Photochemical oxidation of alcohols: Simple derivatization strategy for their analysis by capillary electrophoresis.

The determination of ethanol is one of the most important parameters in the fermentation industry, influencing not only the production yield and the quality of the product, but also its commercial value. In addition to the traditional approach based on distillation/density, procedure that is considered laborious and time-consuming, methods based on chromatography are widely used. Alternatives using electrochemical, spectroscopic and colorimetric techniques have been also proposed for alcohol analysis. In general, these methods not only offer limited throughput, but also require harsh reaction conditions and/or complex instrumentation. Aiming to address these shortcomings, we propose a fast, simple and clean analytical approach for the determination of primary alcohols based on the photochemical oxidation under UV-LED irradiation in the presence of H2O2. The proposed method was successfully applied to the analysis of 12 different types of alcoholic beverages with an alcohol content ranging from 5% v/v (beer) to 53% v/v (whiskey).

Photochemical and photocatalytic degradation of 1-propanol using UV/H2 O2 : Identification of malonate as byproduct.

1-propanol is a primary alcohol extensively used in the pharmaceutical, chemical, and food industries. It has been also found as a contaminant in the atmosphere and is considered a model compound to mimic the behavior and fate of aliphatic alcohols exposed to environmental conditions. In order to understand that role of relevant variables, this paper presents results obtained with a simple experimental set-up to investigate the reactivity of 1-propanol under mild oxidizing conditions. Coupling this system with CE-C4 D allowed the quantification of the carboxylic acids formed. For the described experiments, aqueous solutions of 1-propanol were placed inside a photoreactor and oxidized upon the addition of TiO2 and/or H2 O2 . According to the described results, the addition of H2 O2 (0.1% w/w) was the most significant variable, roughly tripled the amount of carboxylic acids generated and led to the conversion of up to 70% of the initially available 1-propanol (1 mmol/L). More importantly, the reaction yielded the formation (within 10 min) of propionate (50 µmol/L), acetate (400 µmol/L), formate (50 µmol/L), and malonate (200 µmol/L). The latter is critically important because it represents the first example of the photochemical oxidation of both terminal carbons of the C3 -chain of 1-propanol under mild conditions, and opens new avenues for the production of this important chemical building block.

Application of capillary electrophoresis combined with conductometric and UV detection to monitor meteorite simulant bioleaching by Acidithiobacillus ferrooxidans.

The importance of microorganisms and biotechnology in space exploration and future planets colonization has been discussed in the literature. Meteorites are interesting samples to study microbe-mineral interaction focused on space exploration. The chemolithotropic bacterium Acidithiobacillus ferrooxidans has been used as model to understand the iron and sulfur oxidation. In this work, capillary electrophoresis with capacitively coupled contactless conductivity detection and UV detection was used to monitor bacterial growth in a meteorite simulant by measuring the conversion of Fe2+ into Fe+3 . The effect of Co2+ and Ni2+ (metals also found in meteorites) on the bacterial growth was also evaluated. The presented method allowed the analyses of all metals in a single run (less than 8 min). The background electrolyte was composted of 10 mmol/L α-hydroxyisobutyric acid/Histidine. For comparison purpose, the samples were also analyzed by UV-Vis spectrophotometry. The Fe2+ conversion into Fe3+ by A. ferrooxidans was observed up to 36 h with the growth rate constant of 0.19/h and 0.21/h in Tuovinen and Kelly (T&K) and in meteorite simulant media, respectively. The developed method presents favorable prospect to monitor the growth of other chemolithotropic microorganisms for biotechnology applications.

Online monitoring of electrocatalytic reactions of alcohols at platinum and gold electrodes in acidic, neutral and alkaline media by capillary electrophoresis with contactless conductivity detection (EC-CE-C4 D).

An EC-CE-C4 D flow system was applied to the investigation of electrocatalytic processes by monitoring carboxylic acids formed during the electro-oxidation at various potentials of primary alcohols (mixture of 1 mmol/L of ethanol, n-propanol, n-butanol and n-pentanol) in acidic, neutral and alkaline media. The electro-oxidation was carried out on gold and platinum disk electrodes (3 mm of diameter) in a thin-layer electrochemical flow cell. Products were sampled 50 µm apart from the electrode directly into the capillary. All the generated carboxylates were determined in near real time (less than 2 min) by CE-C4 D in counter-flow mode, with Tris/HCl buffer solution (pH 8.6) as BGE. Long sequences of 5-min experiments were run automatically, exploring the applied potential, electrolysis time and solution composition. Electro-oxidation at 1.5 V (versus Ag/AgCl quasi-reference) during 50 s in acidic medium was found appropriate for both Pt and Au electrodes when the determination of alcohols after derivatization is intended. A noteworthy selectivity effect was observed on the Au electrode. The signal corresponding to pentanoate is similar on both electrodes while the signal of ethanoate (acetate) is four times larger on gold than on platinum. The carboxylate signals were lower in alkaline medium (below the determination limit on Pt) than in acidic and neutral media. On gold, the formation of carboxylates was anticipated (0.85 V in alkaline medium versus 1.40 V in neutral medium). The automatic online monitoring of electrochemical processes by EC-CE-C4 D holds great potential to investigate ionic/ionizable intermediates/products of new electrocatalysts and/or alternative fuels.