First-principles analyses were performed for understanding the mechanistic details of Fe-catalysed asymmetric hydrogenation of alkenes in the presence of silane that has recently been experimentally realized. The catalytic hydrogenation is expected to proceed through initial hydride transfer from Fe-H to the CC bond of alkene, followed by σ-bond metathesis of hydrosilane to afford a chiral alkane product and an iron silyl species, which then reacts with H to regenerate the iron hydride species another σ-bond metathesis. The mechanistic details and the origin of the regioselectivity and stereoselectivity of these reactions are understood on the basis of detailed potential energy surface analysis, charge transfer and noncovalent interactions involved therein, strain energy and isodesmic studies in the solvated stage.
View Article and Find Full Text PDFRetrosternal or substernal goitre is a clinical entity defined when a significant proportion of the thyroid gland extends inferiorly through the thoracic inlet into the mediastinum. It has an incidence of 5.1-15.
View Article and Find Full Text PDFBackground: Patient-reported outcome measures (PROMs) are important markers of postsurgical outcomes following total joint arthroplasty (TJA). Recent policies by the Centers for Medicare & Medicaid Services will require hospitals to achieve at least 50% postoperative PROM collection rates in order to qualify for their full annual payment in fiscal year 2028. This study aimed to: (1) quantify provider PROMs collection rates for TJA patients; (2) compare mean improvements in postoperative PROMs in TJA patients; (3) identify the proportion of TJA patients achieving substantial clinical benefit (SCB); and (4) identify factors associated with TJA patient completion of matched PROMs and achievement of SCB at one year.
View Article and Find Full Text PDFBackground: Utilization of and access to total joint arthroplasty (TJA) are disproportionately skewed in patients who have low socioeconomic status (SES) and in minority populations. Patient-reported outcome measures (PROMs) are critical markers of post-surgical outcomes following TJA. This study aimed to: 1) evaluate differences in race, SES, and demographic factors between TJA patients who achieved substantial clinical benefit (SCB) and those who did not; 2) assess differences between preoperative PROMs in these patients; and 3) identify whether race and SES are associated with SCB achievement at 1-year post-TJA.
View Article and Find Full Text PDFBackground: Prognostication of patients with acute disorders of consciousness is imprecise but more accurate technology-supported predictions, such as cognitive motor dissociation (CMD), are emerging. CMD refers to the detection of willful brain activation following motor commands using functional magnetic resonance imaging or machine learning-supported analysis of the electroencephalogram in clinically unresponsive patients. CMD is associated with long-term recovery, but acceptance by surrogates and health care professionals is uncertain.
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