Octahedral Tantalum Bromide Clusters as Catalysts for Light-Driven Hydrogen Evolution.

The development of an efficient hydrogen generation strategy from aqueous protons using sunlight is a current challenge aimed at the production of low-cost, easily accessible, renewable molecular hydrogen. For achieving this goal, non-noble metal containing and highly active catalysts for the hydrogen evolution reaction (HER) are desirable. Octahedral tantalum halide clusters {Ta6(µ-X)12}2+ (X = halogen) represent an emerging class of such HER photocatalysts. In this work, the photocatalytic properties of octahedral aqua tantalum bromide clusters toward HER and in acid and homogeneous aqueous conditions were investigated. The [{Ta6Bri12}Bra2(H2O)a4]·4H2O (i = inner ligand; a = apical ligand) compound is revealed to be an efficient precatalyst in acid (HBr) conditions and with methanol as the sacrificial agent. A response surface methodology (RSM) study was applied for the optimization of the HER conditions, considering the concentrations of both additives (methanol and HBr) as independent variables. An optimal H2 production of 11 mmol·g-1 (TON = 25) was achieved, which displays exceptional catalytic properties compared to regular Ta-based materials. The aqua tantalum bromide clusters assist in the photocatalytic hydrogen generation in agreement with energy-conversion schemes, and plausible active catalytic species and a reaction mechanism were proposed from computational and experimental perspectives.

Case report: Metastatic urothelial cancer with an exceptional response to immunotherapy and comprehensive understanding of the tumor and the tumor microenvironment.

Although immune checkpoint inhibitors (ICIs) are increasingly used as second-line treatments for urothelial cancer (UC), only a small proportion of patients respond. Therefore, understanding the mechanisms of response to ICIs is critical to improve clinical outcomes for UC patients. The tumor microenvironment (TME) is recognized as a key player in tumor progression and the response to certain anti-cancer treatments. This study aims to investigate the mechanism of response using integrated genomic and transcriptomic profiling of a UC patient who was part of the KEYNOTE-045 trial and showed an exceptional response to pembrolizumab. Diagnosed in 2014 and receiving first-line chemotherapy without success, the patient took part in the KEYNOTE-045 trial for 2 years. She showed dramatic improvement and has now been free of disease for over 6 years. Recently described by Bagaev et al., the Molecular Functional (MF) Portrait was utilized to dissect genomic and transcriptomic features of the patient's tumor and TME. The patient's tumor was characterized as Immune Desert, which is suggestive of a non-inflamed microenvironment. Integrated whole-exome sequencing (WES) and RNA sequencing (RNA-seq) analysis identified an ATM mutation and high TMB level (33.9 mut/mb), which are both positive biomarkers for ICI response. Analysis further revealed the presence of the APOBEC complex, indicating the potential for use of APOBEC signatures as predictive biomarkers for immunotherapy response. Overall, comprehensive characterization of the patient's tumor and TME with the MF Portrait revealed important insights that could potentially be hypothesis generating to identify clinically useful biomarkers and improve treatment for UC patients.

Transoral Endoscopic Thyroidectomy Vestibular Approach (TOETVA) learning curve: a regression analysis of complication rates and severity.

BACKGROUND: Transoral Endoscopic Thyroidectomy Vestibular Approach (TOETVA) is a natural orifice transluminal endoscopic surgery that offers a truly scarless approach to thyroidectomy. Introduced in 2008, there is a growing body of literature establishing it as a safe endoscopic approach for thyroid procedures. While it is not yet widely practiced, it is quickly growing in popularity. As more surgeons begin to add this technique to their repertoire the question of the learning curve has to be examined. METHODS: Case series from the initial TOETVA operations of four surgeons at three different hospitals were examined. Binomial and ordinal logistic regression were used to characterize the changes in complication rate and severity as they related to case number in the series. Statistics were performed in Minitab and SAS. RESULTS: Each surgeon performed between 23 and 40 TOETVA operations for a total of 130 cases. Binary logistic regression shows a negative relationship between case number and complication rate (P < 0.001, Odds Ratio: 0.91). Ordinal logistic regression shows a negative relationship between case number and complication severity (P < 0.001, Odds Ratio: 1.07). The maximum slope of improvement of complication rate occurred at case number 12. CONCLUSION: The most significant decrease in complications for TOETVA occurs at case 12. As case number progresses, there is a significant decrease in both the risk of a complication occurring and of the severity of that complication. These results support the previously published data on TOETVA learning curve based on operative time.

Multi-isotopic and morphometric evidence for the migration of farmers leading up to the Inka conquest of the southern Andes.

We present isotopic and morphometric evidence suggesting the migration of farmers in the southern Andes in the period AD 1270-1420, leading up to the Inka conquest occurring ~ AD 1400. This is based on the interdisciplinary study of human remains from archaeological cemeteries in the Andean Uspallata Valley (Argentina), located in the southern frontier of the Inka Empire. The studied samples span AD 800-1500, encompassing the highly dynamic Late Intermediate Period and culminating with the imperial expansion. Our research combines a macro-regional study of human paleomobility and migration based on a new strontium isoscape across the Andes that allows identifying locals and migrants, a geometric morphometric analysis of cranio-facial morphology suggesting separate ancestral lineages, and a paleodietary reconstruction based on stable isotopes showing that the migrants had diets exceptionally high in C4 plants and largely based on maize agriculture. Significantly, this migration influx occurred during a period of regional demographic increase and would have been part of a widespread period of change in settlement patterns and population movements that preceded the Inka expansion. These processes increased local social diversity and may have been subsequently utilized by the Inka to channel interaction with the local societies.

Distribution, habitat suitability, conservation state and natural history of endangered salamander Bolitoglossa pandi.

BACKGROUND: Pandi's mushroom-tongue salamander (Bolitoglossa pandi) is one of the threatened amphibians in South America, as well as a flagship species for the Colombian conservation agenda. This species is endemic to the Andean cloud forests of the western slope of the Cordillera Oriental of Colombia, occurring only in the department of Cundinamarca within a narrow elevational range. At night, B. pandi can be seen perching on the upper side of leaves at heights ranging from ground level to 2.5 m. During the day, it can be found under leaf litter or cover objects. Few studies have provided relevant information that can help the Colombian government to formulate lines of action for the conservation of this species; consequently, its threat assessments so far have been based on very limited information. METHODS: We conducted surveys for salamanders in four municipalities of Cundinamarca, Colombia, using two approaches: visual encounter surveys (Guaduas and Villeta) and the basic sampling protocol for single-species occupancy modeling (Supatá and Venecia). Multivariate analyses were employed to explore the correlation between habitat structure and natural history traits, abundance, and detection/non-detection of B. pandi. We evaluated the B. pandi activity pattern through kernel density curves for each sampling occasion and explored the variability of salamander abundance during their activity period by performing a nested ANOVA. RESULTS: We report the discovery of two new populations of B. pandi, which represent the most northwestern records known. A significant correlation between body length, body mass, and habitat structure was observed. Multivariate analyses indicated that leaf litter depth, mean temperature, percent vegetation cover, and altitude were the habitat variables that together explained 60.3% of the B. pandi abundance variability, as well as the main determinants of its optimal habitat. Bolitoglossa pandi exhibits an activity pattern characterized by two main activity peaks, in which niche time-partitioning was observed. Across the surveyed area, we found a healthy, stable, highly dense population of B. pandi (>1,300 individuals), with seasonal variability between development stages. DISCUSSION: Given the high habitat specificity of B. pandi, the species is highly vulnerable to local changes. Thus, we recommend that B. pandi be retained as Endangered (EN) on the IUCN Red List, based on the IUCN Criterion B, given its restricted extent of occurrence (ca. 2,500 km2) and the ongoing threats from agriculture, cattle ranching, logging, and urban development, which continue to reduce its suitable habitat.

Intrathoracic Sleeve Migrations After Sleeve Gastrectomy: A Compilation of Case Reports.

Background: Laparoscopic sleeve gastrectomy (LSG) is the most commonly performed bariatric procedure in the United States. Postoperative migration of the stomach into the chest is a rare complication of this procedure. In this study, we present a compilation of acute and chronic intrathoracic sleeve migrations (ITSMs) after LSG and present possible underlying mechanisms of this complication, as described in the literature. Methods: We retrospectively reviewed the preoperative, intraoperative, and postoperative course of patients who had an ITSM after LSG between 2011 and 2019. Results: Two patients presented with this complication in the acute setting, whereas 3 patients developed ITSM as a chronic issue years after the primary procedure. All 5 were female patients, with a mean age and body mass index of 55.6 ± 9.5 (years) and 37.8 ± 2.9 kg/m2, respectively. None of the cases had a hiatal hernia repair during the initial operation. All cases were completed laparoscopically with reduction of the migrated sleeve into the abdomen and primary hiatal hernia repair. One case required a return to the operating room for an acute reherniation. Conclusion: In this article, we report a compilation of cases of ITSMs after LSG with distinct clinical features that highlight the diversity of possible reasons and risk factors for its development.

Transoral Endoscopic Thyroidectomy Vestibular Approach: A Single-institution Experience of the First 50 Cases.

Background. Transoral endoscopic thyroidectomy vestibular approach (TOETVA) has evolved from a novel procedure to a cosmetically appealing alternative to the traditional open thyroidectomy. TOETVA is limited to only high-volume centers with the hope to expand and demonstrate the safety, reproducibility, and application for the correct patient with thyroid disease. We present our experience with the first 50 TOETVA procedures performed at our institution. Methods. From September 2016 to June 2018, we performed 50 transoral endoscopic thyroidectomies via the vestibular approach for a variety of thyroid pathologies. Outcomes were analyzed from a prospectively maintained database. Patients were treated for a different range of thyroid pathologies. Results. A total of 12 (24%) patients underwent total thyroidectomy, whereas 38 (76%) patients underwent a subtotal thyroidectomy or thyroid lobectomy. The mean surgical time was 149 ± 40.0 (90-256) minutes for lobectomy and 217.6 ± 33.3 (175-276) minutes for total thyroidectomy. Of our 50 patients, 16 (32%) had postoperative transient lower lip numbness with an average time to recovery of 23.8 (.43-48) weeks, with 1 (2%) patient having persistent, but improving, lower lip numbness beyond the 6-month follow-up. There were 13 (26%) patients with transient chin numbness with an average time to recovery of 15.7 (2-48) weeks. Two (4%) patients had transient recurrent laryngeal nerve (RLN) injury with hoarseness, whereas 1 (2%) patient had permanent injury. Conclusion. The TOETVA is a safe and reproducible procedure. For selected patients, this technique is a viable alternative to conventional thyroidectomy.

International Multi-institutional Experience with the Transoral Endoscopic Thyroidectomy Vestibular Approach.

Background: Surgical approaches to thyroidectomies have undergone a rapid evolution over the past three decades. Transoral endoscopic thyroidectomy vestibular approach (TOETVA) is currently the latest remote access procedure for the treatment of benign and malignant thyroid disease. The purpose of this article is to present the results of TOETVA from five different international institutions. Materials and Methods: From 2016 to 2019, 152 TOETVA procedures were performed on 149 patients at five separate international institutions. Outcomes were analyzed from a prospectively maintained database. There were 12 (8%) men and 137 (92%) women with mean ages of 41.5 ± 10.3 (27-69) and 46.9 ± 1.8 (17-78), respectively. Results: There were 3 (2%) cases that required conversion from the endoscopic approach to an open procedure. A thyroid lobectomy was performed in 111 (73.0%) cases, total thyroidectomy in 38 (25.0%) cases whereas a completion thyroidectomy in 3 (2.0%) cases. Mean operative times were 161.8 ± 42.4 (83-304) minutes for the lobectomy, 213.4 ± 71.7 (120-430) minutes for the total thyroidectomy, and 136.7 ± 109.8 (64-263) minutes for the completion thyroidectomy. The final pathology report revealed 107 (70.4%) benign nodules, 44 (28.9%) nodules with underlying papillary thyroid carcinoma, and 1 (0.7%) case with Hurthle cell carcinoma. Of the 152 cases, 7 (4.7%) patients developed temporary hypoparathyroidism. There were 5 (3.3%) patients who developed transient recurrent laryngeal nerve (RLN) injury and 3 (2.0%) with persistent injury of the RLN. Temporary lower lip numbness was noted in 51 (33.6%) patients whereas 1 (0.7%) patient was noted to have persistent numbness. We reported 57 (38.5%) patients with temporary chin numbness, 9 (5.9%) patients with skin injuries, and 2 (1.3%) with tracheal perforation. Conclusion: To date, the literature and the outcomes from these 5 international institutions have determined that, in select patients, TOETVA can be as safe and efficacious as the traditional trans-cervical technique for the treatment of specific thyroid pathologies.

Transoral Endoscopic Thyroidectomy Vestibular Approach.

BACKGROUND: Remote-access thyroid surgery has gained popularity and has advanced significantly over the past two decades, given the patient desire to avoid cosmetically displeasing scarring. It has only been recently that natural-orifice transluminal endoscopic surgery (NOTES) techniques have been geared for thyroidectomies. The transoral endoscopic thyroidectomy vestibular approach has been categorized as a NOTES procedure-given the approach to the thyroid gland via incisions in the oral cavity. Our aim is to provide a review of the current literature on the transoral endoscopic thyroidectomy vestibular approach (TOETVA), to present the worldwide experience of this novel procedure, and to outline whether individual patients have characteristics that would make the procedure feasible for this technique. METHODS: A literature review was done to compile articles detailing the international experience with TOETVA. Our experience combined with what has been published in the literature was used to establish which pathological and patient characteristics make this particular technique feasible for a thyroidectomy. RESULTS: We detail in the provided tables both feasibility for this surgical technique and the international experience. CONCLUSION: TOETVA represents the latest remote-access endoscopic technique for the excision of the thyroid gland. TOETVA is being performed at various international institutions and multiple hospitals in the United States.

Is bariatric surgery effective for co-morbidity resolution in the super-obese patients?

BACKGROUND: Type 2 diabetes (T2D), obstructive sleep apnea (OSA), hypertension (HTN), and hyperlipidemia (HLD) are common co-morbidities that are strongly associated with obesity. OBJECTIVE: The purpose of this study was to compare the rate of obesity-related co-morbidity remission and percent total body weight loss of super-obese patients with a body mass index (BMI) ≥50 kg/m2 with bariatric patients who have a BMI of 30 to 49.9 kg/m2. SETTING: Academic hospital, United States. METHODS: A retrospective analysis of outcomes of a prospectively maintained database was done on obese patients with a diagnosis of ≥1 co-morbidity (T2D, OSA, HTN, or HLD) who at the time of initial visit had undergone either a sleeve gastrectomy or a Roux-en-Y gastric bypass at our hospital between 2011 and 2015. The patients were stratified based on their preoperative BMI class, BMI of 30 to 49.9 kg/m2 versus BMI ≥50 kg/m2. RESULTS: Of the 930 patients, 732 underwent sleeve gastrectomy and 198 underwent Roux-en-Y gastric bypass. The 6-month follow-up co-morbidity remission rates for patients with a BMI of 30 to 49.9 kg/m2 (n = 759) versus super-obese patients (n = 171) were 46.0% and 36.7% (P = .348) for T2D; 75.0% and 73.2% (P = .772) for OSA; 35.0% and 22.0% (P = .142) for HTN; and 37.0% and 21.0% (P = .081) for HLD, respectively. The 1-year follow-up co-morbidity remission rates for patients with a BMI of 30 to 49.9 kg/m2 versus super-obese patients were 54.2% and 45.5% (P = .460) for T2D; 87.0% and 89.7% (P = .649) for OSA; 37.4% and 23.9% (P = .081) for HTN; and 43.2% and 34.6% (P = .422) for HLD, respectively. Furthermore, there was no difference in the mean percent total weight loss for patients with a preoperative BMI of 30 to 49.9 kg/m2 versus the super-obese at the 6-month (21.4%, 20.9%, P = .612) and 1-year (28.0%, 30.7%, P = .107) follow-ups. CONCLUSION: In our study, preoperative BMI did not have an impact on postoperative co-morbidity remission rates or percent total body weight loss. Future studies should investigate the effect of other factors, such as disease severity and duration.

Impact of milk based micronutrient supplementation in school children in Quito-Ecuador / Impacto de la suplementación de micronutrientes con leche en niños escolares de Quito-Ecuador

Background: The most common micronutrient deficiencies in Ecuadorian schoolchildren are vitamin A (VA), zinc, and iron. The objective of the present study was to test the efficacy of cow’s milk as a vehicle for VA, zinc, and iron supplementation. Methods: Three hundred twenty-eight children aged 6-10 years were included in a randomized, double blind controlled study; 173 children received 480 mL of whole milk (300 Kcals; G1) daily and 155 children received fortified milk (300 Kcals; G2) daily for 23 weeks. Participants had a nutritional evaluation before and after supplementation. Both treatment groups were comparable for gender, age, weight and height at the beginning of the study. Results: Both types of milk were well accepted by the participating children. Data showed that serum concentrations of VA, zinc, and iron significantly increased within both treatment groups. The increase in serum concentrations of the indicated micronutrients was significantly greater in children with deficiencies than in non-deficient ones. There were not significant differences in serum concentrations of VA, zinc, and iron between groups after supplementation. Data also showed that there was an increase in the percentage of children with normal BMI at the expense of a decrease of the percentage of children with excess weight at the end of the treatment period in G1 whereas in G2 it remained unchanged. Blood lipid profiles were normal before and after milk supplementation in both treatment groups. Conclusions: These data indicated that fortified and non-fortified milk are excellent options to increase serum VA, zinc, and iron concentration in schoolchildren (AU)

Introducción: las deficiencias de vitamina A (VA), zinc y hierro son las más comunes en escolares ecuatorianos. El objetivo del presente estudio fue estudiar la eficacia de la leche de vaca como vehículo para la suplementación de VA, zinc y hierro. Métodos: trescientos veintiocho niños en edades entre 6 y 10 años fueron incluidos en un estudio aleatorizado controlado, doble ciego durante 23 semanas; 173 niños recibieron diariamente 480 mL de leche entera (300 Kcals; G1) y 155 niños recibieron leche entera fortificada (300 Kcals, G2). Los niños tuvieron una evaluación nutricional antes y después de la suplementación. Al inicio del estudio, G1 y G2 fueron similares en género, edad, peso, y talla. Los dos tipos de leche fueron bien aceptados. Resultados: las concentraciones séricas de VA, zinc y hierro aumentaron significativamente en ambos grupos después del tratamiento. El aumento de estos micronutrientes fue significativamente mayor en los niños con deficiencias. No hubo diferencias significativas en las concentraciones de VA, zinc y hierro entre los grupos después de la suplementación. Además, hubo un incremento en el porcentaje de niños con IMC-normal dependiente de una disminución en el número de niños con exceso de peso al final del periodo de tratamiento en G1, mientras que en G2 no hubo cambios. Los perfiles lipídicos fueron normales antes y después de la suplementación con leche en los dos grupos. Conclusiones: en resumen, tanto la leche fortificada como la no fortificada son excelentes opciones para aumentar las concentraciones de VA, zinc y hierro en escolares (AU)

Preoperative insulin therapy as a marker for type 2 diabetes remission in obese patients after bariatric surgery.

BACKGROUND: Obesity not only increases the chances of developing diabetes-one of the top causes of death in the United States-but it also results in further medical complications. OBJECTIVE: To compare the 6-month and 1-year postoperative remission rates of type 2 diabetic (T2D) patients after bariatric surgery based on preoperative glycosylated hemoglobin (A1C) stratification and pharmacologic therapy: insulin-dependent diabetic (IDD) versus noninsulin-dependent diabetic (NIDD). SETTING: Academic hospital, United States. METHODS: We retrospectively analyzed a prospectively maintained database of 186 obese patients with a diagnosis T2D who had undergone either a sleeve gastrectomy or a Roux-en-Y gastric bypass surgery at our hospital. RESULTS: At 6 months (n = 180), patients who were stratified by preoperative A1C levels (<6.5; ≥6.5 to<8; ≥8) had 70.5%, 51.7%, and 30.0% remission rates (P<.001) and at 1 year (n = 118) patients had 72.0%, 54.0%, and 42.8% remission rates (P = .053), respectively. When patients were substratified by preoperative pharmacologic therapy, IDD and NIDD patients had different remission rates within the same A1C level. At 6-months follow-up within A1C ≥6.5 to<8 (IDD versus NIDD), the remission rate was 23.5% versus 64.1% (odds ratio [OR]: .173, confidence interval [CI]: .0471, .6308, P = .0079), and within A1C ≥8 the remission was 24.0% versus 37.5% (OR: .5263, CI: .2115, 1.3096, P = .1676), respectively. At 1-year follow-up within A1C ≥6.5 to<8, the remission rate was 30.0% versus 62.9% (OR: .2521, CI: .0529, 1.2019, P = .0838), and within A1C ≥8 the remission was 31.4% versus 61.9% (OR: .2821, CI: .0908, .8762, P = .0286), respectively. Furthermore, when IDD patients were compared between A1C ≥6.5 to<8 and A1C ≥8 the remission rates were nearly identical, and for NIDD patients A1C was not significantly associated with remission regardless of the level, except at 6 months. CONCLUSION: While a difference was observed between overall A1C levels-the lower the A1C level, the higher the remission rate-IDD patients had lower remission rates than NIDD patients irrespective of A1C levels; further, IDD patients performed similarly across A1C levels.

Impact of milk based micronutrient supplementation in school children in Quito-Ecuador.

BACKGROUND: The most common micronutrient deficiencies in Ecuadorian schoolchildren are vitamin A (VA), zinc, and iron. The objective of the present study was to test the efficacy of cow's milk as a vehicle for VA, zinc, and iron supplementation. METHODS: Three hundred twenty-eight children aged 6-10 years were included in a randomized, double blind controlled study; 173 children received 480 mL of whole milk (300 Kcals; G1) daily and 155 children received fortified milk (300 Kcals; G2) daily for 23 weeks. Participants had a nutritional evaluation before and after supplementation. Both treatment groups were comparable for gender, age, weight and height at the beginning of the study. RESULTS: Both types of milk were well accepted by the participating children. Data showed that serum concentrations of VA, zinc, and iron significantly increased within both treatment groups. The increase in serum concentrations of the indicated micronutrients was significantly greater in children with deficiencies than in non-deficient ones. There were not significant differences in serum concentrations of VA, zinc, and iron between groups after supplementation. Data also showed that there was an increase in the percentage of children with normal BMI at the expense of a decrease of the percentage of children with excess weight at the end of the treatment period in G1 whereas in G2 it remained unchanged. Blood lipid profiles were normal before and after milk supplementation in both treatment groups. CONCLUSIONS: These data indicated that fortified and non-fortified milk are excellent options to increase serum VA, zinc, and iron concentration in schoolchildren.

Uso del marcador KI-67 en la toma de decisión del tratamiento de tumor odontogénico quístico queratinizante: presentación de un caso / Use of KI-67 marker in decision making treatment keratinizing cystic odontogenic tumor: a case

El Tumor Odontogénico Quístico Queratinizante (TOQQ) es un tumor benigno de origen odontogénico, el cual fue considerado hasta muy recientemente una lesión quística denominada Queratoquiste odontogénico. El TOQQ es considerado un tumor de estructura quística, sin embargo, debido a su agresivo comportamiento clínico y el alto porcentaje de recurrencia el tratamiento varia desde la enucleación de la lesión hasta la eliminación radical total del hueso afectado. El propósito de este trabajo es la descripción de un caso en paciente femenina de 34 años de edad quien presentó imagen radiolúcida multilocular extensa que ocupó cuerpo y rama mandibular, cuyo estudio histopatológico, previa biopsia incisional, concluyó TOQQ. Se realizó la determinación de Ki-67 mediante inmunohistoquímica para planificar el tratamiento quirúrgico. La baja expresión de Ki-67, a pesar de la extensión de la lesión, fueron los criterios para la realización de tratamiento conservador. La paciente se encuentra sin recidiva después de 5 años de realizado el procedimiento quirúrgico.