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Probing London Dispersion in Proton-Bound Onium Ions: Are Alkyl-Alkyl Steric Interactions Reliably Modeled?

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Laboratorium für Organische Chemie, Department of Chemistry and Applied Biosciences, ETH Zürich, Zürich 8093, Switzerland.

We report spectroscopic and spectrometric experiments that probe the London dispersion interaction between -butyl substituents in three series of covalently linked, protonated -pyridines in the gas phase. Molecular ions in the three test series, along with several reference molecules for control, were electrosprayed from solution into the gas phase and then probed by infrared multiphoton dissociation spectroscopy and trapped ion mobility spectrometry. The observed N-H stretching frequencies provided an experimental readout diagnostic of the ground-state geometry of each ion, which could be furthermore compared to a second, independent structural readout via the collision cross section.

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Objective: Type A insulin resistance syndrome (IRS), characterized by impaired insulin receptor function due to variants of the insulin receptor gene, manifests as severe insulin-resistant diabetes. Differentiation of type A IRS from type 2 diabetes on the basis of hyperinsulinemia can be challenging. Given the association between insulin receptor dysfunction and reduced insulin clearance, we evaluated the potential of the circulating C-peptide reactivity (CPR)/immunoreactive insulin (IRI) molar ratio, a marker of insulin clearance, for distinguishing type A IRS from type 2 diabetes.

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Objectives: We aimed to determine if shared decision-making (SDM) self-assessment of a standardized patient (SP) scenario was reliable, specifically whether students' communication resulted in each SP-student pair reporting internally consistent final treatment choices. We hypothesized student self-assessment would differ from SP and faculty assessment indicating a need for multisource feedback.

Methods: In this observational case study from 2016-2017, all third-year post-clerkship medical students received evidence-based treatment options for sinusitis and SDM lectures followed by a SP encounter on sinusitis.

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A reliable and objective method of measuring soft tissue changes in 2D photographs after distraction osteogenesis in individuals with CL/P.

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Pre- and postoperative photos to assess results are widely used in plastic and reconstructive surgery, for instance, in patients with cleft lip and palate (CL/P). Evaluations are often performed by assessment panels by viewing the photos. However, these are prone to be subjective.

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