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Laser-heated electrospray ionization with mass spectrometry enables melting temperature measurements of aggregation-prone proteins from which thermochemical and mechanistic information about protein unfolding and ligand loss is deduced. 

Variance in predictions across different trained models is a significant, under-explored source of error in fair binary classification. In practice, the variance on some data examples is so large that decisions can be effectively arbitrary. To investigate this problem, we take an experimental approach and make four overarching contributions. We: 1) Define a metric called self-consistency, derived from variance, which we use as a proxy for measuring and reducing arbitrariness; 2) Develop an ensembling algorithm that abstains from classification when a prediction would be arbitrary; 3) Conduct the largest to-date empirical study of the role of variance (vis-a-vis self-consistency and arbitrariness) in fair binary classification; and, 4) Release a toolkit that makes the US Home Mortgage Disclosure Act (HMDA) datasets easily usable for future research. Altogether, our experiments reveal shocking insights about the reliability of conclusions on benchmark datasets. Most fair binary classification benchmarks are close-to-fair when taking into account the amount of arbitrariness present in predictions -- before we even try to apply any fairness interventions. This finding calls into question the practical utility of common algorithmic fairness methods, and in turn suggests that we should reconsider how we choose to measure fairness in binary classification. 

Rotating disc electrode (RDE) voltammetry has been widely adopted for the study of heterogenized molecular electrocatalysts for multi-step fuel-forming reactions but this tool has never been comprehensively applied to their homogeneous analogues. Here, the utility and limitations of RDE techniques for mechanistic and kinetic analysis of homogeneous molecular catalysts that mediate multi-electron, multi-substrate redox transformations are explored. Using the ECEC′ reaction mechanism as a case study, two theoretical models are derived based on the Nernst diffusion layer model and the Hale transformation. Current–potential curves generated by these computational strategies are compared under a variety of limiting conditions to identify conditions under which the more minimalist Nernst Diffusion Layer approach can be applied. Based on this theoretical treatment, strategies for extracting kinetic information from the plateau current and the foot of the catalytic wave are derived. RDEV is applied to a cobaloxime hydrogen evolution reaction (HER) catalyst under non-aqueous conditions in order to experimentally validate this theoretical framework and explore the feasibility of RDE as a tool for studying homogeneous catalysts. Crucially, analysis of the foot-of-the-wave via this theoretical framework provides rate constants for elementary reaction steps that agree with those extracted from stationary voltammetric methods, supporting the application of RDE to study homogeneous fuel-forming catalysts. Finally, obstacles encountered during the kinetic analysis of cobaloxime, along with the voltammetric signatures used to diagnose this reactivity, are discussed with the goal of guiding groups working to improve RDE set-ups and help researchers avoid misinterpretation of RDE data.