do not dissociate the H1•H1 dimer and instead stack on the exterior of the dimer to form Rh6G•H1•H1•Rh6G and ThT•H1•H1•ThT, respectively. Finally, 3 equivalents of NDI+ causes dissociation of H1•H1 and binds both intracavity and on the exterior to form the H1•(NDI+)3 complex.We thank the National Science Foundation (CHE-1807486) for past financial support. We thank the National Institute of General Medical Sciences of the National Institutes of Health (R35GM153362) for current financial support of this project

    Association between smoking cessation and risk for type 2 diabetes, stratified by post-cessation weight change: A systematic review and meta-analysis

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    OBJECTIVE: While smoking cessation reduces health risks, its impact on type 2 diabetes mellitus (T2DM) remains complex when considering post-cessation weight gain. This systematic review and meta-analysis examined the association between smoking cessation and diabetes risk stratified by weight change and cessation duration. METHODS: We searched seven databases through April 14, 2025. Observational studies examining smoking cessation, weight changes, and T2DM were included. Random-effects models pooled hazard ratios (HRs) comparing recent and long-term quitters to continuous/never smokers, stratified by weight gain. RESULTS: Among eleven cohort studies, quitters with weight gain showed increased diabetes risk versus continuous smokers (HR = 1.71, 95 % CI: 1.12, 2.62), with recent quitters having greater risk (HR = 2.20, 95 % CI: 1.27, 3.82) but long-term quitters showing reduced risk (HR = 0.91, 95 % CI: 0.87, 0.95). Quitters without weight gain demonstrated no increased risk (recent: HR = 0.99, 95 % CI: 0.81, 1.02) and lower risk (long-term: HR = 0.84, 95 % CI: 0.81, 0.87). Compared to never-smokers, recent quitters had a higher T2DM risk regardless of weight status (with gain: HR = 1.61, 95 % CI: 1.03, 2.50; without gain: HR = 1.25, 95 % CI: 1.05, 1.48), while long-term quitters showed no significant difference. CONCLUSIONS: Smoking cessation temporarily increases T2DM risk, particularly with weight gain, but becomes protective long-term, emphasizing weight management.https://doi.org/10.1016/j.ypmed.2025.10842

    The cruciferous vegetable Brassica oleracea L. var. acephala, (Kale) protects against pro-inflammatory- lipopolysaccharide formation, translocation, and endotoxicity.

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    Cruciferous vegetables have been widely studied for cancer prevention and cardiovascular health. Broccoli is a cruciferous vegetable whose phytochemistry and physiological effects have been most extensively studied. Kale is often on the list of ‘most healthy foods,’ but there is a paucity of scientific data on it. Easily cultivated with resistance to extreme weather, kale is rich in phytochemicals and micronutrients. Compared to other Brassica, including broccoli, arugula, and cabbage, kale has the highest density of sulforaphane, lutein, zeaxanthin, β-carotene, quercetin, and minerals (Zn, K, P). The gut microbiota influences host phenotype through direct contact with intestinal cells or indirectly via bacterial metabolites. Lipopolysaccharide (LPS) is one of the most potent activators of innate immune signaling, is a causal or complicating factor in several diseases, and is an important mediator of the microbiome’s influence on host physiology. The structure, chemical properties, and immunogenicity of LPS vary depending on the specific gut bacterial species that produce it. Pro-inflammatory LPS (P-LPS) activates the innate immune system, leading to inflammatory responses. In contrast, immunosuppressive or anti-inflammatory LPS (A-LPS) is not a ligand for Toll-like receptor 4 (TLR4) and therefore does not trigger immune signaling. Host-mediated inflammation, whether from the diet, a pathogen, chemical induction, or deficiency in immunity, favors the growth of aerobic bacterial taxa, e.g., Enterobacteriaceae, the main producers of P-LPS. The P-LPS is a highly immunogenic antigen that further exacerbates inflammation and is detrimental to gut barrier function. The goal of this study was to determine the protective impacts of kale supplementation as a functional food against diet-induced fat accumulation, insulin resistance, and inflammation. In two studies in C57BL6 mice, we found that whole ‘curly green kale’ is protective against systemic low-grade inflammation induced by a high fat (HF) diet and acute inflammation induced chemically by dextran sulfate sodium (DSS). The second goal of the study was to determine mechanisms by which kale protects against the formation, translocation, and functioning of P-LPS. Using C56BL6J mice and in vitro models, we show that kale imparts this protection by changing the gut microbiota composition, reducing the abundance of P-LPS-producing Enterobacteriaceae while increasing the representation of Bacteroidaceae, including species like Bacteroides thetaiotaomicron, which is known to produce immunosuppressive A-LPS. Kale thus modulates the P-LPS to A-LPS ratio. Relative levels of this ratio will exacerbate or inhibit inflammation. In addition, kale promotes the outgrowth of gram-positive taxa, specifically the species Turicibacter sanguinis. In follow-up studies in co-cultures of bacteria and intestinal epithelial cells (Caco-2 cells), we show that T. sanguinis protects gut barrier integrity by attenuating the adhesion and proliferation of E.coli O157:H7 (the source of P-LPS) and enhancing the expression of tight junction proteins. Further experiments in Caco-2 cells treated with P-LPS showed that the extract of kale promotes the expression and activity of intestinal alkaline phosphatase (IAP), an enzyme that deactivates P-LPS by dephosphorylating its lipid A moiety, thus rendering it unable to bind to TLR4 and initiate signaling. Lastly, using flow cytometry, we showed that in mouse primary peripheral blood mononuclear cells (PBMCs) and RAW 264.7 macrophages, kale extract inhibited the ability of P-LPS to bind to the TLR4-MD2 complex and CD14 receptors, thus attenuating the downstream inflammatory responses. In summary, dietary supplementation with kale is protective against inflammation. Particularly inflammation induced by the bacterial metabolite P-LPS. It is protective against (i) P-LPS formation (by modulating the gut microbiota), (ii) P-LPS translocation (by strengthening the gut barrier), and (iii) the functioning of P-LPS (promoting its dephosphorylation and hence detoxification and preventing its binding to TLR4

    Scream Queen: Drag, Dance, and the Grotesque Beauty of Queer Imagination

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    Scream Queen is, if anything, an act of adoration for the medium of horror and the power of queer expression. This paper will detail the process and culminating product of my choreographed work, Scream Queen, presented in October 2024. I will discuss persona, drag, and the intimate relationship between horror and queerness. As a queer alternative movement artist, I hope to honor the subversive and revolutionary voices who have come before me. I will explore the belief and theory that queer people gravitate towards that which is grotesque, horrific, and villainous because it allows them to feel a sense of power within their otherness, actively witnessing aspects of their identity within figureheads that oppose the world which has demonized their existence

    Schematic Bodies: Housing, Status Property, and Sexuality in U.S. Literature

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    “Schematic Bodies” examines literary representations of home in the context of housing policy and its transformative effects on sexual order in the United States. I develop a theory of status property that accounts for role of the family home in the naturalization of the “normal” as a racial and sexual category over time. I demonstrate how texts register concealed functions of economy in their depictions of home and the family by using representational strategies like spatial disorientation, narrative fragmentation, debt and value metaphor, and irony. Literary texts render what I call “spectral” processes in language. By reading literature alongside economic flashpoints of US housing policy such as the development of the Federal Housing Administration and mortgage-backed securities, “Schematic Bodies” develops an account of residential real estate’s influence on literary form and sexual categories over the course of the long twentieth century. Moreover, it explains how literature can function as a site for imagining kinship without property

    METRIC GEOMETRY OF FINITE ENERGY CLASSES IN BIG COHOMOLOGY

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    This thesis investigates the metric geometry of finite energy classes in big cohomology. These finite energy classes are made of functions that correspond to singular metrics on compact K\"ahler manifolds. These spaces of functions were introduced to find the canonical K\"ahler metrics. We extend their study to big cohomology classes. On the space of finite energy potentials Ep(X,θ)\mathcal{E}^{p}(X,\theta) where θ\theta represents a big cohomology class, we construct a complete geodesic metric dpd_{p}. We show that several metric properties of (Ep(X,θ),dp)(\mathcal{E}^{p}(X,\theta), d_{p}) are the same as in the K\"ahler setting. In the end, we study the space of geodesic rays in Ep(X,θ)\mathcal{E}^{p}(X,\theta), Rθp\mathcal{R}^{p}_{\theta}, and construct a chordal metric dpcd_{p}^{c} on it. We show that (Rθp,dpc)(\mathcal{R}^{p}_{\theta}, d_{p}^{c}) is a complete geodesic metric as well

    Data Set for Hygroscopicity of Isoprene-Derived Secondary Organic Aerosol Mixture Proxies: Importance of Solute Diffusion and Salting-In Effects

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    Surface tension measurements were obtained using a pendant drop tensiometer over a length of 300 seconds, using the methodology of Fertil et al., 2025 CCN measurements were obtained using a DMT Cloud Condensation Nuclei Counter using the Scanning Mobility CCN Analysis (SMCA) method (Moore et al., 2010). Data obtained was then analyzed using the PyCAT analysis toolkit available for public use (last access: August 27, 2025; https://doi.org/10.5281/zenodo.6329787; Gohil, 2022; Gohil and Asa-Awuku 2022)Raw data (surface tension and cloud condensation nuclei counter (CCNC) measurements) files for publication "Hygroscopicity of Isoprene-Derived Secondary Organic Aerosol Mixture Proxies: The Importance of Solute Diffusion and Salting-In Effects"NSF AGS #2124489https://doi.org/10.5194/egusphere-2025-193

    EFFECTS OF EXTREME MECHANICAL SHOCK ON RELIABILITY OF EMBEDDED COMPONENT INTERCONNECTS IN PRINTED HYBRID ELECTRONICS AT MULTIPLE TEMPERATURES

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    The advantages of Printed Hybrid Electronic (PHE) assemblies are of considerable interest to designers of electro-mechanical systems, especially for applications in extreme environments, defined here as accelerations from 20,000 g to 100,000 g (causing strain rates of 1,000+ /s) and temperatures above .5 × Tmelt. With additional development, PHEs may offer reliability advantages over traditional electronic packages in fields like aerospace or applications such as conformal circuits or integrated sensors. This study focuses on durability of component interconnections in PHEs. For this work, passive components were recessed into machined cavities in injection-molded polysulfone domes and beams by way of a unique ‘mill-and-fill’ method combining traditional subtractive milling with extrusion-based paste printing. The components were interconnected to printed silver traces using printed solder, with circuits then formed from the silver traces. These assemblies were subject to large strains caused by mechanical shock at acceleration levels up to 100,000 g and at temperatures from 25 °C to 125 °C. The populated beam specimens were subjected to drop testing in a clamped-clamped configuration without secondary impact using an accelerated-fall drop tower with dual mass shock amplifier, resulting in substrate strain magnitudes of up to 50,000 µm/m at rates up to ~1,000 /s. Trace degradation characteristics were first assessed, then the number of drops to failure (as defined by component separation from the substrate) were documented across four different component locations on a beam specimen, providing failure data for four different strain histories. These four strain histories were compiled across a total of seven different test points ranging from 25,000 g to 100,000 g and 25 °C to 125 °C. Concurrently, a finite element model of the fully populated assembly was used to simulate the physical response of the sintered silver within the trace adjacent to the recessed component. This model was matched to experiments by direct strain measurement in the substrate, supported by digital image correlation. Circuit failure occurred due to component separation from the substrate caused by cracking within the sintered silver beneath the soldered interconnect – a failure mode common across all acceleration levels, strain rates and temperatures. The dependence of rates of degradation and failure on acceleration level and temperature was quantified based on strain levels expected within the silver trace. Plastic strain magnitude was used as the basis for damage accumulation in the sintered silver. Collectively the experimental results and simulation data were integrated by means of a cumulative damage model to generate an application-agnostic low-cycle fatigue curve for the sintered silver from 25-125 °C, and strain rates from 200 /s to 1,000+ /s

    Lexical categories, (re)categorization, and locality in morphosyntax

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    This dissertation is about the nature of syntactic primitives and principles, their status in the grammar, and their interaction with extra-linguistic cognition. The dissertation has two parts unified by the common goal of streamlining the syntax by asking whether some of its proposed constructs are dispensable, whether the motivation for their existence can be found syntax-externally, and whether they must be assumed to be part of the initial state of the learner. While I discuss a range of phenomena in a number of languages, core empirical evidence throughout comes from adjectival derivation in Bosnian/Croatian/ Serbian (BCS). In the first part of the dissertation, I consider the status of lexical categories (LCs) in grammar. I argue that LCs noun, verb, and adjective are purely formal, abstract categories which have a distributional role in the syntaxes of individual languages, but which do not have a one-to-one mapping to any interpretive property. I argue against proposals that attribute universal syntactic or semantic properties to the specific LCs. In addition to discussing relevant data from a variety of languages, I provide two detailed case studies on mixed categories: passive and active participles. I show that all participles in the languages under discussion are in fact deverbal adjectives, in every syntactic position they appear in and regardless of their interpretation. While participles may denote (predicates of) properties or eventualities, I argue that these different interpretations are not cross-linguistically associated with more or less verbal or adjectival structure. This reinforces the conclusion that a direct one-to-one correspondence between an item’s LC and its interpretation does not exist. If correct, this proposal has significant con- sequences for our understanding of Universal Grammar. If there are no universal syntactic or semantic properties we can attribute to the LCs, then it becomes superfluous to assume that the individual LCs are part of the initial state of the learner. I propose that the cross-linguistic tendencies we observe around LCs may stem from the way non-linguistic knowledge is organized in the mind/brain. In the second part of the dissertation, I turn my attention to the formal principles that operate on grammatical primitives, asking specifically what kinds of locality constraints are employed by the grammar. While locality has been extensively studied in generative linguistics, the current offering of locality theories is arbitrary, redundant, baroque, and/or empirically inadequate. There are in essence three competing locality theories currently in circulation within the field: Featural Relativized Minimality (FRM), Phase theory as currently understood in the syntax literature (where it is a successor of Subjacency), and Phase theory as understood in the context of Distributed Morphology (DM). Despite recent attempts to devise a single, unified Phase theory which is responsible for both syntax-internal lo- cality and interface locality, I argue on both conceptual and empirical grounds that the unification is unfeasible. In a detailed empirical study of deadjectival derivation in BCS, I show that adjectivization imposes a DM-locality boundary (for allomorphy and morphological tone assignment), but not a ‘big syntax’-locality boundary (for punctuated movement paths). Nonetheless, I show that the original inventory of locality principles can be reduced if we assume that (i) syntax-internal locality is regulated by FRM, and (ii) interface locality is regulated by Transfer, a modified version of Phase theory which has no syntax-internal effects. I reinterpret the evidence supporting Phase theory through the lens of FRM and demonstrate that the division of labor in (i)-(ii) not only achieves the right empirical cut, but also offers insight into why the grammar may require two distinct locality principles

    Willingness to Pay for Express Lanes, Heterogeneity Effects, Reliability Measures, and Optimal Control Strategies from Passively Collected Data

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    In March 2020, governments worldwide implemented various social restriction measures, including lockdowns, to mitigate the spread of the COVID-19 virus. This led to a profound shift in travel behavior, accompanied by a notable reduction in congestion. This dissertation investigates travel demand on Express Lanes (ELs) during two time periods: before the pandemic (from January 2020 to mid-March 2020) and during the pandemic (from mid-March 2020 to the end of May 2020). A large data set of trips observed on Express Lanes derived from transponders is combined with vehicle probe measures of travel times and used to estimate the willingness to pay (WTP) for travel time savings and reliability. This dissertation also addresses system-wide performance optimization by integrating multiple control strategies. This dissertation is structured into four main chapters. The first chapter explores the change in travel behavior on Express Lanes and assesses changes in WTP before and during the pandemic across different temporal phases. The second chapter investigates the heterogeneity of among Express Lane users’ WTP under the impact of lockdown policy. The third chapter provides a comprehensive analysis of users’ value of travel time (VOT) and reliability (VOR) on the Express Lane before and during the pandemic. The fourth chapter extends the focus to system-wide optimization, presenting an integrated traffic management system that combines real-time ramp metering with dynamic toll pricing strategies to alleviate congestion and enhance freeway performance

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