Ex-Gaussian analysis of simple response time as a measure of information processing speed and the relationship with brain morphometry in multiple sclerosis.

BACKGROUND: The polyfactorial nature of the widely used symbol digit modalities test (SDMT) introduces significant measurement challenges in characterizing information processing speed (IPS) deficits in multiple sclerosis (MS). Measures with high psychometric IPS-specificity and less contamination from other cognitive domains are necessary to fully understand IPS changes. OBJECTIVE: Investigate how three mathematical modeling ex-Gaussian parameter estimates (mu, sigma, tau) derived from a simple response time (RT) task (1) differentiate MS from healthy control participants and (2) correspond to structural brain changes, to evaluate a novel IPS measurement approach. METHODS: Persons with and without MS completed a two-minute behavioral simple RT task, structural MRI and the MS functional composite. RT distributions were deconvolved into ex-Gaussian parameter estimates using mathematical modeling. Group differences and brain-behavior relationships were statistically evaluated. RESULTS: Persons with MS experienced a general pattern of slowing as evidenced by a shift in the Gaussian (mu) component of the distribution. This correlated with whole brain volume and white matter specifically. Additionally, persons with MS had larger values of tau (elongated positively skewed tail) that may reflect attentional lapses. CONCLUSION: The ex-Gaussian approach is sensitive to disease-related IPS changes and provides nuanced information about IPS slowing in MS.

Photochemical water oxidation by crystalline polymorphs of manganese oxides: structural requirements for catalysis.

Manganese oxides occur naturally as minerals in at least 30 different crystal structures, providing a rigorous test system to explore the significance of atomic positions on the catalytic efficiency of water oxidation. In this study, we chose to systematically compare eight synthetic oxide structures containing Mn(III) and Mn(IV) only, with particular emphasis on the five known structural polymorphs of MnO2. We have adapted literature synthesis methods to obtain pure polymorphs and validated their homogeneity and crystallinity by powder X-ray diffraction and both transmission and scanning electron microscopies. Measurement of water oxidation rate by oxygen evolution in aqueous solution was conducted with dispersed nanoparticulate manganese oxides and a standard ruthenium dye photo-oxidant system. No Ru was absorbed on the catalyst surface as observed by XPS and EDX. The post reaction atomic structure was completely preserved with no amorphization, as observed by HRTEM. Catalytic activities, normalized to surface area (BET), decrease in the series Mn2O3 > Mn3O4 ≫ λ-MnO2, where the latter is derived from spinel LiMn2O4 following partial Li(+) removal. No catalytic activity is observed from LiMn2O4 and four of the MnO2 polymorphs, in contrast to some literature reports with polydispersed manganese oxides and electro-deposited films. Catalytic activity within the eight examined Mn oxides was found exclusively for (distorted) cubic phases, Mn2O3 (bixbyite), Mn3O4 (hausmannite), and λ-MnO2 (spinel), all containing Mn(III) possessing longer Mn-O bonds between edge-sharing MnO6 octahedra. Electronically degenerate Mn(III) has antibonding electronic configuration e(g)(1) which imparts lattice distortions due to the Jahn-Teller effect that are hypothesized to contribute to structural flexibility important for catalytic turnover in water oxidation at the surface.