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Trapping a Highly Reactive Nonheme Iron Intermediate That Oxygenates Strong C-H Bonds with Stereoretention
No full textAn unprecedentedly reactive iron species (2) has been generated by reaction of excess peracetic acid with a mononuclear iron complex [FeII(CF3SO3)2(PyNMe3)] (1) at cryogenic temperatures, and characterized spectroscopically. Compound 2 is kinetically competent for breaking strong C-H bonds of alkanes (BDE ≈ 100 kcal·mol-1) through a hydrogen-atom transfer mechanism, and the transformations proceed with stereoretention and regioselectively, responding to bond strength, as well as to steric and polar effects. Bimolecular reaction rates are at least an order of magnitude faster than those of the most reactive synthetic high-valent nonheme oxoiron species described to date. EPR studies in tandem with kinetic analysis show that the 490 nm chromophore of 2 is associated with two S = 1/2 species in rapid equilibrium. The minor component 2a (∼5% iron) has g-values at 2.20, 2.19, and 1.99 characteristic of a low-spin iron(III) center, and it is assigned as [FeIII(OOAc)(PyNMe3)]2+, also by comparison with the EPR parameters of the structurally characterized hydroxamate analogue [FeIII(tBuCON(H)O)(PyNMe3)]2+ (4). The major component 2b (∼40% iron, g-values = 2.07, 2.01, 1.95) has unusual EPR parameters, and it is proposed to be [FeV(O)(OAc)(PyNMe3)]2+, where the O-O bond in 2a has been broken. Consistent with this assignment, 2b undergoes exchange of its acetate ligand with CD3CO2D and very rapidly reacts with olefins to produce the corresponding cis-1,2-hydroxoacetate product. Therefore, this work constitutes the first example where a synthetic nonheme iron species responsible for stereospecific and site selective C-H hydroxylation is spectroscopically trapped, and its catalytic reactivity against C-H bonds can be directly interrogated by kinetic methods. The accumulated evidence indicates that 2 consists mainly of an extraordinarily reactive [FeV(O)(OAc)(PyNMe3)]2+ (2b) species capable of hydroxylating unactivated alkyl C-H bonds with stereoretention in a rapid and site-selective manner, and that exists in fast equilibrium with its [FeIII(OOAc)(PyNMe3)]2+ precursorFinancial support for this work was provided by the European Commission (2011-CIG-303522 to A.C. and ERC-2009-StG-239910 to M.C.), the Spanish Ministry of Science (CTQ2012-37420-C02-01/BQU to M.C., CTQ2012-37821-C02-02 to M.G.B., CTQ2013-43012-P to A.C., and CSD2010-00065 to M.C., M.G.B., and E.G.E) and Generalitat de Catalunya (ICREA Academia Award to M.C.). The Spanish Ministry of Science is acknowledged for a Juan de la Cierva contract to B.V. (JCI-2011-09302) and for a Ramón y Cajal contract to A.C. (RYC-2011-08683). We are thankful for the financial support from INNPLANTA project INP-2011-0059-PCT-420000-ACT1 to Dr. Xavi Riba
Multiomic characterization of small cell lung cancer: Real‐world insights into therapeutic opportunities
No full textNK, natural killer; STING, Stimulator of Interferon Genes; TCI, T‐cell inflamed
Daytime sleepiness and specific food cravings: The moderating role of insulin sensitivity
No full textDaytime sleepiness is posited to stimulate hunger and food intake of specific macronutrients such that obesity and type 2 diabetes mellitus risk may be elevated. To assess this hypothesis, this study of insulin sensitive and insulin resistant non‑diabetic individuals utilized standardized meal administration conditions to examine: 1) the extent to which self-reported sleepiness was associated with specific food cravings over the course of a day; and 2) whether insulin sensitivity interactively influenced this relationship.
Non-diabetic men and women (N = 143) participated in one session, where a euglycemic-hyperinsulinemia clamp was used to provide an insulin sensitivity index, and in a subsequent 14‑hour session, where four standardized mixed-meals and one pre-bedtime meal were provided. Concurrent pre-meal measures of sleepiness and cravings for sweet, salty, and starchy foods, and fruit, meat, and dairy foods were obtained. Hierarchical linear modeling analyses examined the within- and between-person association of sleepiness with food cravings across meals as a function of insulin sensitivity, controlling for age, sex and caloric intake administration.
Craving ratings were highest for fruits, followed by dairy and starchy foods, meat, and then salty and sweet foods (p < .001). Analyses showed that insulin sensitivity moderated the positive association of daytime sleepiness with all food cravings, except for salty foods (p = .011 to .036), independent of covariates. This moderation effect displayed the strongest magnitude at below-average and average insulin sensitivity levels (p < .001).
Study results extend previous findings to show that daytime sleepiness is positively associated with cravings for a range of food types. The fact that these associations were increased in persons with more diminished insulin sensitivity is novel and supports further examination of underlying mechanisms linking daytime sleepiness and food cravings with food consumption and metabolic dysregulation early in diabetes pathophysiology
Lymphatic System Transfer (LYST) with Pedicled SCIP for Patients with Lymphedema and Concomitant Chronic Venous Disease
No full textLymphatics System Transfer (LYST) is a recently described technique that combines the benefits of the established Vascularized Lymph Node Transfer (VLNT) with the advantages of Vascularized Lymph Vessel Transfer (VLVT). This procedure involves harvesting vascularized tissue that includes superficial lymphatic vessels and their corresponding draining nodes and transferring the tissue flap to the upper or lower extremity by microsurgical anastomosis. We present a novel pedicled LYST technique utilizing a Superficial Circumflex Iliac Perforator (SCIP) flap to treat patients with lower extremity lymphedema and concomitant chronic venous disease. Six patients underwent pedicled SCIP LYST, five of whom also received lymphovenous bypass distally in the lower extremity. Average follow-up period was 31 weeks (range: 10-55 weeks). Postoperative outcomes included a mean 15-point reduction in Lymphedema Life Impact Scale (LLIS) score (0.5 point per week) and a mean 30-unit decrease in bioimpedance spectroscopy (L-dex) measurements (0.9 units per week). No immediate complications were reported. The inclusion of long afferent lymphatic vessels with their draining lymph nodes may reduce the amount of lymphangiogenesis required to achieve physiological function, potentially leading to earlier functional recovery, though continued follow-up is necessary. The pedicled nature of this technique eliminates the need for microsurgical anastomosis, simplifying and shortening the procedure. Additionally, the proximal location of the pedicled flap may specifically offer advantages for patients with concomitant chronic venous disease, as flap lymphatics and lymph nodes drain efferent to the site of venous obstruction
SynthCharge: An Electric Vehicle Routing Instance Generator with Feasibility Screening to Enable Learning-Based Optimization and Benchmarking
No full textThe electric vehicle routing problem with time windows (EVRPTW) extends the classical VRPTW by introducing battery capacity constraints and charging station decisions. Existing benchmark datasets are often static and lack verifiable feasibility, which restricts reproducible evaluation of learning-based routing models. We introduce SynthCharge, a parametric generator that produces diverse, feasibility-screened EVRPTW instances across varying spatiotemporal configurations and scalable customer counts. While SynthCharge can currently generate large-scale instances of up to 500 customers, we focus our experiments on sizes ranging from 5 to 100 customers. Unlike static benchmark suites, SynthCharge integrates instance geometry with adaptive energy capacity scaling and range-aware charging station placement. To guarantee structural validity, the generator systematically filters out unsolvable instances through a fast feasibility screening process. Ultimately, SynthCharge provides the dynamic benchmarking infrastructure needed to systematically evaluate the robustness of emerging neural routing and data-driven approaches
Abstract PS1-07-27: A Single-Institutional Analysis of Survival Outcomes and Predictors in pN1 BreastCancer: Is There a Role for Post-Mastectomy Radiation?
No full textInvestigating Endogenous Hypercortisolism Prevalence in a U.S. Population With Resistant Hypertension: MOMENTUM Rationale and Design
No full textHypertension is a leading modifiable risk factor for cardiovascular disease and premature death among adults. Up to 18% of individuals with hypertension have resistant hypertension (rHTN), which substantially increases the risk of adverse clinical outcomes. Endogenous hypercortisolism can result in rHTN through multiple mechanisms.
MOMENTUM (NCT06829537) is the first large, observational, multicenter study examining the prevalence of endogenous hypercortisolism among adults with rHTN in the United States.
Target enrollment is approximately 1,000 participants. To be eligible, adults aged ≥18 years must have rHTN, defined using the American Heart Association criteria (systolic blood pressure ≥130 mm Hg despite ≥3 antihypertensive medications of different classes at maximally tolerated doses, including a diuretic, or ≥4 medications from different classes regardless of systolic blood pressure). Endogenous hypercortisolism is defined as cortisol level >1.8 μg/dL on the 1-mg overnight dexamethasone suppression test with adequate dexamethasone (≥140 ng/dL). The primary endpoint is endogenous hypercortisolism prevalence.
MOMENTUM will provide new insight into endogenous hypercortisolism in patients with resistant hypertension
Multibeam bathymetry processed data (Kongsberg EM 122 working area dataset) of RV SONNE during cruise SO306, Tanzania
No full textMBES bathymetry data were collected using the ship's own Kongsberg EM 122 multibeam echosounder during the RV SONNE cruise SO306 CoWIO (Port Louis, Mauritius - Durban, South Africa). The primary goal of the cruise was to search for cold-water coral mounds in the West Indian Ocean. Data were recorded in the EEZs of Mayotte, Tanzania, Mozambique, and South Africa. These studies were endorsed as an UN Ocean Decade 2021-2030 of Ocean Science for Sustainable Development activity. This dataset includes a bathymetric grid produced based on the MBES data collected in the EEZ of Tanzania between 2024-08-17 and 2024-08-27. Postprocessing of raw .all files was performed onboard by Evgenia Bazhenova and Alissa Bach, as well as consequently by Md Mumit Hassan in the frame of his work towards the master thesis at the HCU Hamburg. The QPS Qimera software was used to 1) verify that the SVP data were applied correctly based on the time and location; 2) block outer beams and in-turn data to ensure the best possible quality of the overlapping swaths, 3) routinely clean the point cloud using the slice editor. The final grid was interpolated by applying the average interpolation type and 5 minimum neighbours. Depths measured by the MBES are reported in respect to the water level. Only static draft was taken into account. No tidal corrections were applied during the data acquisition or data postprocessing
Accounting for age-related increases in HbA1c more accurately quantifies risk of Type 1 Diabetes progression in islet autoantibody-positive adults
No full textHbA1c thresholds used to define dysglycemia in autoantibody-positive individuals at risk for type 1 diabetes do not account for age-related increases in HbA1c and may overestimate progression risk in adults. We evaluated whether age-adjusted HbA1c or a higher HbA1c threshold improves risk stratification across age groups.
We analyzed 5,024 autoantibody-positive relatives (3,720 children and 1,304 adults) participating in the TrialNet Pathway to Prevention study. Age-related HbA1c effects were modelled using 6,273 adults from the population-based Exeter 10,000 cohort. Progression risk was compared using the standard dysglycemia threshold (HbA1c ≥ 5.7% [39 mmol/mol]), age-adjusted HbA1c, and an alternative threshold of HbA1c ≥6.0% (42 mmol/mol).
Using HbA1c ≥ 5.7%, children had higher 1-year progression risk than adults among single autoantibody-positive participants (38% [95% CI 28, 47] vs. 13% [7.2, 19]) and multiple autoantibody-positive participants (55% [49, 60] vs. 38% [27, 47]; both p<0.001). Age adjustment reduced these differences; progression risk was similar among single autoantibody-positive participants (38% [28, 47] vs. 27% [13, 39]; p=0.32), with attenuated differences among multiple autoantibody-positive participants. An HbA1c threshold ≥6.0% yielded comparable progression risk between adults and children across autoantibody subgroups. In post hoc analyses, adults aged <30 years had progression risk similar to children (p=0.1).
Age-related variation in HbA1c influences dysglycemia classification in adults at risk for type 1 diabetes. Age-adjusted HbA1c or a higher HbA1c threshold (≥6.0% [42 mmol/mol]) in adults ≥30 years identifies individuals with progression risk comparable to children and may improve age-specific risk stratification in prevention seungs
Palliative Care Education for Pediatric Critical Care Trainees: A Scoping Review and a Call to Action
No full textObjective Review the current teaching methods, curricula, and assessment tools for pediatric palliative care (PPC) within the pediatric s intensive care setting for pediatric critical care medicine (PCCM) trainees as it pertains to the following domains: (1) Symptom management, (2) Communication, (3) Spiritual/Psychosocial, (4) End of Life (EOL).Data Sources PubMed, Cochrane CENTRAL, EMBASE, and PsycINFO were searched for articles reporting on PPC educational curricula or interventions for residents and fellows in pediatric intensive care settings. The search strategy used a combination of MeSH terms and keywords to search for items that addressed intensive care, pediatrics, palliative care, residents or fellows, and education.Study Selection Curricula that includes PCCM trainees (fellows and residents) nationally and internationally.Data Extraction Covidence.Data Synthesis Of 105 articles reviewed, 6 articles addressed PPC education in the PICU between 2015 and 2025. All 6 articles were United States-based and included simulation curricula focused on communication regarding EOL care. Evaluation tools varied across articles. There is a paucity of data around complex symptom management, communication on topics other than EOL, and spiritual and psychosocial education.Conclusions Simulation focused on communication and EOL care is frequently used to teach PPC knowledge and skills to PCCM fellows and residents. Currently varied evaluation methods exist with limited PPC domains. This review highlights the need for future PPC curricula development for PCCM trainees