Casey N. Brodsky

PURPOSE: We hypothesized that transgender and gender-nonconforming (TGNC) patients diagnosed with genitourinary (GU) and gynecologic (GYN) cancers may experience unique challenges and barriers to care because of association of these organs with sex assigned at birth but not gender identity. We aimed to explore their experiences in this qualitative study. MATERIALS AND METHODS: TGNC adults diagnosed with a GU/GYN cancer completed an anonymous survey probing experiences with cancer diagnosis, treatment, and clinicians, with the option to complete an additional interview. Participants were accrued to thematic saturation. Analysis included descriptive statistics, open coding, and development of themes. RESULTS: Twenty-one patients completed a survey, and 16 completed an interview. Qualitative analysis yielded six key themes: (1) clinician dismissal and assumptions about gender identity and preferences, (2) inadequate clinician knowledge about TGNC health, (3) avoidance of oncologic care due to dysphoria and fear of discrimination, (4) increased dysphoria associated with GU/GYN cancer, (5) importance of gender identity in patients' decision making, and desire to discuss gender-affirming goals, and (6) wide spectrum of reactions to GU/GYN cancer diagnosis, associated with charged feelings toward affected organ. CONCLUSION: For TGNC patients with GU/GYN cancers, gender identity matters, both for clinical decision making and patients' emotional experience. Clinicians can partner with patients through this challenging journey to ensure that patients feel safe and supported and can make treatment decisions that align with their gender-affirming goals.

Aims: Beyond causing physical discomfort, overactive bladder (OAB) is distressing to patients across a variety of psychosocial domains. In this qualitative component of a larger mixed methods study, we explore patients' lived experience with OAB to understand how this condition impacts individuals on a personal and social level, as well as their experiences interacting with the health care system.Methods: A total of 20 patients and 12 physicians completed a questionnaire and semi‐structured interview. The interview guide, developed in an iterative fashion by the authors, included questions about treatment decision making as well as experiences living with or treating OAB; this manuscript focuses on the questions probing lived experiences and interactions between patients and physicians. The interviews were recorded, transcribed and inductively coded and analyzed according to the principles of interpretive description to develop themes.Results: Analysis of patient and physician interviews yielded five key themes: isolation due to OAB diagnosis, social stigma associated with noticeable OAB symptoms, embarrassment from interactions with the health care system, feeling invalidated and dismissed by physicians, and OAB patients as a “vulnerable” population with “desperation” for cure.Conclusions: OAB causes patients marked distress beyond their physical symptoms; it causes feelings of isolation from friends and family and makes them feel embarrassed to discuss their condition with loved ones and physicians alike. Efforts to destigmatize OAB, validate patient experiences, and improve access to OAB care may help diminish the psychosocial burden of OAB.

We investigated lattice strain on alloyed surfaces using ∼10 nm core–shell nanoparticles with controlled size, shape, and composition.

The mechanism of oxygen activation at a dicobalt bis-μ-hydroxo core is probed by the implementation of synthetic methods to isolate reaction intermediates. Reduction of a dicobalt(III,III) core ligated by the polypyridyl ligand dipyridylethane naphthyridine (DPEN) by two electrons and subsequent protonation result in the release of one water moiety to furnish a dicobalt(II,II) center with an open binding site. This reduced core may be independently isolated by chemical reduction. Variable-temperature ¹H NMR and SQUID magnetometry reveal the reduced dicobalt(II,II) intermediate to consist of two low spin Co(II) centers coupled antiferromagnetically. Binding of O₂ to the open coordination site of the dicobalt(II,II) core results in the production of an oxygen adduct, which is proposed to be a dicobalt(III,III) peroxo. Electrochemical studies show that the addition of two electrons results in cleavage of the O–O bond.

Significance: Small-molecule conversions important to contemporary energy science often involve the reaction of two substrates in a multielectron redox process. The design of catalysts to effect such reactions requires knowledge of the reaction mechanism. It was shown over 30 y ago that quantitative kinetics information may be extracted from the cyclic voltammograms of catalysts that promote reactions involving a single electron and a single substrate. Attempts to extend this model to multielectron, multisubstrate reactions have permitted only qualitative kinetics insights to be extracted. The models developed herein allow quantitative kinetics rate constants to be obtained from peak currents and peak potentials of electrocatalytic reactions beyond a single electron and substrate, and accordingly they should be useful for guiding rational catalyst design.

Significance: The Co-OEC (oxygen-evolving catalyst) is an exemplary OEC that has provided a wealth of kinetics information on the proton-coupled electron transfer mechanism of O–O bond formation. Whereas electrochemical kinetics studies establish a high-valent Co(IV) ₂ oxidation state as a prerequisite for catalysis, this species cannot be spectroscopically examined in thin-film Co-OECs owing to its short lifetime and dilution against a largely Co(III) background. A molecular model of this high-valent active species is provisioned in the form of a doubly oxidized Co(III) ₂ (IV) ₂ cubane. In situ X-ray absorption spectroscopic examination of this high-valent state of the cubane provides direct insights into the electronic structure of a Co(IV) ₂ site and into its role in the mechanism of O–O bond formation.

The formation of high-valent states is a key factor in making highly active transition metal-based catalysts of the oxygen-evolving reaction (OER). These high oxidation states will be strongly influenced by the local geometric and electronic structures of the metal ion, which are difficult to study due to spectroscopically active and complex backgrounds, short lifetimes, and limited concentrations. Here, we use a wide range of complementary X-ray spectroscopies coupled to DFT calculations to study Co(III)₄O₄ cubanes and their first oxidized derivatives, which provide insight into the high-valent Co(IV) centers responsible for the activity of molecular and heterogeneous OER catalysts. The combination of X-ray absorption and 1s3p resonant inelastic X-ray scattering (Kβ RIXS) allow Co(IV) to be isolated and studied against a spectroscopically active Co(III) background. Co K- and L-edge X-ray absorption data allow for a detailed characterization of the 3d-manifold of effectively localized Co(IV) centers and provide a direct handle on the ligand field environment and covalency of the t_2g-based redox active molecular orbital. Kβ RIXS is also shown to provide a powerful probe of Co(IV), and specific spectral features are sensitive to the degree of oxo-mediated metal-metal coupling across Co₄O₄. Guided by the data, calculations show electron-hole delocalization can actually oppose Co(IV) formation. Computational extension of Co₄O₄ to CoM₃O₄ structures (M = redox-inactive metal) defines electronic structure contributions to Co(IV) formation. Redox activity is shown to be linearly related to covalency, and M(III) oxo inductive effects on Co(IV) oxo bonding can tune the covalency of high-valent sites over a large range and thereby tune E⁰ over hundreds of mVs. Additionally, redox-inactive metal substitution can also switch the ground state and modify metal-metal and anti-bonding interactions across the cluster.