Calcium-catalysed synthesis of amines through imine hydrosilylation: an experimental and theoretical study.

A method to reduce aldimines through hydrosilylation is reported. The catalytic system involves calcium triflimide (Ca(NTf2)2) and potassium hexafluorophosphate (KPF6) which have been shown to act in a synergistic manner. The expected amines are obtained in fair to very high yields (40-99%) under mild conditions (room temperature in most cases). To illustrate the potential of this method, a bioactive molecule with antifungal properties was prepared on the gram scale and in high yield in environmentally friendly 2-methyltetrahydrofuran. Moreover, it is shown in this example that the imine can be prepared in situ from the aldehyde and the amine without isolating the imine. The mechanism involved has been explored experimentally and through DFT calculations, and the results are in accordance with an electrophilic activation of the silane by the calcium catalyst.

Enantioselective Intramolecular Iridium-Catalyzed Cyclopropanation of α-Carbonyl Sulfoxonium Ylides.

Enantioselective cyclopropanation of α-carbonyl sulfoxonium ylides (SY) has so far been limited to addition/ring closure reactions on electron-poor olefins. Herein, we report the iridium-catalyzed intramolecular cyclopropanation of SY in the presence of a chiral diene in up to 96% yield and 98% enantioselectivity. Moreover, density functional theory calculations suggest that the re face of the olefin preferably attacks an iridium carbene intermediate in an asynchronous concerted step that is independent of the geometry of the olefin.

Hepatocellular carcinoma radiation segmentectomy treatment intensification prior to liver transplantation increases rates of complete pathologic necrosis: an explant analysis of 75 tumors.

PURPOSE: To verify the correlation between yttrium-90 glass microsphere radiation segmentectomy treatment intensification of hepatocellular carcinoma (HCC) and complete pathologic necrosis (CPN) at liver transplantation. METHODS: A retrospective, single center, analysis of patients with HCC who received radiation segmentectomy prior to liver transplantation from 2016 to 2021 was performed. The tumor treatment intensification cohort (n = 38) was prescribed radiation segmentectomy as per response recommendations identified in a previously published baseline cohort study (n = 37). Treatment intensification and baseline cohort treatment parameters were compared for rates of CPN. Both cohorts were then combined for an overall analysis of treatment parameter correlation with CPN. RESULTS: Sixty-three patients with a combined 75 tumors were analyzed. Specific activity, dose, and treatment activity were significantly higher in the treatment intensification cohort (all p < 0.01), while particles per cubic centimeter of treated liver were not. CPN was achieved in 76% (n = 29) of tumors in the treatment intensification cohort compared to 49% (n = 18) in the baseline cohort (p = 0.013). The combined cohort CPN rate was 63% (n = 47). ROC analysis showed that specific activity ≥ 327 Bq (AUC 0.75, p < 0.001), dose ≥ 446 Gy (AUC 0.69, p = 0.005), and treatment activity ≥ 2.55 Gbq (AUC 0.71, p = 0.002) were predictive of CPN. Multivariate logistic regression demonstrated that a specific activity ≥ 327 Bq was the sole independent predictor of CPN (p = 0.013). CONCLUSION: Radiation segmentectomy treatment intensification for patients with HCC prior to liver transplantation increases rates of CPN. While dose strongly correlated with pathologic response, specific activity was the most significant independent radiation segmentectomy treatment parameter associated with CPN.

Abdominal obesity-related risk factors in children from public schools of Barbacena, Minas Gerais, Brazil / Fatores associados à obesidade abdominal em crianças matriculadas na rede pública de ensino, Barbacena, Minas Gerais

ABSTRACT Objective: To evaluate the sociodemographic and lifestyle factors associated with abdominal obesity in children from public schools in Barbacena, state of Minas Gerais, Brazil. Methods: This is a cross-sectional study conducted on 326 students aged 7 to 9 years from public schools in the urban area of the city. Anthropometric data included body weight, height, body mass index according to age, waist circumference, and waist-to-height ratio. Food consumption was evaluated using the Previous Day Food Questionnaire. Abdominal obesity was assessed based on waist circumference and waist-to-height ratio. The bivariate and multivariate analyses were performed by logistic regression, estimating the crude and adjusted odds ratio (OR), with 95% confidence interval. Results: The prevalence of overweight was 30.7%; whereas the prevalence of abdominal obesity was 9.2 and 12.6% according to waist circumference and waist-to-height ratio, respectively. Boys (OR 2.76; 95%CI 1.22-6.25) and children from central schools (OR 2.73; 95%CI 1.08-6.80) presented an increased chance of abdominal obesity according to waist circumference. Abdominal obesity according to waist-to-height ratio was associated with the central location of the schools (OR 2.18; 95%CI 1.02-4.63) and the habit of skipping supper (OR 2.01; 95%CI 1.00-4.09). Conclusions: The findings showed that being a boy, studying in a central school, and skipping supper were the main risk factors associated with abdominal obesity.

RESUMO Objetivo: Avaliar os fatores sociodemográficos e de estilo de vida associados à obesidade abdominal em crianças de escolas públicas de Barbacena, Minas Gerais. Métodos: Trata-se de estudo transversal realizado com 326 escolares de sete a nove anos, matriculados em escolas da zona urbana da cidade. As variáveis antropométricas avaliadas foram peso, estatura, índice de massa corpórea por idade, circunferência da cintura e relação cintura-estatura. O consumo alimentar foi registrado pelo Questionário Alimentar do Dia Anterior. A obesidade abdominal foi avaliada com base na circunferência da cintura e relação cintura-estatura. As análises bivariada e multivariada foram realizadas por meio de regressão logística, estimando-se a Odds Ratio (OR) bruta e ajustada, com os intervalos de confiança de 95% (IC95%). Resultados: A prevalência de excesso de peso foi de 30,7%, enquanto a prevalência de obesidade abdominal foi de 9,2 e 12,6%, de acordo com circunferência da cintura e relação cintura-estatura, respectivamente. Crianças do sexo masculino (OR 2,76; IC95% 1,22-6,25) e de escolas centrais (OR 2,73; IC95% 1,08-6,80) tiveram maior chance de apresentar obesidade abdominal segundo a circunferência da cintura. A obesidade abdominal, de acordo com a relação cintura-estatura, associou-se à localização central das escolas (OR 2,18; IC95% 1,02-4,63) e à omissão da ceia (OR 2,01; IC95% 1,00-4,09). Conclusões: Os achados mostraram que ser do sexo masculino, estudar em escola central e omitir a ceia foram os principais fatores de risco associados à obesidade abdominal.

Abdominal obesity-related risk factors in children from public schools of Barbacena, Minas Gerais, Brazil.

OBJECTIVE: To evaluate the sociodemographic and lifestyle factors associated with abdominal obesity in children from public schools in Barbacena, state of Minas Gerais, Brazil. METHODS: This is a cross-sectional study conducted on 326 students aged 7 to 9 years from public schools in the urban area of the city. Anthropometric data included body weight, height, body mass index according to age, waist circumference, and waist-to-height ratio. Food consumption was evaluated using the Previous Day Food Questionnaire. Abdominal obesity was assessed based on waist circumference and waist-to-height ratio. The bivariate and multivariate analyses were performed by logistic regression, estimating the crude and adjusted odds ratio (OR), with 95% confidence interval. RESULTS: The prevalence of overweight was 30.7%; whereas the prevalence of abdominal obesity was 9.2 and 12.6% according to waist circumference and waist-to-height ratio, respectively. Boys (OR 2.76; 95%CI 1.22-6.25) and children from central schools (OR 2.73; 95%CI 1.08-6.80) presented an increased chance of abdominal obesity according to waist circumference. Abdominal obesity according to waist-to-height ratio was associated with the central location of the schools (OR 2.18; 95%CI 1.02-4.63) and the habit of skipping supper (OR 2.01; 95%CI 1.00-4.09). CONCLUSIONS: The findings showed that being a boy, studying in a central school, and skipping supper were the main risk factors associated with abdominal obesity.

Pathologic Response of Hepatocellular Carcinoma Treated with Yttrium-90 Glass Microsphere Radiation Segmentectomy Prior to Liver Transplantation: A Validation Study.

PURPOSE: To evaluate the pathologic outcomes of hepatocellular carcinoma (HCC) treated with Yttrium-90 radiation segmentectomy using glass microspheres prior to liver transplantation and explore parameters associated with pathologic necrosis. MATERIALS AND METHODS: A single-institution retrospective analysis of HCC patients who received radiation segmentectomy prior to liver transplantation from November 2016 to May 2020 was performed. Patients were included if the treatment angiosome encompassed the entire tumor and could be correlated with available gross pathology. Archived histology slides were reviewed for percentage of pathologic necrosis. Thirty-three patients with 37 tumors were evaluated. The median tumor size was 2.3 cm (range, 1-6.7 cm). RESULTS: All tumors received a single treatment. The median time from radiation segmentectomy to transplantation was 206 days (range, 58-550 days). Objective response per Modified Response Evaluation Criteria in Solid Tumors (mRECIST) was 92% (complete response, 76%; partial response, 16%). A total of 68% (n = 25) of tumors demonstrated ≥99% pathologic necrosis. Complete pathologic necrosis was present in 53% and 75% of tumors treated with >190 Gy (n = 18) and >500 Gy (n = 8) single-compartment Medical Internal Radiation Dose, respectively. Complete response per mRECIST, posttreatment angiosome T1 hypointensity, dose >190 Gy, microsphere specific activity >297 Bq, and a longer time between treatment and transplant were associated with ≥99% tumor necrosis (P < .05). No posttransplant tumor recurrences occurred within a median follow-up of 604 days (range, 138-1,223 days). CONCLUSIONS: Radiation segmentectomy can serve as an ablative modality for the treatment of HCC prior to liver transplant.

Albumin-bilirubin grade as a prognostic indicator for patients with non-hepatocellular primary and metastatic liver malignancy undergoing Yttrium-90 radioembolization using resin microspheres.

BACKGROUND: Studies have shown that the albumin-bilirubin (ALBI) grade can be a superior prognosticator for patients undergoing Yttrium-90 (Y90) glass microsphere radioembolization for hepatocellular carcinoma (HCC) compared to the Child-Pugh (CP) scoring system. Less is known about the applicability of this score in non-hepatocellular malignancies using Y90 resin microspheres. This study evaluates the ALBI grade's ability to predict overall survival and biochemical toxicity in patients undergoing resin Y90 radioembolization and body surface area dosimetry (BSA) for non-hepatocellular primary and metastatic liver malignancies compared to the CP class and Model for End-Stage Liver Disease (MELD) score. METHODS: A retrospective review of patients with intrahepatic metastatic colorectal and neuroendocrine cancers and cholangiocarcinoma undergoing resin radioembolization from 2006-2015 at a single tertiary medical center was performed. ALBI, MELD, and CP scores were compared and correlated with biochemical toxicity and overall survival. RESULTS: There was a significant difference in overall survival between CP class A and class B liver function (P=0.04) for the entire patient cohort. ALBI grade (P=0.36) and MELD score (P=0.19) were not independently associated with survival. When stratified by CP class, the ALBI grade revealed a trend for survival difference in CP class B (P=0.05). Baseline ALBI grade was associated with post-procedural albumin reduction (P=0.01) and bilirubin elevation (P=0.007). CONCLUSIONS: ALBI grade predicted post-procedural biochemical toxicity, but did not predict survival after resin radioembolization of non-hepatocellular liver malignancies using BSA dosimetry. Given the heterogeneity of this study population, dedicated prospective analyses are required.

Individualized Ablation of Hepatocellular Carcinoma: Tailored Approaches across the Phenotype Spectrum.

Ablation is now recommended by international guidelines for the definitive treatment of hepatocellular carcinoma (HCC). Extensive clinical studies have demonstrated outcomes comparable to surgical resection with shorter hospital stays, decreased costs, and improved quality of life. Successful ablation requires complete treatment of both tumor and margin while preserving critical adjacent structures. HCC exhibits highly variable presentations in both anatomic involvement and biology which have significant implications on choice of ablative therapy. There are now abundant ablation modalities and adjunctive techniques which can be used to individualize ablation and maximize curative results. This article provides a patient-centered summary of approaches to HCC ablation in the context of patient performance, hepatic reserve, tumor phenotype and biology, intra- and extrahepatic anatomy, and ablation technology.

Safety and efficacy of locoregional therapy for metastatic pancreatic ductal adenocarcinoma to the liver: a single-center experience.

BACKGROUND: Many patients with pancreatic ductal adenocarcinoma (PDAC) are diagnosed with liver metastatic disease (mPDAC), and few are surgical candidates. Interventional oncology (IO) locoregional therapies (LRT) have proven beneficial in other primary and metastatic hepatic malignancies. Systemic chemotherapy is the standard of care for patients with mPDAC. This study assessed the safety and efficacy of LRT including thermal ablation, chemoembolization, and radioembolization for mPDAC. METHODS: A retrospective analysis was performed of 28 patients with mPDAC referred to IR clinic for consideration of LRT from 01/2006 to 08/2017, of whom 20 underwent treatment. Laboratory values were analyzed at 0, 3, and 6 months post-treatment. Imaging response was evaluated at 1, 3, and 6 months post-intervention by modified Response Evaluation Criteria in Solid Tumors (mRECIST) criteria. Adverse events (AE) were classified by CTCAE v5.0. Overall survival (OS) from the diagnosis of PDAC, survival from the time of mPDAC diagnosis, and survival from the time of LRT were calculated. RESULTS: Median OS (mOS) was 25 months. Median survival from time of mPDAC diagnosis and post LRT were 16.25 and 9.7 months, respectively. At one month post-intervention, 12 of 17 patients demonstrated disease response (CR or PR per mRECIST). Survival among responders was 9 months vs. 6 months for patients with stable or progressive disease (P=0.08). There were two grade 3 AE which included post-embolization syndrome and transient renal failure. Chemotherapy was briefly delayed in one of these patients, but ultimately resumed. CONCLUSIONS: The use of LRT in patients with mPDAC is safe. Additionally, no significant chemotherapy limiting toxicities were observed. Responders to therapy demonstrated a survival benefit trend in this small and heterogeneous cohort. Further investigations with randomized trials are warranted.

Biometria ocular, estimativa matemática e variação esférica pós-facectomia / Ocular biometry, mathematical estimation and spherical variation after facectomy

RESUMO Objetivo: Avaliar os parâmetros biométricos oculares por meio da biometria óptica e observar uma possível diferença refratométrica esférica, assim como sua variação, baseada no cálculo pré-cirúrgico estimado e na refração esférica pós-cirurgia de catarata pela facoemulsificação com implante de lente intraocular (LIO). Métodos: Foram revisados 252 prontuários eletrônicos entre 2013 e 2014 dos quais foram selecionados 117 pacientes adultos (189 olhos) submetidos à facoemulsificação com implante de LIO dobrável pelo mesmo cirurgião e examinados através do IOLMaster® 500. O poder dióptrico da LIO foi calculado pela fórmula de Haigis. O teste de Wilcoxon foi empregado para testar a existência de diferença significativa (p<0,05) entre o grau esférico esperado (GEE) e o grau esférico final (GEF). Resultados: Foram operados 98 olhos direitos (OD) e 91 esquerdos (OE). Após calculada a variação entre o GEE e o GEF observou-se que 55% dos OD alcançaram resultados dentro de ± 0,5 dioptrias (D) e 89% resultados dentro de ± 1D. Quanto ao OE, 46% alcançaram resultados dentro de ± 0,5D e 78% dentro de ± 1D. Conclusão: A biometria óptica pode ser utilizada como um método confiável, previsível e reprodutível para que seja estimado o GEF de ambos olhos.

ABSTRACT Objective: To assess ocular biometric parameters by optical biometry and to observe a possible spherical refractive difference, as well as its variation based on estimated preoperative calculation and the spherical refraction post cataract surgery by phacoemulsification with intraocular lens implant (IOL). Methods: After reviewing 252 electronic medical records between 2013 and 2014, 117 adult patients (189 eyes) were selected.The patients underwent phacoemulsification with foldable IOL implantation by the same surgeon and were examined by IOLMaster® 500.The IOL power was calculated using the Haigis formula.The Wilcoxon test was applied to identify the existence of significant differences (p<0.05) between the spherical expected refraction (SER) and the final spherical refraction (FSR) of the eyes. Results: There were operated 98 right eyes (OD) and 91 left (OS). A calculation of the variation between FSR and SER indicated that 55% of the OD reached results within ± 0.5 diopters (D) and 89% within ± 1D. With respect to OS, 46% achieved results within ± 0.5D and 78% within ± 1D. Conclusion: Optical biometry is a reliable, predictable and reproducible method to estimate the FSR of both eyes.