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.

Capillary electrophoresis tandem mass spectrometry determination of glutamic acid and homocysteine's metabolites: Potential biomarkers of amyotrophic lateral sclerosis.

Amyotrophic lateral sclerosis (ALS) is a neurodegenerative disease that affects both lower and upper motor neurons, leading to muscle atrophy, paralysis, and death caused by respiratory failure or infectious complications. Altered levels of homocysteine, cysteine, methionine, and glutamic acid have been observed in plasma of ALS patients. In this context, a method for determination of these potential biomarkers in plasma by capillary electrophoresis tandem mass spectrometry (CE-MS/MS) is proposed herein. Sample preparation was carefully investigated, since sulfur-containing amino acids may interact with plasma proteins. Owing to the non-thiol sulfur atom in methionine, it was necessary to split sample preparation into two methods: i) determination of homocysteine and cysteine as S-acetyl amino acids; ii) determination of glutamic acid and methionine. All amino acids were separated within 25min by CE-MS/MS using 5molL-1 acetic acid as background electrolyte and 5mmolL-1 acetic acid in 50% methanol/H2O (v/v) as sheath liquid. The proposed CE-MS/MS method was validated, presenting RSD values below 6% and 11% for intra- and inter-day precision, respectively, for the middle concentration level within the linear range. The limits of detection ranged from 35 (homocysteine) to 268nmolL-1 (glutamic acid). The validated method was applied to the analysis of plasma samples from a group of healthy individuals and patients with ALS, showing the potential of glutamic acid and homocysteine metabolites as biomarkers of ALS.

Metabolomic investigation of human diseases biomarkers by CE and LC coupled to MS.

Metabolomics is one of the most recent trends in the "omics" era that investigates the end products of an organism activity, that is, all metabolites in a biological system, which are small molecules (less than 1000 Da) from different chemical classes. Metabolomics represents a tool to assess the biochemical activity of a living system through the analysis of substrates and products processed during the metabolism. The analysis of the metabolic profile (nontargeted analysis, i.e. a comparison between samples profiles of individuals) and of specific metabolites (targeted analysis, which quantifies a selected group of metabolites) in biological samples provides an insight into the metabolic state and the biochemical processes of the organism and, therefore, may indicate the onset and the stage of different diseases. An early and accurate diagnosis is essential for successful treatment and probable cure of most illnesses; hence, the investigation of metabolites as disease biomarkers has increased considerably in recent years. This review aims to present the most relevant works that address the nontargeted and targeted analysis of metabolites in different diseases for the past 10 years, including kidney and neurological disorders, cardiovascular diseases, diabetes, and cancer, using CE and LC coupled with the accurate detection of mass spectroscopy.