Metallacarboranes as Photoredox Catalysts in Water

Metallacarboranes with the shape of the Greek letter θ, such as [Co(C₂B₉H₁₁)₂]⁻, were tested, for the first time, as efficient photoredox catalysts in the oxidation of aromatic and aliphatic alcohols in water. Their efficiency is linked to their high solubility in water, their high oxidizing power (Co^4+/3+), and their absence of fluorescence on excitation, among others. In most of the studied examples, using a catalyst load of 0.4 mol % gave high yields of 90–95 % with selectivity greater than 99 %. By reducing the catalyst load to 0.01 mol %, quantitative conversion of reactants to products was achieved, in some cases with greater than 99 % yield, high catalyst efficiency reaching a turnover number of 10 000, and a higher yield with a 45 times lower concentration of catalyst. The metallacarboranes can be recovered easily by precipitation on addition of [NMe₄]Cl. A pathway for the photoredox-catalyzed oxidation of alcohols is proposed.     

Highlights on the Binding of Cobalta-Bis-(Dicarbollide) with Glucose Units

Metalla-bis-dicarbollides, such as the cobalta-bis-dicarbollide (COSAN) anion [Co(C₂B₉H₁₁)₂]⁻, have attracted much attention in biology but a deep understanding of their interactions with cell components is still missing. For this purpose, we studied the interactions of COSAN with the glucose moiety, which is ubiquitous at biological interfaces. Octyl-glucopyranoside surfactant (C8G1) was chosen as a model as it self-assembles in water and creates a hydrated glucose-covered interface. At low COSAN content and below the critical micellar concentration (CMC) of C8G1, COSAN binds to C8G1 monomers through the hydrophobic effect. Above the CMC of C8G1, COSAN adsorbs onto C8G1 micelles through the superchaotropic effect. At high COSAN concentrations, COSAN disrupts C8G1 micelles and the assemblies become similar to COSAN micelles but with a small amount of solubilized C8G1. Therefore, COSAN binds in a versatile way to C8G1 through either the hydrophobic or superchaotropic effect depending on their relative concentrations.     

Biomedical application of VIMP: screening of malignant cells in the prostate

An electrochemical method for discriminating healthy and malignant tissues in prostate biopsies using the voltammetry of immobilized particles methodology is described. The method involves the sampling with graphite bars 0.5 mm in diameter on paraffin-impregnated cross sections of prostate tissues used in ordinary cytological evaluation after local staining with methylene blue (MB). The subsequent record of the voltammetric response of sample-modified graphite electrodes displays clearly different MB-centered features for healthy and malignant regions due to the different association of the dye to the respective cells.

     

Asymptotics of relative heat traces and determinants on open surfaces of finite area

The goal of this article is to prove that on surfaces with asymptotically cusp ends the relative determinant of pairs of Laplace operators is well defined. We consider a surface with cusps $(M,g)$ and a metric $h$ on the surface that is a conformal transformation of the initial metric $g$ . We prove the existence of the relative determinant of the pair $(\Delta _{h},\Delta _{g})$ under suitable conditions on the conformal factor. The core of the paper is the proof of the existence of an asymptotic expansion of the relative heat trace for small times. We find the decay of the conformal factor at infinity for which this asymptotic expansion exists and the relative determinant is defined. Following the paper by B. Osgood, R. Phillips, and P. Sarnak about extremal of determinants on compact surfaces, we prove Polyakov’s formula for the relative determinant and discuss the extremal problem inside a conformal class. We discuss necessary conditions for the existence of a maximizer.     

An approximate dynamic programming approach for the vehicle routing problem with stochastic demands

This paper examines approximate dynamic programming algorithms for the single-vehicle routing problem with stochastic demands from a dynamic or reoptimization perspective. The methods extend the rollout algorithm by implementing different base sequences (i.e. a priori solutions), look-ahead policies, and pruning schemes. The paper also considers computing the cost-to-go with Monte Carlo simulation in addition to direct approaches. The best new method found is a two-step lookahead rollout started with a stochastic base sequence. The routing cost is about 4.8% less than the one-step rollout algorithm started with a deterministic sequence. Results also show that Monte Carlo cost-to-go estimation reduces computation time 65% in large instances with little or no loss in solution quality. Moreover, the paper compares results to the perfect information case from solving exact a posteriori solutions for sampled vehicle routing problems. The confidence interval for the overall mean difference is (3.56%, 4.11%).     

Effect of temperature on the chromatographic retention of ionizable compounds. III. Modeling retention of pharmaceuticals as a function of eluent pH and column temperature in RPLC

We propose a general simple equation for accurately predicting the retention factors of ionizable compounds upon simultaneous changes in mobile phase pH and column temperature at a given hydroorganic solvent composition. Only four independent experiments provide the input data: retention factors measured in two pH buffered mobile phases at extreme acidic and basic pH values (e. g., at least +/- 2 pH units far from the analyte pK(a)) and at two column temperatures. The equations, derived from the basic thermodynamics of the acid-base equilibria, additionally require the knowledge of the solute pK(a )and enthalpies of acid-base dissociation of both the solute and the buffer components in the hydroorganic solvent mixture. The performance of the predictive model is corroborated with the comparison between theoretical and experimental retention factors of several weak acids and bases of important pharmacological activity, in mobile phases containing different buffer solutions prepared in 25% w/w ACN in water and at several temperatures.