Catalytic, Spectroscopic, and Theoretical Studies of Fe4S4-Based Coordination Polymers as Heterogenous Coupled Proton-Electron Transfer Mediators for Electrocatalysis.

Iron-sulfur clusters play essential roles in biological systems, and thus synthetic [Fe4S4] clusters have been an area of active research. Recent studies have demonstrated that soluble [Fe4S4] clusters can serve as net H atom transfer mediators, improving the activity and selectivity of a homogeneous Mn CO2 reduction catalyst. Here, we demonstrate that incorporating these [Fe4S4] clusters into a coordination polymer enables heterogeneous H atom transfer from an electrode surface to a Mn complex dissolved in solution. A previously reported solution-processable Fe4S4-based coordination polymer was successfully deposited on the surfaces of different electrodes. The coated electrodes serve as H atom transfer mediators to a soluble Mn CO2 reduction catalyst displaying good product selectivity for formic acid. Furthermore, these electrodes are recyclable with a minimal decrease in activity after multiple catalytic cycles. The heterogenization of the mediator also enables the characterization of solution-phase and electrode surface species separately. Surface enhanced infrared absorption spectroscopy (SEIRAS) reveals spectroscopic signatures for an in situ generated active Mn-H species, providing a more complete mechanistic picture for this system. The active species, reaction mechanism, and the protonation sites on the [Fe4S4] clusters were further confirmed by density functional theory calculations. The observed H atom transfer reactivity of these coordination polymer-coated electrodes motivates additional applications of this composite material in reductive H atom transfer electrocatalysis.

Algorithmic Midline Approach to Perineal Urethrostomy is Associated With Long-term Success and High Patient Satisfaction.

OBJECTIVE: To assess surgical success and patient-reported outcomes of perineal urethrostomy via midline approach. MATERIALS AND METHODS: Charts of patients undergoing primary perineal urethrostomy between May 2008 and June 2022 were reviewed. Background characteristics were assessed; success was defined as freedom from re-intervention. Patient-reported outcome measures were assessed using a cross-sectional phone survey. Several validated questionnaires were used to assess lower urinary tract symptoms, quality of life, and erectile dysfunction. RESULTS: Among 1768 urethroplasties performed over the study period, 103 patients (5.8%) underwent midline perineal urethrostomy. Surgery was successful in 95.1% of cases (98/103); 5 patients (4.9%) required re-intervention at a median of 8.7 months. Post-operative complications occurred in 5.8% of cases (6/103) and were both mild and self-limited. Forty-nine patients (47.6%) were reached via phone survey at a median of 61 months post-operatively. Some questions were not answered by all patients. Most patients (42/49, 86%) were satisfied or very satisfied with surgical results, and 82% (40/49) reported an improvement in their overall health. Most patients (31/41, 76%) were unbothered by sitting to urinate. Although 20% of patients (10/49) reported post-operative urinary symptoms that interfered "a lot" with their daily life, only 3 (6%) of these patients reported dissatisfaction with the outcome. Regarding sexual function, 64% (27/42) reported indifference to or increased satisfaction with sexual encounters vs before surgery. The rate of de novo erectile dysfunction was 24% (12/49). CONCLUSION: The midline approach to perineal urethrostomy provides excellent, durable success rates with high levels of patient satisfaction.

Optilume drug-coated balloon for anterior urethral stricture: 2-year results of the ROBUST III trial.

Objective: The aim of this study is to report the updated 2-year results of the intervention arm of the ROBUST III randomized trial evaluating the safety and efficacy of the Optilume drug-coated balloon (DCB) versus standard endoscopic management of recurrent male anterior urethral stricture. Materials and Methods: Eligible patients included men with recurrent anterior urethral stricture ≤3 cm in length and ≤12Fr in diameter, International Prostate Symptom Score (IPSS) ≥11 and peak flow rate (Qmax) <15 mL/s. Patients were randomized to treatment with the Optilume DCB or standard-of-care endoscopic management. Primary efficacy endpoints measured at 2 years included freedom from re-intervention and changes in IPSS, Qmax and post-void residual (PVR). Secondary endpoint was impact on sexual function using the International Index of Erectile Function (IIEF). Primary safety endpoint was freedom from serious procedure- or device-related adverse events (AEs). Results: A total of 127 patients enrolled at 22 sites in the United States and Canada (48 randomized to standard-of-care dilation and 79 to DCB dilation). Seventy-five patients in the DCB arm entered the open-label phase after 6 months. Participants averaged 3.2 prior endoscopic interventions (range 2-10); most (89.9%) had bulbar strictures with an average stricture length of 1.63 cm (SD 0.76). Significant improvements in IPSS, average Qmax and PVR were maintained at 2 years. Freedom from repeat intervention was significantly higher in the Optilume DCB arm at 2 years versus the Control arm at 1 year (77.8% vs. 23.6%, p < 0.001). During the follow-up period, there were 15 treatment failures and two non-study-related deaths. Treatment-related AEs were rare and generally self-limited (haematuria, dysuria and urinary tract infection). Conclusion: The Optilume DCB shows sustained improvement in both objective and subjective voiding parameters at 2-year follow-up. Optilume appears to provide a safe and effective endoscopic treatment alternative for short recurrent anterior urethral strictures among men who wish to avoid or delay formal urethroplasty.

Electrocatalytic Semihydrogenation of Terminal Alkynes Using Ligand-Based Transfer of Protons and Electrons.

Alkyne semihydrogenation is a broadly important transformation in chemical synthesis. Here, we introduce an electrochemical method for the selective semihydrogenation of terminal alkynes using a dihydrazonopyrrole Ni complex capable of storing an H2 equivalent (2H+ + 2e-) on the ligand backbone. This method is chemoselective for the semihydrogenation of terminal alkynes over internal alkynes or alkenes. Mechanistic studies reveal that the transformation is concerted and Z-selective. Calculations support a ligand-based hydrogen-atom transfer pathway instead of a hydride mechanism, which is commonly invoked for transition metal hydrogenation catalysts. The synthesis of the proposed intermediates demonstrates that the catalytic mechanism proceeds through a reduced formal Ni(I) species. The high yields for terminal alkene products without over-reduction or oligomerization are among the best reported for any homogeneous catalyst. Furthermore, the metal-ligand cooperative hydrogen transfer enabled with this system directs the efficient flow of H atom equivalents toward alkyne reduction rather than hydrogen evolution, providing a blueprint for applying similar strategies toward a wide range of electroreductive transformations.

Current opinions on the management of prolonged ischemic priapism: does penoscrotal decompression outperform corporoglanular tunneling?

Prolonged ischemic priapism presents a treatment challenge given the difficulty in achieving detumescence and effects on sexual function. To evaluate current practice patterns, an open, web-based multi-institutional survey querying surgeons' experience with and perceived efficacy of tunneling maneuvers (corporoglanular tunneling and penoscrotal decompression), as well as impressions of erectile recovery, was administered to members of societies specializing in male genital surgery. Following distribution, 141 responses were received. Tunneling procedures were the favored first-line surgical intervention in the prolonged setting (99/139, 71.2% tunneling vs. 14/139, 10.1% implant, p < .001). Although respondents were more likely to have performed corporoglanular tunneling than penoscrotal decompression (124/138, 89.9% vs. 86/137, 62.8%, p < .001), penoscrotal decompression was perceived as more effective among those who had performed both (47.3% Very or Extremely Effective for penoscrotal decompression vs. 18.7% for corporoglanular tunneling; p < .001). Many respondents who had performed both tunneling procedures felt that most regained meaningful sexual function after either corporoglanular tunneling or penoscrotal decompression (33/75, 44.0% vs. 33/74, 44.6%, p = .942). While further patient-centered investigation is warranted, this study suggests that penoscrotal decompression may outperform corporoglanular tunneling for prolonged priapism, and that recovery of sexual function may be higher than previously thought after tunneling procedures.

Electrocatalytic C-H activation and fluorination using high-valent Cu.

In this issue of Chem Catalysis, Zhang and co-workers demonstrate the utility of electrochemical methods to enable catalytic turnover, employing high-valent Cu for C-H bond fluorination with selectivity for more hydridic bonds. Corresponding mechanistic investigations offer a rare catalytic example of oxidation driven C-H activation.

Needle visualization during ultrasound-guided puncture: image optimization.

Background: Obtaining an adequate image of the needle by ultrasound reduces complications resulting from punctures, increasing patient safety and reducing hospitalization costs. Objectives: To verify human perception in relation to number of pixels, while also identifying the best puncture angle and which needle should be used, and to evaluate whether there is a difference if needle visualization software is used. Methods: 20 images were analyzed by 103 students who classified them as being sufficient or insufficient and were compared with the quality observed using photoshop. We evaluated whether there were differences between puncture angles of less than 45º and more than 45º, between IV catheter and introducer needles, and between images obtained with and without visualization software. Results: There was a higher percentage of sufficient ratings for images those that had more than 60 pixels and when the puncture angle was less than 45º, with significant associations between students' evaluations and each of these groups (p < 0.001). The percentages of images classified as sufficient were higher for images in which a IV catheter was used and also higher for those using the needle visualization software, with significant associations between the results for students' classifications and each of these groups (p < 0.001). Conclusions: The human eye classifies an image as sufficient according to higher numbers of pixels. Images of punctures at angles smaller than 45º in relation to the surface, of punctures performed with a IV catheter, and when using specific visualization software are also better detected by the human eye.

Contexto: A obtenção de uma imagem adequada da agulha pelo ultrassom diminui complicações decorrentes de punções, trazendo segurança para os pacientes e diminuindo custos com hospitalização. Objetivos: Verificar a percepção do olho humano em relação aos pixels, identificar qual o melhor ângulo da punção e qual agulha deve ser utilizada e avaliar se há diferença com o uso de software de visualização de agulha. Métodos: Vinte imagens foram analisadas por 103 alunos, que as classificaram como sendo suficientes ou insuficientes, e comparadas com a qualidade observada pelo photoshop. Avaliou-se se havia diferença entre punções com menos de 45º e mais de 45º, entre cateter EV e agulha introdutora e entre imagens obtidas com e sem software de visualização. Resultados: Houve um percentual mais elevado de imagens suficientes entre aquelas que tinham mais de 60 pixels e quando o ângulo era menor que 45º, com associação significativa entre a classificação das avaliações pelos alunos e cada um desses grupos (p < 0,001). O percentual de imagens suficientes foi maior nas imagens realizadas com cateter EV e naquelas que utilizaram o software de visualização da agulha, ocorrendo associação significativa entre os resultados da classificação pelos alunos e cada um desses grupos (p < 0,001). Conclusões: O olho humano classifica a imagem como sendo suficiente de acordo com a maior quantidade de pixels. Imagens puncionadas com ângulos menores que 45º em relação à superfície, realizadas com cateter EV e utilizando software específico de visualização também são mais bem detectadas pelo olho humano.

Surgical Management of Male Stress Incontinence: Techniques, Indications, and Pearls for Success.

Purpose: Male stress urinary incontinence (SUI) has detrimental and long-lasting effects on patients. Management of this condition is an evolving field with multiple options for surgical treatment. We sought to review the pre-operative evaluation, intra-operative considerations, post-operative care, and future directions for treatment of male SUI. Methods: A literature review was performed using the PubMed platform to identify peer-reviewed, English-language articles published within the last 5 years pertaining to management of male stress urinary incontinence with an emphasis on devices currently on the market in the United States including the artificial urinary sphincter (AUS), male urethral slings, and the ProACTTM system. Patient selection criteria, success rates, and complications were compared between the studies. Results: Twenty articles were included in the final contemporary review. Pre-operative workup most commonly included demonstration of incontinence, PPD, and cystoscopy. Definition of success varied by study; the most common definition used was social continence (0-1 pads per day). Reported rates of success were higher for the AUS than for male urethral slings (73-93% vs 70-90%, respectively). Complications for these procedures include urinary retention, erosions, infections, and device malfunction. Newer treatment options including adjustable balloon systems and adjustable slings show promise but lack long-term follow-up. Conclusion: Patient selection remains the primary consideration for surgical decision-making for management of male SUI. The AUS continues to be the gold standard for moderate-to-severe male SUI but comes with inherent risk of need for revision. Male slings may be a superior option for appropriately selected men with mild incontinence but are inferior to the AUS for moderate and severe incontinence. Ongoing research will shed light on long-term results for newer options such as the ProACT and REMEEX systems.

Mechanical indications for inflatable penile prosthesis revision: analysis and implications for revision surgery.

BACKGROUND: Despite technical advancements, inflatable penile prostheses (IPPs) are inherently at risk of mechanical failure given their nature as hydraulic devices. AIM: To characterize IPP component failure location at the time of device revision and stratify by manufacturer: American Medical Systems (Boston Scientific [BSCI]) and Coloplast (CP). METHODS: A retrospective review of penile prosthesis cases from July 2007 to May 2022 was conducted, identifying men who underwent revision surgery. Cases were excluded if documentation did not denote the cause of failure or the manufacturer. Mechanical indications for surgery were categorized by location (eg, tubing, cylinder, or reservoir leak; pump malfunction). Nonmechanical revisions were excluded (component herniation, erosion, or crossover). Categorical variables were assessed with Fisher exact or chi-square analysis; Student t-test and Mann-Whitney U test were used for continuous variables. OUTCOMES: Primary outcomes included specific location of IPP mechanical failure among BSCI and CP devices and time to mechanical failure. RESULTS: We identified 276 revision procedures, 68 of which met inclusion criteria (46 BSCI and 22 CP). Revised CP devices were longer than BSCI devices (median cylinder length, 20 vs 18 cm; P < .001). Log-rank analysis revealed a similar time to mechanical failure between brands (P = .096). CP devices failed most often due to tubing fracture (19/22, 83%). BSCI devices had no predominant site of failure. Between manufacturers, tubing failure was more common in CP devices (19/22 vs 15/46 for BSCI, P < .001), while cylinder failure was more common among BSCI devices (10/46 vs 0/22 for CP, P = .026). CLINICAL IMPLICATIONS: The distribution of mechanical failure is significantly different between BSCI and CP devices; this has implications regarding the approach to revision surgery. STRENGTHS AND LIMITATIONS: This is the first study to directly compare when and where mechanical failure occurs in IPPs and to compare the 2 main manufacturers head-to-head. This study would be strengthened by being repeated in a multi-institutional fashion to provide more robust and objective evaluation. CONCLUSION: CP devices commonly failed at the tubing and rarely elsewhere, while BSCI devices showed no predominant failure site; these findings may inform decision making regarding revision surgery.

Needle visualization during ultrasound-guided puncture: image optimization / Visualização da agulha durante punção guiada por ultrassom: otimização de imagem

Abstract Background Obtaining an adequate image of the needle by ultrasound reduces complications resulting from punctures, increasing patient safety and reducing hospitalization costs. Objectives To verify human perception in relation to number of pixels, while also identifying the best puncture angle and which needle should be used, and to evaluate whether there is a difference if needle visualization software is used. Methods 20 images were analyzed by 103 students who classified them as being sufficient or insufficient and were compared with the quality observed using photoshop. We evaluated whether there were differences between puncture angles of less than 45º and more than 45º, between IV catheter and introducer needles, and between images obtained with and without visualization software. Results There was a higher percentage of sufficient ratings for images those that had more than 60 pixels and when the puncture angle was less than 45º, with significant associations between students' evaluations and each of these groups (p < 0.001). The percentages of images classified as sufficient were higher for images in which a IV catheter was used and also higher for those using the needle visualization software, with significant associations between the results for students' classifications and each of these groups (p < 0.001). Conclusions The human eye classifies an image as sufficient according to higher numbers of pixels. Images of punctures at angles smaller than 45º in relation to the surface, of punctures performed with a IV catheter, and when using specific visualization software are also better detected by the human eye.

Resumo Contexto A obtenção de uma imagem adequada da agulha pelo ultrassom diminui complicações decorrentes de punções, trazendo segurança para os pacientes e diminuindo custos com hospitalização. Objetivos Verificar a percepção do olho humano em relação aos pixels, identificar qual o melhor ângulo da punção e qual agulha deve ser utilizada e avaliar se há diferença com o uso de software de visualização de agulha. Métodos Vinte imagens foram analisadas por 103 alunos, que as classificaram como sendo suficientes ou insuficientes, e comparadas com a qualidade observada pelo photoshop. Avaliou-se se havia diferença entre punções com menos de 45º e mais de 45º, entre cateter EV e agulha introdutora e entre imagens obtidas com e sem software de visualização. Resultados Houve um percentual mais elevado de imagens suficientes entre aquelas que tinham mais de 60 pixels e quando o ângulo era menor que 45º, com associação significativa entre a classificação das avaliações pelos alunos e cada um desses grupos (p < 0,001). O percentual de imagens suficientes foi maior nas imagens realizadas com cateter EV e naquelas que utilizaram o software de visualização da agulha, ocorrendo associação significativa entre os resultados da classificação pelos alunos e cada um desses grupos (p < 0,001). Conclusões O olho humano classifica a imagem como sendo suficiente de acordo com a maior quantidade de pixels. Imagens puncionadas com ângulos menores que 45º em relação à superfície, realizadas com cateter EV e utilizando software específico de visualização também são mais bem detectadas pelo olho humano.

Dynamic properties of a self-replicating peptide network with inhibition.

In this paper, we report an open system consisting of three self-replicating peptides, in which peptide 1 inhibits the duplex template of peptide 2, peptide 2 inhibits duplex 3, and peptide 3 inhibits duplex 1 to complete the negative feedback loop. This interacting chemical network yields oscillations in the concentrations of all species over time and establishes a possible mechanism for pre-biotic chemical systems organization. The first focus of our analysis is the effect of altering rates of duplex formation and inhibition on oscillations. We then examine the autocatalytic rate constant in the symmetric and asymmetric cases.

Generation and Aerobic Oxidative Catalysis of a Cu(II) Superoxo Complex Supported by a Redox-Active Ligand.

Cu systems feature prominently in aerobic oxidative catalysis in both biology and synthetic chemistry. Metal ligand cooperativity is a common theme in both areas as exemplified by galactose oxidase and by aminoxyl radicals in alcohol oxidations. This has motivated investigations into the aerobic chemistry of Cu and specifically the isolation and study of Cu-superoxo species that are invoked as key catalytic intermediates. While several examples of complexes that model biologically relevant Cu(II) superoxo intermediates have been reported, they are not typically competent aerobic catalysts. Here, we report a new Cu complex of the redox-active ligand tBu,TolDHP (2,5-bis((2-t-butylhydrazono)(p-tolyl)methyl)-pyrrole) that activates O2 to generate a catalytically active Cu(II)-superoxo complex via ligand-based electron transfer. Characterization using ultraviolet (UV)-visible spectroscopy, Raman isotope labeling studies, and Cu extended X-ray absorption fine structure (EXAFS) analysis confirms the assignment of an end-on κ1 superoxo complex. This Cu-O2 complex engages in a range of aerobic catalytic oxidations with substrates including alcohols and aldehydes. These results demonstrate that bioinspired Cu systems can not only model important bioinorganic intermediates but can also mediate and provide mechanistic insight into aerobic oxidative transformations.

Self-collected nasopharyngeal swab and molecular test using pool testing as strategies to detect severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2): feasibility in medical students at the Universidade Federal de Minas Gerais, Brazil, 2021. / Autocoleta de swab nasofaríngeo e teste molecular em pool testing como estratégias para detecção de coronavírus da síndrome respiratória aguda grave 2 (SARS-CoV-2): viabilidade em estudantes de medicina da Universidade Federal de Minas Gerais, 2021.

OBJECTIVE: To show the feasibility of the combined use of self-collected nasopharyngeal swab and pool testing to detect SARS-CoV-2 in epidemiological surveys. METHODS: This experience included a sample of 154 students at the Universidade Federal de Minas Gerais, who performed self-collected nasopharyngeal swab in individual cabins and without supervision. The molecular test was performed using the pool testing technique. RESULTS: It took each person 5 minutes to collect the sample. An analysis was performed to detect endogenous RNA in 40 samples. The results showed that there were no failures resulting from self-collection. None of the pools detected the presence of viral RNA. The cost of molecular testing (RT-PCR), by pool testing, with samples obtained by self-collection was about ten times lower than the usual methods. CONCLUSION: The strategies that were investigated proved to be economically feasible and valid for the research on SARS-CoV-2 in epidemiological surveys.

Evaluation of ultrasound measurements of abdominal fat for the prediction of gestational diabetes in the first and second trimesters of pregnancy.

OBJECTIVE: To evaluate whether ultrasound abdominal fat measurements in the first and second trimesters can predict adverse gestational outcomes, particularly gestational diabetes mellitus (GDM), and identify early patients at higher risk for complications. METHODS: A prospective cohort study of 126 pregnant women at 11-14 and 20-24 weeks of gestation with normal fasting glucose levels during early pregnancy. From 126 participants with complete data, 13.5% were diagnosed with GDM, based on the cutoffs established for the peripherical blood glucose. Subcutaneous, visceral, and maximum preperitoneal abdominal fat were measured using ultrasound techniques. GDM status was determined by oral glucose tolerance test (OGTT) with 75 g glucose overload, and the following values were considered abnormal: fasting glucose ≥92 mg/dl and/or 1 h after overload ≥180 mg/dl and/or 2 h after overload ≥153 mg/dl. The receiver operator characteristic (ROC) curve was used to determine the optimal threshold to predict GDM. RESULTS: Maximum preperitoneal fat measurement was predictive of GDM, and subcutaneous and visceral abdominal fat measurements did not show significant differences in the prediction of GDM. According to the ROC curve, a threshold of 45.25 mm of preperitoneal fat was identified as the optimal cutoff point, with 87% sensitivity and 41% specificity to predict GDM. The raw and adjusted odds ratios for age and pre-pregnancy body mass index were 0.730 (95% confidence interval [CI], 0.561-0.900) and 0.777 (95% CI, 0.623-0.931), respectively. CONCLUSION: The use of a 45.25 mm threshold for maximum preperitoneal fat, measured by ultrasound to predict the risk of GDM, appears to be a feasible, inexpensive, and practical alternative to incorporate into clinical practice during the first trimester of pregnancy.

Self-collection of nasopharyngeal swab and molecular test in pool testing as strategies for detecting Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2): feasibility in medical students at the Universidade Federal de Minas Gerais, 2021 / Autocollección de swabs nasofaríngeos y pruebas moleculares en pool testing como estrategias para la detección del Coronavirus Síndrome Respiratorio Agudo Severo 2 (SARS-CoV-2): viabilidad en estudiantes de medicina de la Universidade Federal de Minas Gerais, 2021 / Autocoleta de swab nasofaríngeo e teste molecular em pool testing como estratégias para detecção de coronavírus da síndrome respiratória aguda grave 2 (SARS-CoV-2): viabilidade em estudantes de medicina da Universidade Federal de Minas Gerais, 2021

Objective: To show the feasibility of using combined nasopharyngeal swab auto-collection and pool testing to detect SARS-CoV-2 in epidemiological surveys. Methods: The study involved a sample of 154 students from the Universidade Federal de Minas Gerais, who performed the self-collection of the nasopharyngeal swab in individual booths without supervision. Molecular testing was performed using the pool testing technique. Results: Obtaining samples lasted about 5 minutes each. Analysis 6 was performed to detect endogenous RNA in 40 samples, and the results indicated that no failures resulted from self-collection. None of the pools detected the presence of viral RNA. The cost of performing the molecular test (RT-PCR) by pool testing with samples obtained by self-collection was about 10 times lower than with the usual methods. Conclusion: The investigated strategies showed to be economically feasible and valid for the research of SARS-CoV-2 in epidemiological surveys.

Objetivo: Demostrar la viabilidad de utilizar el uso combinado de la autocollección de swabs nasofaríngeos y pool testing para la detección del SARS-CoV2 en encuestas epidemiológicas. Métodos: El estudio involucró a una muestra de 154 estudiantes de la Universidade Federal de Minas Gerais, quienes realizaron la autocolección del hisopo nasofaríngeo en cabinas individuales sin supervision. La prueba molecular se realizó utilizando la técnica de prueba de grupo. Resultados: La obtención de muestras duró unos 5 minutos por persona. Se realizó un análisis para detectar RNA endógeno en 40 muestras y los resultados indicaron que no hubo fallas derivadas de la autocolección. Ninguno de los grupos detectó la presencia de RNA viral. El costo de realizar una prueba molecular (RT-PCR) por pool con muestras obtenidas por auto-recolección fue aproximadamente 10 veces menor que con los métodos habituales. Conclusión: Las estrategias investigadas demonstraram ser económicamente viables y válidas para la investigación del SARS-CoV-2 en encuestas epidemiológicas.

Objetivo: Demonstrar a viabilidade da utilização combinada da autocoleta de swab nasofaríngeo e pool testing para detecção do SARS-CoV-2 em inquéritos epidemiológicos. Métodos: O estudo envolveu amostra de 154 estudantes da Universidade Federal de Minas Gerais, que realizaram a autocoleta do swab nasofaríngeo em cabines individuais e sem supervisão. O teste molecular foi realizado utilizando-se a técnica de pool testing. Resultados: A obtenção de amostras durou cerca de 5 minutos por pessoa. Realizou-se análise para detecção de RNA endógeno em 40 amostras e os resultados indicaram que não houve falhas decorrentes da autocoleta. Nenhum dos pools detectou presença de RNA viral. O custo da realização do teste molecular (RT-PCR) por pool testing com amostras obtidas por autocoleta foi cerca de dez vezes menor do que nos métodos habituais. Conclusão: As estratégias investigadas mostraram-se economicamente viáveis e válidas para a pesquisa de SARS-CoV-2 em inquéritos epidemiológicos.

Autocoleta de swab nasofaríngeo e teste molecular em pool testing como estratégias para detecção de coronavírus da síndrome respiratória aguda grave 2 (SARS-CoV-2): viabilidade em estudantes de medicina da Universidade Federal de Minas Gerais, 2021 / Autocolección de hiopados nasofaríngeos y pruebas moleculares en pool testing como estrategias para la detección del Coronavirus Síndrome Respiratorio Agudo Severo 2 (SARS-CoV-2): viabilidad en estudiantes de medicina de la Universidad Federal de Minas Gerais, Brasil, 2021 / Self-collected nasopharyngeal swab and molecular test using pool testing as strategies to detect severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2): feasibility in medical students at the Universidade Federal de Minas Gerais, Brazil, 2021

Objetivo: Demonstrar a viabilidade da utilização combinada da autocoleta de swab nasofaríngeo e pool testing para detecção do SARS-CoV-2 em inquéritos epidemiológicos. Métodos: A experiência envolveu amostra de 154 estudantes da Universidade Federal de Minas Gerais, que realizaram a autocoleta do swab nasofaríngeo em cabines individuais e sem supervisão. O teste molecular foi realizado utilizando-se a técnica de pool testing. Resultados: A obtenção de amostras durou cerca de 5 minutos por pessoa. Realizou-se análise para detecção de RNA endógeno em 40 amostras e os resultados indicaram que não houve falhas decorrentes da autocoleta. Nenhum dos pools detectou presença de RNA viral. O custo da realização do teste molecular (RT-PCR) por pool testing com amostras obtidas por autocoleta foi cerca de dez vezes menor do que nos métodos habituais. Conclusão: As estratégias investigadas mostraram-se economicamente viáveis e válidas para a pesquisa de SARS-CoV-2 em inquéritos epidemiológicos.

Objetivo: Demostrar la viabilidad del uso combinado de la auto recolección de swabs nasofaríngeos y tests por agrupamiento (pool testing) para la detección del SARS-CoV-2 en encuestas epidemiológicas. Métodos: La prueba involucró a una muestra de 154 estudiantes de la Universidade Federal de Minas Gerais, quienes realizaron e autorecolectado del hisopo nasofaríngeo en cabinas individuales sin supervisión. La prueba molecular se realizó utilizando la técnica de prueba de grupo. Resultados: La obtención de muestras duró unos 5 minutos por persona. Se realizó un análisis para detectar ARN endógeno en 40 muestras y los resultados indicaron que no hubo fallas derivadas de la autorecolección. Ninguno de los grupos detectó la presencia de ARN viral. El costo de realizar una prueba molecular (RT-PCR) por pool con muestras obtenidas por auto-recolección fue aproximadamente 10 veces menor que con los métodos habituales. Conclusión: Las estrategias investigadas demostraron ser económicamente viables y válidas para la investigación del SARS-CoV-2 en encuestas epidemiológicas.

Objective: To show the feasibility of the combined use of self-collected nasopharyngeal swab and pool testing to detect SARS-CoV-2 in epidemiological surveys. Methods: This experience included a sample of 154 students at the Universidade Federal de Minas Gerais, who performed self-collected nasopharyngeal swab in individual cabins and without supervision. The molecular test was performed using the pool testing technique. Results: It took each person 5 minutes to collect the sample. An analysis was performed to detect endogenous RNA in 40 samples. The results showed that there were no failures resulting from self-collection. None of the pools detected the presence of viral RNA. The cost of molecular testing (RT-PCR), by pool testing, with samples obtained by self-collection was about ten times lower than the usual methods. Conclusion: The strategies that were investigated proved to be economically feasible and valid for the research on SARS-CoV-2 in epidemiological surveys.

Distribution of galling insects and their parasitoids on Caryocar brasiliense tree crowns

Abstract Caryocar brasiliense Camb. (Malpighiales: Caryocaraceae) is widely distributed in the Brazilian savanna and its fruits are used by humans for food, production of cosmetics, lubricants, and in the pharmaceutical industry. This plant is damaged by galling insects. Number of these galling insects and their parasitoids was recorded, in the field (galls) and in the laboratory (adults emerged from the galls), from three C. brasiliense crown heights, during three years. Numbers of adults of Eurytoma sp. (Hymenoptera: Eurytomidae), galling insect (younger attack) and Sycophila sp. (Hymenoptera: Eurytomidae) (a parasitoid of Eurytoma sp.), were greater on the apical parts of C. brasiliense tree crowns. Numbers and groups of Eurytoma sp. globoid galls (older attack) were higher in the median and basal crown parts. The numbers of Eurytoma sp. galls were higher on apical part of C. brasiliense tree crown and also of their parasitoids.

Resumo Caryocar brasiliense Camb. (Malpighiales: Caryocaraceae) é, amplamente, distribuída no cerrado brasileiro e seus frutos são utilizados para alimentação humana, produção de cosméticos, lubrificantes e na indústria farmacêutica, no entanto, é danificada por insetos galhadores. O número de insetos galhadores e seus parasitoides foram avaliados, em campo (galhas) e em laboratório (emergência de adultos das galhas), em três alturas do dossel de C. brasiliense, durante três anos. Os números de adultos Eurytoma sp. (Hymenoptera: Eurytomidae), inseto galhador (galhas novas) e de Sycophila sp. (Hymenoptera: Eurytomidae), parasitoide de Eurytoma sp., foram maiores na parte apical do dossel da copa de árvores de C. brasiliense. A quantidade de galhas globoides de Eurytoma sp., isoladas ou em grupo (galhas velhas), foi maior na parte mediana e basal da copa. Os números de adultos do galhador Eurytoma sp. e de seus parasitoides, que os seguem, foram maiores na parte apical da copa de árvores de C. brasiliense.

Distribution of galling insects and their parasitoids on Caryocar brasiliense tree crowns / Distribuição de insetos galhadores e seus parasitoides em copas de pequizeiros (Caryocar brasiliense)

Caryocar brasiliense Camb. (Malpighiales: Caryocaraceae) is widely distributed in the Brazilian savanna and its fruits are used by humans for food, production of cosmetics, lubricants, and in the pharmaceutical industry. This plant is damaged by galling insects. Number of these galling insects and their parasitoids was recorded, in the field (galls) and in the laboratory (adults emerged from the galls), from three C. brasiliense crown heights, during three years. Numbers of adults of Eurytoma sp. (Hymenoptera: Eurytomidae), galling insect (younger attack) and Sycophila sp. (Hymenoptera: Eurytomidae) (a parasitoid of Eurytoma sp.), were greater on the apical parts of C. brasiliense tree crowns. Numbers and groups of Eurytoma sp. globoid galls (older attack) were higher in the median and basal crown parts. The numbers of Eurytoma sp. galls were higher on apical part of C. brasiliense tree crown and also of their parasitoids.

Caryocar brasiliense Camb. (Malpighiales: Caryocaraceae) é, amplamente, distribuída no cerrado brasileiro e seus frutos são utilizados para alimentação humana, produção de cosméticos, lubrificantes e na indústria farmacêutica, no entanto, é danificada por insetos galhadores. O número de insetos galhadores e seus parasitoides foram avaliados, em campo (galhas) e em laboratório (emergência de adultos das galhas), em três alturas do dossel de C. brasiliense, durante três anos. Os números de adultos Eurytoma sp. (Hymenoptera: Eurytomidae), inseto galhador (galhas novas) e de Sycophila sp. (Hymenoptera: Eurytomidae), parasitoide de Eurytoma sp., foram maiores na parte apical do dossel da copa de árvores de C. brasiliense. A quantidade de galhas globoides de Eurytoma sp., isoladas ou em grupo (galhas velhas), foi maior na parte mediana e basal da copa. Os números de adultos do galhador Eurytoma sp. e de seus parasitoides, que os seguem, foram maiores na parte apical da copa de árvores de C. brasiliense.

Direct Aerobic Generation of a Ferric Hydroperoxo Intermediate Via a Preorganized Secondary Coordination Sphere.

Enzymes exert control over the reactivity of metal centers with precise tuning of the secondary coordination sphere of active sites. One particularly elegant illustration of this principle is in the controlled delivery of proton and electron equivalents in order to activate abundant but kinetically inert oxidants such as O2 for oxidative chemistry. Chemists have drawn inspiration from biology in designing molecular systems where the secondary coordination sphere can shuttle protons or electrons to substrates. However, a biomimetic activation of O2 requires the transfer of both protons and electrons, and molecular systems where ancillary ligands are designed to provide both of these equivalents are comparatively rare. Here, we report the use of a dihydrazonopyrrole (DHP) ligand complexed to Fe to perform exactly such a biomimetic activation of O2. In the presence of O2, this complex directly generates a high spin Fe(III)-hydroperoxo intermediate which features a DHP• ligand radical via ligand-based transfer of an H atom. This system displays oxidative reactivity and ultimately releases hydrogen peroxide, providing insight on how secondary coordination sphere interactions influence the evolution of oxidizing intermediates in Fe-mediated aerobic oxidations.

Penile Extra-Tunical Graft Reconstruction of Peyronie's Disease Concavity Deformities.

OBJECTIVES: To report our initial experience with the extra-tunical grafting (ETG) procedure. This procedure was recently introduced by UCSF investigators as a tunica-sparing technique for management of penile concavity deformities. METHODS: We retrospectively reviewed records of patients who underwent ETG at our tertiary-care referral center between 2017 - 2020.  A collagen graft made from bovine pericardium (Lyoplant) was placed overlying the defect without violating the tunica albuginea or mobilizing the neurovascular bundle. The stretched penile length (SPL) and circumference at the location of deformity were measured intra-operatively. Patient reported outcomes were evaluated by an anonymous 10-question online survey. RESULTS: 19 men underwent ETG with a median follow-up of 59 (IQR: 24 - 708) days. ETG was performed via either a window (15/19, 78%) or a de-gloving (4/19, 21%) incision with concomitant penile plication performed in 16/19 (84%) patients. Penile circumference increased by an average of 1.4 cm + 0.5 (P = 0.03) at the location of deformity, while pre- and post-operative SPL were similar (14.0 + 1.4 vs 14.0 + 1.3 cm, P = 0.95). Overall patient satisfaction was reported by 13/15 (86%) patients. Twelve out of 15 (80%) patients reported concavity deformity to be "improved", with 73% reporting "much better". Among 8 patients with follow up greater than six months, graft palpability was reported in 4/8 (50%) patients but was not bothersome. CONCLUSION: The ETG procedure appears to be safe and effective for the treatment of penile concavity deformities.  Patient outcomes and satisfaction are favorable at intermediate follow up.