Forging structural complexity: diastereoselective synthesis of densely substituted β-lactams with dual functional handles for enhanced core modifications.

The preparation of the β-lactam motif containing both C-Br and N-O bonds as functional handles remains an unmet synthetic challenge. Described herein is a novel and highly diastereoselective NBS-mediated cyclization of alkoxy α,β-unsaturated silyl imino ethers to furnish nearly three dozen α-bromo -alkoxy β-lactams. The reaction gives rapid and convenient access to structurally diverse monocyclic, spirocyclic and fused β-lactams in moderate to good yields.

Nickel-Catalyzed Electrochemical Cross-Electrophile C(sp)-C(sp) Coupling via a Ni Aryl Amido Intermediate.

Cross-electrophile coupling (XEC) between aryl halides and alkyl halides is a streamlined approach for C(sp)-C(sp) bond construction, which is highly valuable in medicinal chemistry. Based on a key Ni aryl amido intermediate, we developed a highly selective and scalable Ni-catalyzed electrochemical XEC reaction between (hetero)aryl halides and primary and secondary alkyl halides. Experimental and computational mechanistic studies indicate that an amine secondary ligand slows down the oxidative addition process of the Ni-polypyridine catalyst to the aryl bromide and a Ni aryl amido intermediate is formed in situ during the reaction process.

Electro/Ni Dual-Catalyzed Decarboxylative C(sp)-C(sp) Cross-Coupling Reactions of Carboxylates and Aryl Bromide.

Paired redox-neutral electrolysis offers an attractive green platform for organic synthesis by avoiding sacrificial oxidants and reductants. Carboxylates are non-toxic, stable, inexpensive, and widely available, making them ideal nucleophiles for C-C cross-coupling reactions. Here, we report the electro/Ni dual-catalyzed redox-neutral decarboxylative C(sp)-C(sp) cross-coupling reactions of pristine carboxylates with aryl bromides.

Gender differences in receipt of telehealth versus in person behavioral therapy, medication for opioid use disorder (MOUD), and 90-day MOUD retention during the pandemic: A retrospective veteran cohort study.

Background: COVID-19 significantly negatively impacted access to care among patients with opioid use disorder (OUD). The Veterans Health Administration (VHA) enacted policies to expand telehealth and medication for OUD (MOUD) during the public health emergency, which offset risk of treatment disruption. In this study, we evaluated gender differences in utilization of behavioral therapy in person and via telehealth, MOUD utilization, and achieving 90-day MOUD retention pre-post pandemic onset, given known gender differences in treatment utilization between men and women.

HIV Prevalence and HIV Screening History Among a Veterans Association Cohort of People with Opioid and Alcohol Use Disorders.

Background: Veterans face high risk for HIV and substance use, and thus could be disproportionately impacted by the HIV and substance use disorder (SUD) "syndemic." HIV prevalence among veterans with SUD is unknown.

Objective: To project HIV prevalence and lifetime HIV screening history among US veterans with alcohol use disorder (AUD), opioid use disorder (OUD), or both.

Dynamic-dependent selectivity in a bisphosphine iron spin crossover C-H insertion/π-coordination reaction.

Reaction pathway selectivity is generally controlled by competitive transition states. Organometallic reactions are complicated by the possibility that electronic spin state changes rather than transition states can control the relative rates of pathways, which can be modeled as minimum energy crossing points (MECPs). Here we show that in the reaction between bisphosphine Fe and ethylene involving spin state crossover (singlet and triplet spin states) that neither transition states nor MECPs model pathway selectivity consistent with experiment.

Directing-Group-Free Arene C(sp)-H Amination Using Bulky Aminium Radicals and DFT Analysis of Regioselectivity.

A hydroxylamine-derived electrophilic aminating reagent produces a transient and bulky aminium radical intermediate upon activation by either TMSOTf or TFA and a subsequent electron transfer from an iron(II) catalyst. Density functional theory calculations were used to examine the regioselectivity of arene C-H amination reactions on diversely substituted arenes. The calculations suggest a simple charge-controlled regioselectivity model that enables prediction of the major C(sp)-H amination product.

Mechanistic studies of Ni-catalyzed electrochemical homo-coupling reactions of aryl halides.

Ni-catalyzed electrochemical arylation is an attractive, emerging approach for molecular construction as it uses air-stable Ni catalysts and efficiently proceeds at room temperature. However, the homo-coupling of aryl halide substrates is one of the major side reactions. Herein, extensive experimental and computational studies were conducted to examine the mechanism of Ni-catalyzed electrochemical homo-coupling of aryl halides.

Understanding Formation and Roles of Ni Aryl Amido and Ni Aryl Amido Intermediates in Ni-Catalyzed Electrochemical Aryl Amination Reactions.

Ni-catalyzed electrochemical aryl amination (e-amination) is an attractive, emerging approach to building C-N bonds. Here, we report in-depth experimental and computational studies that examined the mechanism of Ni-catalyzed e-amination reactions. Key Ni-amine dibromide and Ni aryl amido intermediates were chemically synthesized and characterized.

The impact of COVID-19 and rapid policy exemptions expanding on access to medication for opioid use disorder (MOUD): A nationwide Veterans Health Administration cohort study.

Background: In March 2020, Veterans Health Administration (VHA) enacted policies to expand treatment for Veterans with opioid use disorder (OUD) during COVID-19. In this study, we evaluate whether COVID-19 and subsequent OUD treatment policies impacted receipt of therapy/counseling and medication for OUD (MOUD).

Methods: Using VHA's nationwide electronic health record data, we compared outcomes between a comparison cohort derived using data from prior to COVID-19 (October 2017-December 2019) and a pandemic-exposed cohort (January 2019-March 2021).

Preventing the need for revision surgery after penile plication reconstruction of Peyronie's deformities.

Background: The need for repeat penile plication (PP) for persistent penile deformity has previously been associated with (I) poor initial erectile response to intracavernosal injection (ICI), (II) an inadequate number of corrective sutures, and (III) a lack of sutures along the proximal shaft of the penis. We present our current experience with PP after implementing corrective measures to assess whether our need for revision surgery was reduced.

Methods: We performed a retrospective review of patients who underwent PP for Peyronie's disease (PD) between 2009-2018 and had a minimum follow-up of 6 months.

Comparison of 3.5 cm and transcorporal cuffs in high-risk artificial urinary sphincter populations.

Background: The transcorporal (TC) artificial urinary sphincter (AUS) has traditionally been utilized in high-risk patients with urethral atrophy or prior urethral erosion. The 3.5 cm AUS cuff has been developed for use in a similar population.

Urethral atrophy is now a rare cause for artificial urinary sphincter revision surgery in the contemporary 3.5 cm cuff era.

Background: Urethral atrophy has long been suggested as the leading cause of artificial urinary sphincter (AUS) revision. Since the introduction of the 3.5 cm AUS cuff in 2010, precise cuff sizing primarily has been suggested to reduce revisions due to urethral atrophy.

An update on oxidized regenerated cellulose (fibrillar™) in reducing postoperative corporal bleeding following inflatable penile prosthesis surgery.

Background: Scrotal hematoma formation is a dreaded complication of penile prosthesis surgery that increases patient pain and healthcare costs, as well the risk for eventual device infection and failure. The efficacy of hemostatic agents in reducing the incidence of scrotal hematoma development has not been extensively studied in urologic prosthetic surgery. In this paper we further evaluate our experience with oxidized regenerated cellulose (ORC; Surgicel Fibrillar™) as an adjunct to standard hemostatic practices in inflatable penile prosthesis (IPP) implantation.

Long-term sequelae of inflatable penile prosthesis: clinical characteristics of patients who develop distal cylinder tip extrusion.

Background: Impending distal cylinder tip extrusions (DCTE) make up approximately 5-33% of all inflatable penile prosthesis (IPP) reoperations. While there have been a few case reports of DCTE in patients with diabetes and trauma, the current literature regarding risk factors for DCTE is limited. In this study, we examined the long-term sequelae among a large cohort of IPP patients to identify clinical risk factors for impending DCTE.

Outpatient buccal mucosal graft urethroplasty outcomes are comparable to inpatient procedures.

Background: We sought to compare outcomes between inpatient and outpatient buccal mucosal graft (BMG) urethroplasty among a large tertiary referral center series.

Methods: A retrospective review of consecutive patients who underwent BMG urethroplasty between 2007 and 2018 was performed, including only first stage and one stage graft procedures. Patients were divided into inpatient and outpatient groups.

Age ≤40 is an independent predictor of anastomotic urethroplasty and successful repair of bulbar urethral strictures.

Background: Among men with bulbar strictures, we aimed to analyze stricture characteristics, repair type, and treatment success in younger versus older patient cohorts.

Methods: We retrospectively reviewed our single surgeon database with patients undergoing bulbar urethroplasty from 2007 to 2017. This population was then age-stratified into ≤40 and >40-year-old cohorts.

Long-term outcomes of anastomotic urethroplasty for radiation-induced strictures.

Purpose: To present our experience with excision and primary anastomosis (EPA) of radiation-induced urethral strictures (RUS) in men, including risk factors for stricture recurrence and long-term recurrence rates.

Methods: A retrospective review was performed of patients who underwent EPA of RUS between 2007 and 2018 at a single tertiary referral center. Demographic information, stricture location and length, complications, and stricture recurrence were analyzed.

Total Synthesis of Clavatadine B.

The first total synthesis of clavatadine B (), a natural product found to be a selective human blood coagulation factor XIa inhibitor, is described. A convergent approach that exemplifies the advantages of direct, early stage guanidinylation provided an immediate clavatadine B precursor, which was assembled in an efficient manner using known synthetic precursors of the structurally related natural product clavatadine A (). Global deprotection cleanly provided clavatadine B in only four steps from a known derivative of homogentisic acid lactone (longest linear sequence, 75% overall yield).

Strong correlation between standing cough test and 24-hour pad weights in the evaluation of male stress urinary incontinence.

Aims: We sought to compare in-office physical exam findings via standing cough test (SCT) versus 24-hour pad weights among men seeking treatment for postprostatectomy stress urinary incontinence (SUI).

Methods: A retrospective review of a single surgeon database of incontinence procedures was performed. Documentation of SUI severity (grades 0-4) was completed by SCT preoperatively utilizing the Male Stress Incontinence Grading Scale (MSIGS).

Synchronous Urethral Repair During Prosthetic Surgery: Safety of Planned and Damage Control Approaches Using Suprapubic Tube Urinary Diversion.

Background: Urethral injury during inflatable penile prosthesis (IPP) or artificial urinary sphincter (AUS) placement is rare, and traditionally most prosthetic surgeons abort prosthetic implantation when urethral repair is necessary.

Aim: To report our experience with synchronous urethroplasty (SU) as a planned or damage control surgery during urologic prosthetic surgery, to evaluate the safety and outcomes of the procedure.

Methods: A retrospective review of our IPP and AUS database was completed to identify patients who underwent an SU between 2007 and 2018.

Heterogeneous silicon photonics sensing for autonomous cars.

Heterogeneous silicon photonics is uniquely positioned to address the photonic sensing needs of upcoming autonomous cars and provide the necessary cost reduction for widespread deployment. This is because it allows for wafer-scale active/passive integration, including optical sources. We present our recent research and the development of interferometric optical gyroscopes and LiDAR sensors.

Does the Degree of Cystocele Predict De Novo Stress Urinary Incontinence After Prolapse Repair? Further Analysis of the Colpopexy and Urinary Reduction Efforts Trial.

Introduction: Cystoceles may cause urethral obstruction by altering the vesicourethral angle. Restoration of normal anatomy after pelvic organ prolapse (POP) repair can relieve this obstruction but may unmask stress urinary incontinence (SUI). The association between the severity of cystocele and developing de novo SUI after prolapse repair, however, is poorly understood.

Reflection sensitivity of 1.3 μm quantum dot lasers epitaxially grown on silicon.

We present measurements of relative intensity noise versus various levels of optical feedback for 1.3 μm quantum dot lasers epitaxially grown on silicon for the first time. A systematic comparison is made with heterogeneously integrated 1.