Metal-Free Homogeneous O2 Reduction by an Iminium-Based Electrocatalyst.

The oxygen reduction reaction (ORR) is important for alternative energy and industrial oxidation processes. Herein, an iminium-based organoelectrocatalyst (im+) for the ORR with trifluoroacetic acid as a proton source in acetonitrile solution under both electrochemical and spectrochemical conditions using decamethylferrocene as a chemical reductant is reported. Under spectrochemical conditions, H2O2 is the primary reaction product, while under electrochemical conditions H2O is produced. This difference in selectivity is attributed to the interception of the free superoxide intermediate under electrochemical conditions by the reduced catalyst, accessing an alternate inner-sphere pathway.

The phenomenon of phototoxicity and long-term risks of commonly prescribed and structurally diverse drugs.

Photosensitivity to structurally diverse drugs is a common but under-reported adverse cutaneous reaction and can be classified as phototoxic or photoallergic. Phototoxic reactions occur when the skin is exposed to sunlight after administering topical or systemic medications that exhibit photosensitizing activity. These reactions depend on the dose of medication, degree of exposure to ultraviolet light, type of ultraviolet light, and sufficient skin distribution volume. Accurate prediction of the incidence and phototoxic response severity is challenging due to a paucity of literature, suggesting that phototoxicity may be more frequent than reported. This paper reports an extensive literature review on phototoxic drugs; the review employed pre-determined search criteria that included meta-analyses, systematic reviews, literature reviews, and case reports freely available in full text. Additional reports were identified from reference sections that contributed to the understanding of phototoxicity. The following drugs and/or drug classes are discussed: amiodarone, voriconazole, chlorpromazine, doxycycline, fluoroquinolones, hydrochlorothiazide, nonsteroidal anti-inflammatory drugs, and vemurafenib. In reviewing phototoxic skin reactions, this review highlights drug molecular structures, their reactive pathways, and, as there is a growing association between photosensitizing drugs and the increasing incidence of skin cancer, the consequential long-term implications of photocarcinogenesis.

Twelve Steps to Financial Freedom for Plastic Surgeons.

Financial stress and lack of financial well-being are significant contributors to physician burnout. Many trainees believe little can contribute to developing financial freedom during their training years. However, residency is a pivotal moment in a young attending's life; strategic financial steps taken during this time can lead to a path of financial freedom and well-being for years to come. Methods: We introduce 12 effective financial steps physicians can take at the start of their careers. These essential steps were compiled both anecdotally and from published financial resources such as White Coat Investigator and the Millionaire Next Door. Steps include building your "why," becoming financially educated, eliminating debt, attaining insurance, optimizing contracts, awareness of self-net worth, budgeting, maximizing investment strategies, smart investing, wise spending, K.I.S.S, and creating a personal financial plan. Results: As an example, an IRA is a retirement account set up by you, and to take advantage of the tax benefits, you must have a modified adjusted gross income of less than $124,000 as a single tax filer for 2022. Most physicians are compensated at a rate higher than this; however, there is a legal loophole to take advantage of to allow earners to still contribute to a Roth IRA that is discussed. Conclusions: Financial education is the first step toward a path to financial success in a young physician's life. Implementation of these 12 financial steps early in a physician's career will enrich one's financial freedom and well-being.

Vinylazaarenes as dienophiles in Lewis acid-promoted Diels-Alder reactions.

Described are the first examples of Lewis acid-promoted Diels-Alder reactions of vinylpyridines and other vinylazaarenes with unactivated dienes. Cyclohexyl-appended azaarenes constitute a class of substructures of rising prominence in drug discovery. Despite this, thermal variants of the vinylazaarene Diels-Alder reaction are rare and have not been adopted for synthesis, and Lewis acid-promoted variants are virtually unexplored. The presented work addresses this gap and in the process furnishes increased scope, dramatically higher yields, improved regioselectivity, and high levels of diastereoselectivity compared to prior thermal examples. These reactions provide scalable access to druglike scaffolds not readily available through other methods. More broadly, these studies establish a useful new class of dienophiles that, based on preliminary mechanistic studies, should be amenable to conventional strategies for enantioselective catalysis.