[reaction: see text] Alpha-tocopherol (alpha-TOH), the main oil component making up vitamin E, and its nonnatural solid 6-hydroxy-2,2,5,7,8-pentamethylchroman and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid structurally related analogues were oxidized quantitatively with 2 mol equiv of NO+ SbF6(-) in CH3CN at 233 K to form phenoxonium cations (alpha-TO+ SbF6(-)) in a chemically reversible two-electron/one-proton process. Solution-phase infrared spectroscopy, 1H and 13C NMR spectroscopy, and corresponding theoretical calculations of the spectroscopic data using density-based and wave-function-based models support the identity of the remarkably stable phenoxonium cations. The presence of an oxygen atom in the para position to the hydroxyl group and the chromanol ring structure appear to be important factors in stabilization of the phenoxonium ions, which raises the interesting possibility that the cations play a crucial role in the mode of action of vitamin E in biological systems. Although the phenoxonium cations are reactive toward nucleophiles such as water, they may be moderately stable in the hydrophobic (lipophilic) environment where vitamin E is known to occur naturally.

Supplemental Digital Content is available in the text.

The phenoxonium cation of a vitamin E model compound has been crystallized using the non-nucleophilic carborane and tetrakis(pentafluorophenyl)borate counteranions. The crystal structures confirm the assignment of the unusually stable phenoxonium cation and indicate that there is a substantial shortening of the carbon-oxygen bond lengths of the para-carbon atoms in the phenolic ring and a substantial increase of the carbon-oxygen bond length at the quaternary carbon. The crystallographic data are in excellent agreement with structural predictions from molecular orbital calculations.

Clinical outcomes in solid organ transplant (SOT) recipients with breakthrough COVID (BTCo) after two doses of mRNA vaccination compared to the non‐immunocompromised/immunosuppressed (ISC) general population, are not well described. In a cohort of adult patients testing positive for COVID‐19 between December 10, 2020 and April 4, 2022, we compared the cumulative incidence of BTCo in a non‐ISC population to SOT recipients (overall and by organ type) using the National COVID Cohort Collaborative (N3C) including data from 36 sites across the United States. We assessed the risk of complications post‐BTCo in vaccinated SOT recipients versus SOT with unconfirmed vaccination status (UVS) using multivariable Cox proportional hazards and logistic regression. BTCo occurred in 4776 vaccinated SOT recipients over a median of 149 days (IQR 99–233), with the highest cumulative incidence in heart recipients. The relative risk of BTCo was greatest in SOT recipients (relative to non‐ISC) during the pre‐Delta period (HR 2.35, 95% CI 1.80–3.08). The greatest relative benefit with vaccination for both non‐ISC and SOT cohorts was in BTCo mortality (HR 0.37, 95% CI 0.36–0.39 for non‐ISC; HR 0.67, 95% 0.57–0.78 for SOT relative to UVS). While the relative benefit of vaccine was less in SOT than non‐ISC, SOT patients still exhibited significant benefit with vaccination.

While older males are at the highest risk for poor coronavirus disease 2019 (COVID‐19) outcomes, it is not known if this applies to the immunosuppressed recipient of a solid organ transplant (SOT), nor how the type of allograft transplanted may impact outcomes. In a cohort study of adult (>18 years) patients testing positive for COVID‐19 (January 1, 2020‐June 21, 2021) from 56 sites across the United States identified using the National COVID Cohort Collaborative (N3C) Enclave, we used multivariable Cox proportional hazards models to assess time to MARCE after COVID‐19 diagnosis in those with and without SOT. We examined the exposure of age‐stratified recipient sex overall and separately in kidney, liver, lung, and heart transplant recipients. 3996 (36.4%) SOT and 91 646 (4.8%) non‐SOT patients developed MARCE. Risk of post‐COVID outcomes differed by transplant allograft type with heart and kidney recipients at highest risk. Males with SOT were at increased risk of MARCE, but to a lesser degree than the non‐SOT cohort (HR 0.89, 95% CI 0.81–0.98 for SOT and HR 0.61, 95% CI 0.60–0.62 for non‐SOT [females vs. males]). This represents the largest COVID‐19 SOT cohort to date and the first‐time sex‐age–stratified and allograft‐specific COVID‐19 outcomes have been explored in those with SOT.

The reaction of [RuRCl(CO)(PPh 3 ) 2 ] (R = C 6 H 5 , CHdCHPh) with the Yamashita-Nozaki ligand C 6 H 4 {N(CH 2 PPh 2 )} 2 BH (dppBH) results in facile elimination of benzene or styrene and formation of the ruthenium [PBP]pincer complex [Ru{κ 3 B,P,P 0 -dppB)Cl(CO)(PPh 3 )] via a stepwise sequence that recalls the formation of the ruthenaboratrane [Ru(CO)(PPh 3 ){B(mt) 3 }] (mt = methimazolyl) from [RuRCl-(CO)(PPh 3 ) 2 ] and Na[HB(mt) 3 ]. This analogy is explored herein, including observations regarding notionally similar processes for triboronate ligands. Thus, while the major product of the reaction ofalso obtained, consistent with alcoholic transfer hydrogenation of the putative complex [B 3 H 7 Ru(CO)(PPh 3 ) 2 ]. a Legend: (i) K[H 2 B(mt) 2 ]; 6 (ii) Tl[B 3 H 8 ]; 8 (iii) [Me 4 N][C 2 B 9 H 12 ]; 9 (iv) C 6 H 4 N 2 (CH 2 PPh 2 ) 2 BH (dppBH).10a

Background Antiretrovirals (ARVs) are key in the management of HIV. Although no cure exists, ARVs help patients live healthy lives and prevent transmission to others. Adherence to complex regimens is paramount to outcomes and in avoiding the emergence of drug-resistant viruses. The goal of therapy is to reach an undetectable viral load. However, adherence is a common problem, stemming from issues such as mental health, chaotic home situations, and busy work schedules. Mobile health (mHealth) represents a new approach in improving medication adherence, and multiple studies have been performed in this area. Objective This study aims to review the current implementation of mHealth in the management of HIV among different groups of patients. Methods We used PubMed, Academic Search Elite, and 1 journal database with various search terms to review the current implementation of mHealth in HIV care. Results Titles and abstracts were screened, and 61 papers were identified and fully reviewed. The literature was divided into lower- and higher-income nations, as defined by the United Nations. A total of 20 studies with quantitative results were identified, with 10 being text- and SMS-based interventions (the majority of these being in lower-income countries) and 8 being smartphone-based apps (primarily in higher-income countries). The majority of these studies determined whether there was an effect on adherence or biochemical parameters (viral load and CD4 count). Various qualitative studies have also been conducted, and many have focused on determining the specific design of interventions that were successful (frequency of messaging, types of messages, etc) as well as priorities for patients with regard to mHealth interventions. Conclusions There seems to be a role of mHealth in the management of HIV in lower-income nations; however, the optimal design of an intervention needs to be delineated. In higher-income countries, where the 2 significant risk factors were injection drugs and men who have sex with men, the benefit was less clear, and more research is needed.

We correlated antibiotic consumption measured by point prevalence survey with defined daily doses (DDD) across multiple hospitals. Point prevalence survey had a higher correlation (1) with monthly DDDs than annual DDDs, (2) in nonsurgical versus surgical wards, and (3) on high- versus low-utilization wards. Findings may be hospital specific due to hospital differences.