Gender dysphoria and gender-affirming surgery: The New York state experience.

BACKGROUND: Transgender and gender nonconforming (TGNC) individuals experience incongruence between their self-identified gender versus their birth-assigned sex. In some cases, TGNC patients undergo gender-affirming surgical (GAS) procedures. Although GAS is an evolving surgical field, there is currently limited literature documenting patient characteristics and procedures. Addressing this knowledge gap, this retrospective cohort analysis described the characteristics of New York State's TGNC residents with gender dysphoria (GD) diagnosis, including patients undergoing at least one gender-affirming surgical procedure. METHODS: Using the New York Statewide Planning and Research Cooperative System (SPARCS) database from 2002 to 2018, we identified patients' first-time TCNC records and their risk characteristics. Patients who received GAS procedures were sub-classified as top-only, bottom-only, or combined top/bottom procedures and were compared with TGNC patients who did not receive GAS. RESULTS: Of 24,615 records extracted from TGNC SPARCS database, 11,427 (46.4%) were transmasculine (female-to-male) and 13,188 (53.6%) were transfeminine (male-to-female). Overall, 2.73% of transgender patients received at least one GAS procedure. Of these patients, 78.2% had masculinizing and 21.8% had feminizing surgeries. After a diagnosis of GD, the positive predictors for a GAS-based procedure included female birth sex, pediatric age (<18 years) or older age (60+ years), commercial insurance coverage, and Hispanic race. In contrast, negative GAS predictors included male birth sex and government insurance coverage (i.e., Medicare and Medicaid). CONCLUSIONS: Compared with transgender women, transgender men were more likely to receive at least one GAS procedure. Because the race, ethnicity, and payor status of TGNC patients can impact GAS treatment rates, additional research is warranted to examine post-diagnosis GAS treatment disparities among TGNC patients.

Photoinduced cerium-catalyzed C-H acylation of unactivated alkanes.

Ketones are ubiquitous motifs in the realm of pharmaceuticals and natural products. Traditional approaches to accessing these species involve the addition of metal reagents to carboxyl compounds under harsh conditions. Herein, we report a cerium-catalyzed acylation of unactivated C(sp3)-H bonds using bench-stable acyl azolium reagents under mild and operationally-friendly conditions. This reaction exhibits excellent generality, accommodating a wide range of feedstock chemicals such as cycloalkanes and acyclic compounds as well as facilitating the late-stage functionalization of pharmaceuticals. We demonstrate further applications of our strategy with a three-component radical relay reaction and an enantioselective N-heterocyclic carbene (NHC) and cerium dual-catalyzed reaction.

Cooperative Carbene Photocatalysis for ß-Amino Ester Synthesis.

ß-Amino acids are useful building blocks of bioactive molecules, including peptidomimetics and pharmaceutical compounds. The current limited accessibility to ß2,2-type amino acids which bear an α-quaternary center has limited their use in chemical synthesis and biological investigations. Disclosed herein is the development of a new N-heterocyclic carbene/photocatalyzed aminocarboxylation of olefins, affording ß2,2-amino esters with high regioselectivity. The generation of nitrogen-centered radicals derived from simple imides via a sequence of deprotonation and single-electron oxidation allows for the subsequent addition to geminal-disubstituted olefins regioselectively. The intermediate tertiary radicals then cross-couple with a stabilized azolium-based radical generated in situ to efficiently construct the quaternary centers. Mechanistic studies, including Stern-Volmer fluorescence quenching experiments, support the proposed catalytic cycle.

Impact of surgical technique on outcome measures in chest masculinization: A systemic review and meta-analysis.

BACKGROUND: Among plastic surgeons, there are several conventional techniques for performing chest surgery. Research on surgical approaches has focused cis-gender patients with medical conditions, such as breast cancer or gynecomastia, but has never studied transgender populations. The aim of this study is to perform the first systematic review of gender-affirming surgery (GAS) in transgender populations and determine postoperative outcomes differences in relation to surgical technique. METHODS: Two reviewers independently searched Medline, Embase, CINAHL, Web of Science, and Cochrane databases for studies published prior to 2021. Studies selected for inclusion were retrospective or prospective studies of adult transgender men undergoing GAS that utilized appropriate operative techniques and reported complications and/or patient-reported outcomes. RESULTS: A total of 26 randomized controlled trials, including 40 distinct populations and 3055 patients, were identified. Surgical techniques compared double incision free nipple graft (DIFNG) (2053 patients [67.20%]), pedicled nipple techniques (PNT) (297 [9.72%]), and periareolar techniques (PAT) (705 [23.08%]). Pairwise analysis found the lowest complication rates associated with procedures utilizing DIFNG, followed by PNT, then PAT. Patients with PAT had significantly higher satisfaction scores than DIFNG. CONCLUSIONS: This is the first systematic review to evaluate outcomes of chest surgery techniques among the transgender population. Results indicate significantly more complications for PAT compared to DIFNG or PNT. Analysis of patient-reported outcomes was limited due to heterogeneity in reporting.

Photoinduced Acylations Via Azolium-Promoted Intermolecular Hydrogen Atom Transfer.

Photoinduced hydrogen atom transfer (HAT) has been developed as a powerful tool to generate synthetically valuable radical species. The direct photoexcitation of ketones has been known to promote HAT or to generate acyl radicals through Norrish-type pathways, but these modalities remain severely limited by radical side reactions. We report herein a catalyst- and transition metal-free method for the acylation of C-H bonds that leverages the unique properties of stable, isolable acyl azolium species. Specifically, acyl azolium salts are shown to undergo an intermolecular and regioselective HAT upon LED irradiation with a range of substrates bearing active C-H bonds followed by C-C bond formation to afford ketones. Experimental and computational studies support photoexcitation of the acyl azolium followed by facile intersystem crossing to access triplet diradical species that promote selective HAT and radical-radical cross-coupling.

Photoredox-Catalyzed Radical-Radical Coupling of Potassium Trifluoroborates with Acyl Azoliums.

Potassium trifluoroborates have gained significant utility as coupling partners in organic synthesis, particularly in the Suzuki-Miyaura coupling reaction. Recently, they have also been used as radical precursors under oxidative conditions to generate carbon-centered radicals. These versatile reagents have found new applications in photoredox catalysis, including radical substitution, conjugate addition reactions, and transition metal dual catalysis. In addition, this photomediated redox neutral process has enabled radical-radical coupling with persistent radicals in the absence of a metal, and this process remains to be fully explored. In this study, we report the radical-radical coupling of benzylic potassium trifluoroborate salts with isolated acyl azolium triflates, which are persistent radical precursors. The reaction is catalyzed by an organic photocatalyst and forms isolable tertiary alcohol species. These compounds can be transformed into a range of substituted ketone products by simple treatment with a mild base.

Photocatalytic acyl azolium-promoted alkoxycarbonylation of trifluoroborates.

Despite recent advancements in the selective generation and coupling of organic radical species, the alkoxycarbonyl radical remains underexplored relative to other carbon-containing radical species. Drawing inspiration from new strategies for generating acyl radical equivalents utilizing dual N-heterocyclic carbene catalysis and photocatalysis, we have prepared dimethylimidazolium esters that can function as an alkoxycarbonyl radical surrogate under photocatalytic conditions. We demonstrate the synthetic utility of these azolium-based partners through the preparation of esters arising from the coupling of this radical surrogate with an oxidatively generated alkyl radical.

Assessing the Feasibility of an Open-Source Virtual Reality Mirror Visual Feedback Module for Complex Regional Pain Syndrome: Pilot Usability Study.

BACKGROUND: Complex regional pain syndrome (CRPS) is a rare and severe chronic pain condition, with effective treatment options not established for many patients. The underlying pathophysiology remains unclear, but there is a growing appreciation for the role of central mechanisms which have formed the basis for brain-based therapies such as transcranial magnetic stimulation and mirror visual feedback (MVF). MVF has been deployed in the treatment of CRPS using both conventional mirrors and virtual reality (VR). OBJECTIVE: The aim of this study was to further investigate the use of VR in the treatment of patients with unilateral upper limb CRPS. VR has the potential advantage of more flexible and more motivating tasks, as well as the option of tracking patient improvement through the use of movement data. METHODS: We describe the development, acceptability, feasibility, and usability of an open-source VR program MVF module designed to be used with consumer VR systems for the treatment of CRPS. The development team was an interdisciplinary group of physical therapists, pain researchers, and VR researchers. Patients recruited from a pain clinic completed 3-5 visits each to trial the system and assessed their experiences in pre- and post-treatment questionnaires. RESULTS: All 9 (100%) participants were able to use the system for 3, 4, or 5 trials each. None of the participants quit any trial due to cybersickness. All 9 (100%) participants reported interest in using the module in the future. Participants' reported average pain scores in the affected limb were not significantly different from baseline during treatment or after treatment (P=.16). We did not find a statistically significant effect on participants' self-reported average pain scores. CONCLUSIONS: We propose that this module could be a useful starting point for modification and testing for other researchers. We share modifications to make this module usable with standalone headsets and finger tracking. Next steps include adapting this module for at-home use, or for use with participants with lower limb pain.

Radical coupling of ß-ketoesters and amides promoted by Brønsted/Lewis acids.

Recent advances in photocatalysis have enabled radical methods with complementary chemoselectivity to established two electron bond forming approaches. While this radical strategy has previously been limited to substrates with favorable redox potentials, Brønsted/Lewis acid activation has emerged as a means of facilitating otherwise difficult reductions. We report herein our investigations into the Lewis acid-promoted redox activation of ß-ketocarbonyls in a model photocatalytic radical alkylation reaction. Rapid evaluation of substrates and reactions conditions was achieved by high throughput experimentation using 96-well plate photoreactors.

Carbene-Catalyzed Enantioselective Decarboxylative Annulations to Access Dihydrobenzoxazinones and Quinolones.

A direct decarboxylative strategy for the generation of aza-o-quinone methides (aza-o-QMs) by N-heterocyclic carbene (NHC) catalysis has been discovered and explored. This process requires no stoichiometric additives in contrast with current approaches. Aza-o-QMs react with trifluoromethyl ketones through a formal [4+2] manifold to access highly enantioenriched dihydrobenzoxazin-4-one products, which can be converted to dihydroquinolones through an interesting stereoretentive aza-Petasis-Ferrier rearrangement sequence. Complementary dispersion-corrected density functional theory (DFT) studies provided an accurate prediction of the reaction enantioselectivity and lend further insight to the origins of stereocontrol. Additionally, a computed potential energy surface around the major transition structure suggests a concerted asynchronous mechanism for the formal annulation.