Targeting STAT6-mediated synovial macrophage activation improves pain in experimental knee osteoarthritis.

BACKGROUND: Pain from osteoarthritis (OA) is one of the top causes of disability worldwide, but effective treatment is lacking. Nociceptive factors are released by activated synovial macrophages in OA, but depletion of synovial macrophages paradoxically worsens inflammation and tissue damage in previous studies. Rather than depleting macrophages, we hypothesized that inhibiting macrophage activation may improve pain without increasing tissue damage. We aimed to identify key mechanisms mediating synovial macrophage activation and test the role of STAT signaling in macrophages on pain outcomes in experimental knee OA. METHODS: We induced experimental knee OA in rats via knee destabilization surgery, and performed RNA sequencing analysis on sorted synovial tissue macrophages to identify macrophage activation mechanisms. Liposomes laden with STAT1 or STAT6 inhibitors, vehicle (control), or clodronate (depletion control) were delivered selectively to synovial macrophages via serial intra-articular injections up to 12 weeks after OA induction. Treatment effects on knee and hindpaw mechanical pain sensitivity were measured during OA development, along with synovitis, cartilage damage, and synovial macrophage infiltration using histopathology and immunofluorescence. Lastly, crosstalk between drug-treated synovial tissue and articular chondrocytes was assessed in co-culture. RESULTS: The majority of pathways identified by transcriptomic analyses in OA synovial macrophages involve STAT signaling. As expected, macrophage depletion reduced pain, but increased synovial tissue fibrosis and vascularization. In contrast, STAT6 inhibition in macrophages led to marked, sustained improvements in mechanical pain sensitivity and synovial inflammation without worsening synovial or cartilage pathology. During co-culture, STAT6 inhibitor-treated synovial tissue had minimal effects on healthy chondrocyte gene expression, whereas STAT1 inhibitor-treated synovium induced changes in numerous cartilage turnover-related genes. CONCLUSION: These results suggest that STAT signaling is a major mediator of synovial macrophage activation in experimental knee OA. STAT6 may be a key mechanism mediating the release of nociceptive factors from macrophages and the development of mechanical pain sensitivity. Whereas therapeutic depletion of macrophages paradoxically increases inflammation and fibrosis, blocking STAT6-mediated synovial macrophage activation may be a novel strategy for OA-pain management without accelerating tissue damage.

Rapid and sustained contact tracing training for COVID-19 in San Francisco: a training model for developing an emergency public health workforce.

The City and County of San Francisco was the first municipality in the United States to institute a COVID-19 contact tracing program. The San Francisco Department of Public Health (SFDPH) and the University of California, San Francisco (UCSF) created an outcome-based fully remote contact tracing curriculum using participatory learning methods to train non-public health emergency workers as contact tracers. Between April and December 2020, we trained over 300 individuals in contact tracing skills and procedures over three training phases. Using iterative curriculum design and Kirkpatrick's evaluation methodology, we aimed to ensure high quality and successful person-centered contact tracing. The resulting curriculum consisted of 24 learning outcomes taught with six participatory skills development activities, asynchronous materials, and one-on-one contact tracer support. We collected more than 700 responses from trainees using various evaluation tools across the training phases, and contact tracers interviewed more than 24,000 contacts after training in our program. Our evaluations showed that knowledge and skills improved for most trainees and demonstrated the utility of the training program in preparing trainees to perform person-centered contact tracing in San Francisco. Local health jurisdictions and state health agencies can use this model of curriculum development and evaluation to rapidly train a non-public health workforce to respond to future public health emergencies.

Ag(III)···Ag(III) Argentophilic Interaction in a Cofacial Corrole Dyad.

Metallophilic interactions between closed-shell metal centers are exemplified by d10 ions, with Au(I) aurophilic interactions as the archetype. Such an interaction extends to d8 species, and examples involving Au(III) are prevalent. Conversely, Ag(III) argentophilic interactions are uncommon. Here, we identify argentophilic interactions in silver corroles, which are authentic Ag(III) species. The crystal structure of a monomeric silver corrole is a dimer in the solid state, and the macrocycle exhibits an atypical domed conformation. In order to evaluate whether this represents an authentic metallophilic interaction or a crystal-packing artifact, the analogous cofacial or "pacman" corrole was prepared. The conformation of the monomer was recapitulated in the silver pacman corrole, exhibiting a short 3.67 Å distance between metal centers and a significant compression of the xanthene backbone. Theoretical calculations support the presence of a rare Ag(III)···Ag(III) argentophilic interaction in the pacman complex.

Solvent-Induced Spin-State Change in Copper Corroles.

The electronic structure of copper corroles has been a topic of debate and revision since the advent of corrole chemistry. The ground state of these compounds is best described as an antiferromagnetically coupled Cu(II) corrole radical cation. In coordinating solvents, these molecules become paramagnetic, and this is often accompanied by a color change. The underlying chemistry of these solvent-induced properties is currently unknown. Here, we show that a coordinating solvent, such as pyridine, induces a change in the ground spin state from an antiferromagnetically coupled Cu(II) corrole radical cation to a ferromagnetically coupled triplet. Over time, the triplet reacts to produce a species with spectral signatures that are characteristic of the one-electron-reduced Cu(II) corrole. These observations account for the solvent-induced paramagnetism and the associated color changes that have been observed for copper corroles in coordinating solvents.

Syntheses and Properties of Metalated Tetradehydrocorrins.

The monoanionic tetrapyrrolic macrocycle B,C-tetradehydrocorrin (TDC) resides chemically between corroles and corrins. This chemical space remains largely unexplored due to a lack of reliable synthetic strategies. We now report the preparation and characterization of Co(II)- and Ni(II)-metalated TDC derivatives ([Co-TDC]+ and [Ni-TDC]+, respectively) with a combination of crystallographic, electrochemical, computational, and spectroscopic techniques. [Ni-TDC]+ was found to undergo primarily ligand-centered electrochemical reduction, leading to hydrogenation of the macrocycle under cathodic electrolysis in the presence of acid. Transient absorption (TA) spectroscopy reveals that [Ni-TDC]+ and the two-electron-reduced [Ni-TDC]- possess long-lived excited states, whereas the excited state of singly reduced [Ni-TDC] exhibits picosecond dynamics. The Co(I) compound [Co-TDC] is air stable, highlighting the notable property of the TDC ligand to stabilize low-valent metal centers in contradistinction to other tetrapyrroles such as corroles, which typically stabilize metals in higher oxidation states.

Use of HIV Recency Assays for HIV Incidence Estimation and Other Surveillance Use Cases: Systematic Review.

BACKGROUND: HIV assays designed to detect recent infection, also known as "recency assays," are often used to estimate HIV incidence in a specific country, region, or subpopulation, alone or as part of recent infection testing algorithms (RITAs). Recently, many countries and organizations have become interested in using recency assays within case surveillance systems and routine HIV testing services to measure other indicators beyond incidence, generally referred to as "non-incidence surveillance use cases." OBJECTIVE: This review aims to identify published evidence that can be used to validate methodological approaches to recency-based incidence estimation and non-incidence use cases. The evidence identified through this review will be used in the forthcoming technical guidance by the World Health Organization (WHO) and United Nations Programme on HIV/AIDS (UNAIDS) on the use of HIV recency assays for identification of epidemic trends, whether for HIV incidence estimation or non-incidence indicators of recency. METHODS: To identify the best methodological and field implementation practices for the use of recency assays to estimate HIV incidence and trends in recent infections for specific populations or geographic areas, we conducted a systematic review of the literature to (1) understand the use of recency testing for surveillance in programmatic and laboratory settings, (2) review methodologies for implementing recency testing for both incidence estimation and non-incidence use cases, and (3) assess the field performance characteristics of commercially available recency assays. RESULTS: Among the 167 documents included in the final review, 91 (54.5%) focused on assay or algorithm performance or methodological descriptions, with high-quality evidence of accurate age- and sex-disaggregated HIV incidence estimation at national or regional levels in general population settings, but not at finer geographic levels for prevention prioritization. The remaining 76 (45.5%) described the field use of incidence assays including field-derived incidence (n=45), non-incidence (n=25), and both incidence and non-incidence use cases (n=6). The field use of incidence assays included integrating RITAs into routine surveillance and assisting with molecular genetic analyses, but evidence was generally weaker or only reported on what was done, without validation data or findings related to effectiveness of using non-incidence indicators calculated through the use of recency assays as a proxy for HIV incidence. CONCLUSIONS: HIV recency assays have been widely validated for estimating HIV incidence in age- and sex-specific populations at national and subnational regional levels; however, there is a lack of evidence validating the accuracy and effectiveness of using recency assays to identify epidemic trends in non-incidence surveillance use cases. More research is needed to validate the use of recency assays within HIV testing services, to ensure findings can be accurately interpreted to guide prioritization of public health programming.

Performance of a novel rapid test for recent HIV infection among newly-diagnosed pregnant adolescent girls and young women in four high-HIV-prevalence districts-Malawi, 2017-2018.

Tests for recent HIV infection (TRI) distinguish recent from long-term HIV infections using markers of antibody maturation. The limiting antigen avidity enzyme immunoassay (LAg EIA) is widely used with HIV viral load (VL) in a recent infection testing algorithm (RITA) to improve classification of recent infection status, estimate population-level HIV incidence, and monitor trends in HIV transmission. A novel rapid test for recent HIV infection (RTRI), Asanté™, can determine HIV serostatus and HIV recency within minutes on a lateral flow device through visual assessment of test strip or reader device. We conducted a field-based laboratory evaluation of the RTRI among pregnant adolescent girls and young women (AGYW) attending antenatal clinics (ANC) in Malawi.We enrolled pregnant AGYW aged <25 years testing HIV-positive for the first time at their first ANC visit from 121 ANCs in four high-HIV burden districts. Consenting participants provided blood for recency testing using LAg EIA and RTRI, which were tested in central laboratories. Specimens with LAg EIA normalized optical density values ≤2.0 were classified as probable recent infections. RTRI results were based on: (1) visual assessment: presence of a long-term line (LT) indicating non-recent infection and absence of the line indicating recent infection; or (2) a reader; specimens with LT line intensity units <3.0 were classified as probable recent infections. VL was measured for specimens classified as a probable recent infections by either assay; those with HIV-1 RNA ≥1,000 copies/mL were classified as confirmed recent infections. We evaluated the performance of the RTRI by calculating correlation between RTRI and LAg EIA results, and percent agreement and kappa between RTRI and LAg EIA RITA results.Between November 2017 to June 2018, 380 specimens were available for RTRI evaluation; 376 (98.9%) were confirmed HIV-positive on RTRI. Spearman's rho between RTRI and LAg EIA was 0.72 indicating strong correlation. Percent agreement and kappa between RTRI- and LAg EIA-based RITAs were >90% and >0.65 respectively indicating substantial agreement between the RITAs.This was the first field evaluation of an RTRI in sub-Saharan Africa, which demonstrated good performance of the assay and feasibility of integrating RTRI into routine HIV testing services for real-time surveillance of recent HIV infection.

MERS-CoV Confirmation among 6,873 suspected persons and relevant Epidemiologic and Clinical Features, Saudi Arabia - 2014 to 2019.

BACKGROUND: Of the three lethal coronaviruses, in addition to the ongoing pandemic-causing SARS-CoV 2, Middle East Respiratory Syndrome Coronavirus (MERS-CoV) remains in circulation. Information on MERS-CoV has relied on small sample of patients. We updated the epidemiology, laboratory and clinical characteristics, and survival patterns of MERS-CoV retrospectively with the largest sample of followed patients. METHODS: We conducted a retrospective review of line-listed records of non-random, continuously admitted patients who were suspected (6,873) or confirmed with MERS-CoV (501) admitted to one of the four MERS-CoV referral hospitals in Saudi Arabia, 2014-2019. FINDINGS: Of the 6,873 MERS-CoV suspected persons, the majority were male (56%) and Saudi nationals (83%) and 95% had no known history that increased their risk of exposure to MERS-CoV patients or vectors (95%). More confirmed cases reported history that increased their risk of MERS-CoV infection (41%). Among the suspected, MERS-CoV confirmation (7.4% overall) was independently associated with being male, known transmission link to MERS-CoV patients or vectors, fever, symptoms for 7 days, admission through intensive care unit, and diabetes. Among persons with confirmed MERS-CoV, single symptoms were reported by 20%, 3-symptom combinations (fever, cough and dyspnea) reported by 21% and 2-symptom combinations (fever, cough) reported by 16%. Of the two-thirds (62%) of MERS-CoV confirmed patients who presented with co-morbidity, 32% had 2-"comorbidities (diabetes, hypertension). More than half of the MERS-CoV patents showed abnormal chest X-ray, elevated aspartate aminotransferase, and creatinine kinase. About a quarter of MERS-CoV patients had positive cultures on blood, urine, or respiratory secretions. During an average hospital stay of 18 days (range 11 to 30), 64% developed complications involving liver, lungs, or kidneys. Ventilation requirement (29% of MERS-CoV cases) was independently associated with abnormal chest X-ray, viremia (Ct value <30), elevated creatinine, and prothrombin time. Death (21% overall) was independently associated with older age, dyspnea and abnormal chest X-ray on admission, and low hemoglobulin levels. INTERPRETATIONS: With two-thirds of the symptomatic persons developing multiorgan complications MERS-CoV remains the coronavirus with the highest severity (29%) and case fatality rate (21%) among the three lethal coronaviruses. Metabolic abnormalities appear to be an independent risk factor for sustained MERS-CoV transmission. The poorly understood transmission dynamics and non-specific clinical and laboratory features call for high index of suspicion among respiratory disease experts to help early detection of outbreaks. We reiterate the need for case control studies on transmission. FUNDING: No special funding to declare.

Establishment and Evaluation of a Large Contact-Tracing and Case Investigation Virtual Training Academy.

During the COVID-19 pandemic, the Virtual Training Academy (VTA) was established to rapidly develop a contact-tracing workforce for California. Through June 2021, more than 10 000 trainees enrolled in a contact-tracing or case investigation course at the VTA. To evaluate program effectiveness, we analyzed trainee pre- and postassessment results using the Wilcoxon signed-rank test. There was a statistically significant (P < .001) improvement in knowledge and self-perceived skills after course completion, indicating success in training a competent contact-tracing workforce. (Am J Public Health. 2021;111(11):1934-1938. https://doi.org/10.2105/AJPH.2021.306468).

California's COVID-19 Virtual Training Academy: Rapid Scale-Up of a Statewide Contact Tracing and Case Investigation Workforce Training Program.

Case investigation (CI) and contact tracing (CT) are key to containing the COVID-19 pandemic. Widespread community transmission necessitates a large, diverse workforce with specialized knowledge and skills. The University of California, San Francisco and Los Angeles partnered with the California Department of Public Health to rapidly mobilize and train a CI/CT workforce. In April through August 2020, a team of public health practitioners and health educators constructed a training program to enable learners from diverse backgrounds to quickly acquire the competencies necessary to function effectively as CIs and CTs. Between April 27 and May 5, the team undertook a curriculum design sprint by performing a needs assessment, determining relevant goals and objectives, and developing content. The initial four-day curriculum consisted of 13 hours of synchronous live web meetings and 7 hours of asynchronous, self-directed study. Educational content emphasized the principles of COVID-19 exposure, infectious period, isolation and quarantine guidelines and the importance of prevention and control interventions. A priority was equipping learners with skills in rapport building and health coaching through facilitated web-based small group skill development sessions. The training was piloted among 31 learners and subsequently expanded to an average weekly audience of 520 persons statewide starting May 7, reaching 7,499 unique enrollees by August 31. Capacity to scale and sustain the training program was afforded by the UCLA Extension Canvas learning management system. Repeated iteration of content and format was undertaken based on feedback from learners, facilitators, and public health and community-based partners. It is feasible to rapidly train and deploy a large workforce to perform CI and CT. Interactive skills-based training with opportunity for practice and feedback are essential to develop independent, high-performing CIs and CTs. Rigorous evaluation will continue to monitor quality measures to improve the training experience and outcomes.

Improving the benefits of HIV testing and referrals in large household surveys through active linkages to care: lessons and recommendations from the Namibia population-based HIV impact assessment (NAMPHIA), 2017.

In household-based surveys that include rapid HIV testing services (HTS), passive referral systems that give HIV-positive participants information about how and where to access ART but minimal follow-up support from survey staff may result in suboptimal linkage. In the 2017 Namibia Population-based HIV Impact Assessment (NAMPHIA), we piloted a system of active linkage to care and ART (ALCART) that utilized the infrastructure of existing community-based partner organizations (CBPOs). All HIV-positive participants age 15-64 years not on ART were given standard passive referrals to ART plus the option to participate in ALCART. Cases were assigned to CBPOs in participants' localities. Healthcare workers from the CBPO's contacted cases and facilitated their linkage to facility-based ART. A total of 510 participants were eligible and consented to ALCART. The majority were new diagnoses (80.8%), while the remainder were previously diagnosed but not on ART (19.2%). Of the 510, 473 (92.7%) were successfully linked into care. Of these, all but one initiated ART. Our ALCART system used existing CBPOs and contributed to >90% linkage-to-care and >99% ART-initiation among linked participants in a large, nationally-representative survey. This approach can be used to improve the potential benefits of HTS in other large population-based surveys.

HIV Prevalence, Risk Factors for Infection, and Uptake of Prevention, Testing, and Treatment among Female Sex Workers in Namibia.

BACKGROUND: In most settings, Female Sex Workers (FSW) bear a disproportionate burden of Human Immunodeficiency Virus (HIV) disease worldwide. Representative data to inform the development of behavioral and biomedical interventions for FSW in Namibia have not been published. OBJECTIVES: Our objectives were to measure HIV prevalence, identify risk factors for infection, and describe uptake of prevention, testing, and treatment among FSW in Namibia. METHODS: We conducted cross-sectional surveys using Respondent-driven Sampling (RDS) in the Namibian cities of Katima Mulilo, Oshikango, Swakopmund/Walvis Bay, and Windhoek. Participating FSW completed behavioral questionnaires and rapid HIV testing. RESULTS: City-specific ranges of key indicators were: HIV prevalence (31.0-52.3%), reached by prevention programs in the past 12 months (46.9-73.6%), condom use at last sex with commercial (82.1-91.1%) and non-commercial (87.0-94.2%) partners, and tested for HIV within past 12 months or already aware of HIV-positive serostatus (56.9-82.1%). Factors associated with HIV infection varied by site and included: older age, having multiple commercial or non-commercial sex partners, unemployment, being currently out of school, and lower education level. Among HIV-positive FSW, 57.1% were aware of their HIV-positive serostatus and 33.7% were on antiretroviral treatment. DISCUSSION: Our results indicate extremely high HIV prevalence and low levels of case identification and treatment among FSW in Namibia. Our results, which are the first representative community-based estimates among FSW in Namibia, can inform the scale-up of interventions to reduce the risk for HIV acquisition and onward transmission, including treatment as prevention and pre-exposure prophylaxis.

Rates and Correlates of HIV Incidence in Namibia's Zambezi Region From 2014 to 2016: Sentinel, Community-Based Cohort Study.

BACKGROUND: Direct measures of HIV incidence are needed to assess the population-level impact of prevention programs but are scarcely available in the subnational epidemic hotspots of sub-Saharan Africa. We created a sentinel HIV incidence cohort within a community-based program that provided home-based HIV testing to all residents of Namibia's Zambezi region, where approximately 24% of the adult population was estimated to be living with HIV. OBJECTIVE: The aim of this study was to estimate HIV incidence, detect correlates of HIV acquisition, and assess the feasibility of the sentinel, community-based approach to HIV incidence surveillance in a subnational epidemic hotspot. METHODS: Following the program's initial home-based testing (December 2014-July 2015), we purposefully selected 10 clusters of 60 to 70 households each and invited residents who were HIV negative and aged ≥15 years to participate in the cohort. Consenting participants completed behavioral interviews and a second HIV test approximately 1 year later (March-September 2016). We used Poisson models to calculate HIV incidence rates between baseline and follow-up and multivariable Cox proportional hazard models to assess the correlates of seroconversion. RESULTS: Among 1742 HIV-negative participants, 1624 (93.23%) completed follow-up. We observed 26 seroconversions in 1954 person-years (PY) of follow-up, equating to an overall incidence rate of 1.33 per 100 PY (95% CI 0.91-1.95). Among women, the incidence was 1.55 per 100 PY (95% CI 1.12-2.17) and significantly higher among those aged 15 to 24 years and residing in rural areas (adjusted hazard ratio [aHR] 4.26, 95% CI 1.39-13.13; P=.01), residing in the Ngweze suburb of Katima Mulilo city (aHR 2.34, 95% CI 1.25-4.40; P=.01), who had no prior HIV testing in the year before cohort enrollment (aHR 3.38, 95% CI 1.04-10.95; P=.05), and who had engaged in transactional sex (aHR 17.64, 95% CI 2.88-108.14; P=.02). Among men, HIV incidence was 1.05 per 100 PY (95% CI 0.54-2.31) and significantly higher among those aged 40 to 44 years (aHR 13.04, 95% CI 5.98-28.41; P<.001) and had sought HIV testing outside the study between baseline and follow-up (aHR 8.28, 95% CI 1.39-49.38; P=.02). No seroconversions occurred among persons with HIV-positive partners on antiretroviral treatment. CONCLUSIONS: Nearly three decades into Namibia's generalized HIV epidemic, these are the first estimates of HIV incidence for its highest prevalence region. By creating a sentinel incidence cohort from the infrastructure of an existing community-based testing program, we were able to characterize current transmission patterns, corroborate known risk factors for HIV acquisition, and provide insight into the efficacy of prevention interventions in a subnational epidemic hotspot. This study demonstrates an efficient and scalable framework for longitudinal HIV incidence surveillance that can be implemented in diverse sentinel sites and populations.

Multielectron C-H photoactivation with an Sb(v) oxo corrole.

Pnictogen complexes are ideal for mediating multi-electron chemical reactions in two-electron steps. We report an Sb(v) bis-µ-oxo corrole that photochemically oxidises the C-H bonds of organic substrates. In the case of toluene, the substrate is oxidised to benzaldehyde, a rare example of a four-electron photoreaction.

Ligand Noninnocence in Nickel Porphyrins: Nickel Isobacteriochlorin Formation under Hydrogen Evolution Conditions.

An electron-deficient nickel porphyrin complex undergoes facile ring reduction to form a nickel isobacteriochlorin complex under hydrogen evolution conditions. Spectroscopic experiments indicate that the reduced nickel porphyrin undergoes subsequent reduction and protonation to form a phlorin anion rather than a metal hydride, demonstrating that the key initial proton-coupled electron transfer step is directed toward the ligand versus the metal. The phlorin anion facilely converts to the isobacteriochlorin in the presence of two-electron and three-proton equivalents. Cyclic voltammetry (CV) and spectroscopic experiments reveal that the four-electron, four-proton electrochemical reduction of nickel porphyrin to isobacteriochlorin occurs promptly in the presence of the strong proton donor tosic acid, followed by hydrogen evolution reaction (HER) catalysis at slightly more negative potentials. CVs of independently synthesized Ni isobacteriochlorin show a catalytic HER at the same potentials as those observed for the HER in CVs of the Ni porphyrin. We find that, under strongly acidic conditions, the HER catalysis arises from conversion of the Ni isobacteriochlorin into a nickel-containing, catalytically active electrode-adsorbed species. These results show that Ni porphyrin converts to Ni isobacteriochlorin under HER catalysis conditions via a ligand-based PCET process and that it is the isobacteriochlorin complex which gives rise to an active HER catalysis.

Estimating the Population Size of Female Sex Workers in Namibia Using a Respondent-Driven Sampling Adjustment to the Reverse Tracking Method: A Novel Approach.

BACKGROUND: Key populations, including female sex workers (FSWs), are at a disproportionately high risk for HIV infection. Estimates of the size of these populations serve as denominator data to inform HIV prevention and treatment programming and are necessary for the equitable allocation of limited public health resources. OBJECTIVE: This study aimed to present the respondent-driven sampling (RDS) adjusted reverse tracking method (RTM; RadR), a novel population size estimation approach that combines venue mapping data with RDS data to estimate the population size, adjusted for double counting and nonattendance biases. METHODS: We used data from a 2014 RDS survey of FSWs in Windhoek and Katima Mulilo, Namibia, to demonstrate the RadR method. Information from venue mapping and enumeration from the survey formative assessment phase were combined with survey-based venue-inquiry questions to estimate population size, adjusting for double counting, and FSWs who do not attend venues. RadR estimates were compared with the official population size estimates, published by the Namibian Ministry of Health and Social Services (MoHSS), and with the unadjusted RTM. RESULTS: Using the RadR method, we estimated 1552 (95% simulation interval, SI, 1101-2387) FSWs in Windhoek and 453 (95% SI: 336-656) FSWs in Katima Mulilo. These estimates were slightly more conservative than the MoHSS estimates-Windhoek: 3000 (1800-3400); Katima Mulilo: 800 (380-2000)-though not statistically different. We also found 75 additional venues in Windhoek and 59 additional venues in Katima Mulilo identified by RDS participants' responses that were not detected during the initial mapping exercise. CONCLUSIONS: The RadR estimates were comparable with official estimates from the MoHSS. The RadR method is easily integrated into RDS studies, producing plausible population size estimates, and can also validate and update key population maps for outreach and venue-based sampling.

Observation of a Photogenerated Rh2 Nitrenoid Intermediate in C-H Amination.

Rh2-catalyzed C-H amination is a powerful method for nitrogenating organic molecules. While Rh2 nitrenoids are often invoked as reactive intermediates in these reactions, the exquisite reactivity and fleeting lifetime of these species has precluded their observation. Here, we report the photogeneration of a transient Rh2 nitrenoid that participates in C-H amination. The developed approach to Rh2 nitrenoids, based on photochemical cleavage of N-Cl bonds in N-chloroamido ligands, has enabled characterization of a reactive Rh2 nitrenoid by mass spectrometry and transient absorption spectroscopy. We anticipate that photogeneration of metal nitrenoids will contribute to the development of C-H amination catalysis by providing tools to directly study the structures of these critical intermediates.

Halogen Photoelimination from SbV Dihalide Corroles.

Main-group p-block metals are ideally suited for mediating two-electron reactions because they cycle between M n and M n+2 redox states, as the one-electron state is thermodynamically unstable. Here, we report the synthesis and structure of an SbIII corrole and its SbVX2 (X = Cl, Br) congeners. SbIII sits above the corrole ring, whereas SbV resides in the corrole centroid. Electrochemistry suggests interconversion between the SbIII and SbVX2 species. TD-DFT calculations indicate a HOMO → LUMO+2 parentage for excited states in the Soret spectral region that have significant antibonding character with respect to the Sb-X fragment. The photochemistry of 2 and 3 in THF is consistent with the computational results, as steady-state photolysis at wavelengths coincident with the Soret absorption of SbVX2 corrole lead to its clean conversion to the SbIII corrole. This ability to photoactivate the Sb-X bond reflects the proclivity of the pnictogens to rely on the PnIII/V couple to drive the two-electron photochemistry of M-X bond activation, an essential transformation needed to develop HX-splitting cycles.