The ability to tame high-energy intermediates is important for synthetic chemistry, enabling the construction of complex molecules and propelling advances in the field of synthesis. Along these lines, carbenes and carbenoid intermediates are particularly attractive, but often unknown, high-energy intermediates. Classical methods to access metal carbene intermediates exploit two-electron chemistry to form the carbon-metal bond.
View Article and Find Full Text PDFMetallaphotoredox cross-coupling is a well-established strategy for generating clinically privileged aliphatic scaffolds via single-electron reactivity. Correspondingly, expanding metallaphotoredox to encompass new C()-coupling partners could provide entry to a novel, medicinally relevant chemical space. In particular, alkenes are abundant, bench-stable, and capable of versatile C()-radical reactivity via metal-hydride hydrogen atom transfer (MHAT), although metallaphotoredox methodologies invoking this strategy remain underdeveloped.
View Article and Find Full Text PDFThere exists a variety of specialized fire dynamics routines, zone fire models, and field fire models. Many of these heuristics and correlations rely on experimental data from fires fueled by gas burners or liquid pool fires and have had minimal, if any, validation against data from fires with solid, more complex fuels, such as upholstered furniture. One hundred and twenty fire experiments were conducted inside a compartment that contained a single ventilation opening in the form of a doorway that was either open or closed for the entirety of each experiment.
View Article and Find Full Text PDFBackground: Sex dimorphisms in coagulation are well established, with female-specific hypercoagulability conferring a survival benefit in the setting of trauma-induced coagulopathy (TIC). The mechanism behind these phenomena remains to be elucidated. We hypothesize that estradiol provokes a hypercoagulable profile and alters clot proteomics and fibrin crosslinking.
View Article and Find Full Text PDFJ Trauma Acute Care Surg
November 2022
Background: Trauma patients with abnormal fibrinolysis have increased morbidity and mortality. Knowledge of mechanisms differentiating fibrinolytic phenotypes is important to optimize treatment. We hypothesized that subjects with abnormal fibrinolysis identified by whole blood viscoelastometry can also be distinguished by plasma thrombin generation, clot structure, fibrin formation, and plasmin generation measurements.
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