Treatment of refractory, unresectable cutaneous squamous cell carcinoma presents a great challenge in head and neck oncology with poor prognosis. Prior case reports have shown off-label pembrolizumab, a programed cell death receptor antagonist, can be effective in unresectable cutaneous squamous cell carcinoma. Furthermore, prior reports have suggested enhanced efficacy when high mutational burden is present. In this study we present a severe case of unresectable cutaneous squamous cell carcinoma invading the orbit and cavernous sinus with documented tumor MLH1 mutation. The patient had a complete response to palliative, off-label pembrolizumab therapy.
In situations where primary recipient vessel sites are unavailable, the maxillary artery represents an innovative option to be considered with suitable recipient artery characteristics.
We report the results of a joint theoretical and experimental investigation into the copolymerisation of acrylamides and acrylates with α-olefins in free-radical processes. The transition-state structures of models for free-radical homo-and copolymerisation involving acrylamide, methylacrylamide, methacrylate, methyl methacrylate, and ethylene have been determined using density functional theory. The reaction energies and barrier heights comport with the experimentally observed properties, including the prevalence of monomer alternation, the realised stereospecificity, and the reaction yield. Continuum solvation models have been applied to determine the sensitivity of the relative energies to the bulk solvent properties. Experimentally, a Lewis acid catalyst is demonstrated to increase the incorporation of nonpolar 1-alkenes in copolymerisations with polar acrylamides and acrylates. In the presence of the Lewis acid, scandium (III) trifluoromethanesulfonate, the copolymerisation of 1-hexene and acrylamide results in an 8.5 mol % incorporation, up from 3.9 mol % in the absence of the Lewis acid. Computations incorporating Mg 2 + as a model Lewis acid elucidate the mechanism of this catalysis. In the addition of methacrylate to a methyl methacrylate radical terminated polymer, the Lewis acid binds to the carbonyls on both promoting isotactic addition, while for the addition of an alkene to the same polymer, the Lewis acid binds to the polymer, reducing the barrier for alkenyl addition inductively by withdrawing electron density. We have demonstrated the ability of computational studies to aid experimentalists in the synthesis of new copolymers with desired properties.
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