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Chemistry in Confined Spaces: Photochemistry of Ketones, Thioketones, and Nitrites within an Organic Capsule
No full textThe research detailed in this thesis delves into host-guest chemistry involving the above water-soluble deep cavity cavitand and diverse organic molecules containing carbonyl, thiocarbonyl, or nitrite chromophore. Chapter 1 introduces the fundamental concept and historical background of supramolecular systems, with a specific focus on water-soluble macrocycles including octa acid (OA). This chapter provides a brief overview of the properties and applications of distinctive hydrophobic, water-soluble receptors, laying the foundation for the utilization of octa acid as a reaction vessel for conducting molecular photochemistry. In Chapter 2, the photochemical behavior of a range of α-alkyl dibenzylketones encapsulated within octa acid in borate buffer is elucidated through molecular dynamics (MD) simulations. Chapter 3 explores the impact of organized media (OA) on the reactivity of α,α-dimethyl substituted aryl alkyl ketones, and thioketones within confined spaces.The study highlights the crucial role of free space and time in supramolecular photochemistry. Chapter 4 utilizes octa acid as a supramolecular catalytic vessel for showcasing the cavity's role as a template for visible light-induced photocatalysis of a novel photo-transformation featuring β-enaminones leading to the bioactive molecular core. The results emphasize the connection between the binding affinities of the reactant (β-enaminone) and the resulting photoproduct with a hydrophobic OA cavity in an aqueous environment. Chapter 5 explores the photochemical behavior of alpha-methylated dibenzyl ketones which undergo δ-hydrogen abstraction from the singlet state in solution with a lower quantum efficiency. Chapter 6 delves into the photochemistry of nitrites confined within the OA cavity. The findings presented in this chapter elucidate the unexpected selectivity achieved in the enclosed system provided by OA influencing the secondary photochemical processes of nitrites.</p
Lalovavi: An Afrofuturist Grand Opera (Examining the Composition Process by Comparing Two Versions of Act 1)
No full textLalovavi is a grand opera for a cast of ten principal roles, chorus, and symphony orchestra. In this doctoral essay, I will be comparing two different versions of the first act of Lalovavi. Commissioned by Cincinnati Opera, the libretto underwent significant edits in the development process. This changed most of the plot points and lyrics of the original story, necessitating similar changes to the original score. Previously set in the year 2119, the story is now set in the year 2425. It follows the journey of Persephone, the daughter of Titan Musan, the reigning Primus of Atlas (formerly Atlanta, Georgia). Persephone is betrayed by her family and leaves everything she knows behind when it is discovered she has the key to everlasting life in her blood. Guided by a mysterious nightmare, she must run for her life in an epic adventure that leads to her true destiny. The musical style of Lalovavi focuses primarily on contemporary classical techniques, while the production itself will have an Afrofuturist theme. The libretto utilizes English and Tut, a secret language that was spoken by enslaved peoples in the 1800s and passed down through generations to modern times. Lalovavi is the Tut word for love.</p
Integrating Generative AI into Prevention Science: Using Large Language Models to Enhance the Implementation of Preventive Interventions
No full textRecent advances in artificial intelligence (AI) have transformed scientific innovation across multiple disciplines. However, within prevention science, AI has been used primarily for risk detection, leaving its potential to enhance program implementation largely unexplored. This dissertation provides empirical evidence that AI, particularly Generative AI, can play a transformative role in implementation science. Three studies are presented to demonstrate this potential. Study 1 developed an AI-driven chatbot that simulates adolescent participants to support facilitator training in a brief preventive intervention. Study 2 evaluated the validity and reliability of an AI-based system for automatically identifying and coding facilitator delivery skills to assess implementation fidelity. Study 3 generated an automated feedback report translating AI-coded data into actionable insights for facilitators. Together, these studies advance prevention science by demonstrating practical and ethical approaches to integrating AI into the implementation of preventive interventions. This research strengthens implementation practices, bridges the gap between technological innovation and real-world application, and ensures that AI-driven tools make meaningful contributions to prevention science.</p
Chronic Urticaria Part II: Clinical management and therapeutics
No full textChronic urticaria (CU) is a mast-cell driven disease characterized by recurrent wheals, angioedema, or both, lasting more than six weeks. Timely, appropriate treatment is essential to achieve complete disease control, minimize burden, and improve quality of life. The goal of management is elimination of symptoms with safe, effective therapies at the lowest necessary dose. This two-part continuing medical education series provides a comprehensive review of CU. Part II focuses on the complex management of CU including the role of antihistamines, immunosuppressants, and biologics, as well as novel approaches. The CU therapeutic landscape is evolving, with investigations ongoing for biologics, small molecules, and specific mast cell-directed agents
Douching Is Associated With Dysregulated Rectal Mucosal Immunity in Sexual Minority Men
No full textReceptive condomless anal sex (CAS) associates with elevated rectal inflammation and mucosal injury, increasing HIV acquisition risk. Although douching may amplify rectal inflammation and alter microbial communities, this has not been well characterized in sexual minority men (SMM).Ninety-two SMM (median age, 34.6 years) who were HIV negative and reported receptive CAS provided rectal swabs during sexually transmitted infection (STI) clinic visits. Associations among rectal douching, rectal cytokine/chemokine levels, and microbial communities, evaluated via immunoassay and 16S rRNA gene sequencing, respectively, were assessed.When compared with nondouching SMM (n = 27), SMM who douched (n = 64) reported more receptive CAS partners and displayed elevations in rectal cytokine/chemokines linked to immune activation and inflammation. Lower microbial richness, evenness, and Shannon diversity in SMM who reported douching were observed. Significant associations were identified between microbial alpha diversity metrics and rectal chemokine/cytokine levels. Finally, significant correlations were observed between rectal cytokine/chemokine levels and individual microbial genera.Among SMM engaging in receptive CAS, douching may identify those with amplified biobehavioral HIV and STI risk. Elucidating the mechanisms whereby douching dysregulates rectal immune function and alters rectal microbial communities could yield targets for biomedical approaches to optimize HIV/STI prevention in SMM during receptive CAS
Strengthening JOSA A—our new topical editors in action: editorial
No full textEditor-in-Chief Olga Korotkova summarizes the Journal’s progress in 2025, recognizes editors who have completed their terms, and introduces editors who have recently joined the board
Evaluating Photochemical Interactions Between Rose Bengal Photodynamic Antimicrobial Therapy and Topical Antifungals in Fungal Keratitis Isolates
No full textThe purpose of this study was to evaluate the in vitro effects of combining rose bengal (RB) photodynamic antimicrobial therapy (PDAT) with conventional topical antifungals (amphotericin B, natamycin, and voriconazole) on clinical Fusarium and Aspergillus isolates and to determine the antifungal stability under experimental conditions.
Clinical isolates of Fusarium spp. (n = 3) and Aspergillus spp. (n = 3) were cultured using standard microbiology techniques. Agar plates were prepared with three concentrations of amphotericin B, natamycin, or voriconazole along with plates containing no antifungals. The following groups were tested in both dark and light conditions: (1) antifungal monotherapy (antifungal only), (2) RB monotherapy (RB only), and (3) antifungal and RB combination therapy. Plates were incubated for 7 days and percent growth inhibition was quantified. UV-visible spectroscopy and mass spectrometry was performed to assess antifungal stability.
Overall, Fusarium isolates were more susceptible to RB-PDAT than Aspergillus isolates. RB-PDAT combination therapy with natamycin reduced growth inhibition, whereas combination therapy with voriconazole increased growth inhibition compared to antifungal monotherapy. UV-visible spectroscopy demonstrated 70% degradation of amphotericin B and full degradation of natamycin when combined with RB-PDAT, whereas voriconazole remained stable.
Across both Fusarium and Aspergillus isolates, treatment responses to antifungals with or without RB-PDAT demonstrated strain-specific effects. The increased fungal inhibition and maintained stability of voriconazole when combined with RB-PDAT highlight its potential compatibility with RB-PDAT. In contrast, the reduced inhibition and degradation of natamycin and amphotericin B with RB-PDAT suggests that drug stability may be a factor to consider when integrating RB-PDAT into fungal keratitis management
Enlarged Perivascular Spaces Among Hispanic and Latino Adults in SOL-INCA-MRI
No full textTo examine preliminary associations between enlarged perivascular spaces (ePVS) and cerebrovascular small-vessel disease, cortical atrophy, and cognitive impairment among a select cohort of Hispanic and Latino adults. The Hispanic and Latino population has a higher prevalence of dementia and vascular disease but is underrepresented in dementia research. This study addresses this gap by investigating ePVS in a large convenience cohort of Hispanic and Latino individuals.
Brain magnetic resonance images from a convenience sample of 2161 participants, including 28.8% of individuals aged >50 years with cognitive impairment from the SOL-INCA-MRI (Study of Latinos-Investigation of Neurocognitive Aging Magnetic Resonance Imaging) study were analyzed. ePVS volume in the cerebral white matter was quantified using an automated method and then residualized with total cerebral volume. Associations between residualized mean ePVS volumes and demographic factors, magnetic resonance imaging measures, and cognitive impairment were assessed using regression models.
Residualized mean ePVS volume was significantly associated with age (
<0.001) and varied significantly by Hispanic and Latino heritage. After adjusting for age, sex, education, and heritage, ePVS volume was associated with infarction on magnetic resonance imaging (
=0.03), white matter hyperintensity volume (
<0.001), presence of cerebral microbleeds (
=0.009), cortical gray matter (
<0.001), and hippocampal (
<0.001) atrophy. Participants who are cognitively impaired also had significantly larger ePVS volumes (
=0.004). No significant sex differences in ePVS volume were observed when adjusting for head size.
This convenience sample of Hispanic and Latino individuals demonstrates significant associations between ePVS volume and established markers of cerebrovascular small-vessel disease, cortical atrophy, and cognitive impairment. These findings suggest that ePVS may be useful as an additional marker of vascular brain injury within this cohort
