Oxidation Mechanism of 1-Methyl-tryptophan and Tryptophan on Glassy Carbon Electrode: A Comparative Study

The anodic behaviour of 1-methyl-tryptophan (1-mTrp) in aqueous electrolytes was investigated on a glassy carbon electrode (GCE), using voltammetric techniques. The oxidation of 1-mTrp was associated with an electrochemical-chemical (EC) mechanism: one electron and one proton were removed of C2 to form an intermediate radical, 1-mTrp⋅. This was followed by a two-way reaction, producing a 1-mTrp dimer and/or reaction with water to form a final hydroxylated product. The oxidation mechanism of 1-mTrp proposed was also compared with the anodic oxidation Trp on GCE. Differential pulse voltammetry was also explored for quantification of Trp and 1-mTrp in neutral medium with low detection limits, on an anodically pre-treated GCE.     

Simultaneous determination of serum tryptophan metabolites in an older Chinese population

Tryptophan (TRP) and its metabolites exhibit significant biological effects and are strongly associated with age-related disease and mortality. However, reports on quantitatively analyzing these metabolites in older individuals are not available. We used ultra-high-performance liquid chromatography–tandem mass spectrometry to optimize and validate a method for isotope dilution analysis of TRP metabolites in older individuals. The targeted analytes are TRP, serotonin or 5-hydroxytryptamine, kynurenine, kynurenic acid, xanthurenic acid, indole-3-acetic acid, indole-3-propionic acid, and tryptamine. The serum sample was purified using solid-phase extraction and was separated on a Waters HSS T3 column (100 mm × 2.1 mm, 1.8 μm). The analytes were detected in the multiple reaction monitoring mode under positive ionization. TRP was confirmed and measured after being diluted 100 times. This method exhibited satisfactory linearity (r > 0.99). The intrabatch and interbatch accuracies (85.7–114%) and precisions (<15%) were acceptable. The standard-normalized matrix effects ranged from 51.6 to 145%. This method was successfully applied to a cohort of 1021 older Chinese individuals, and this study may enable further understanding of the metabolic phenotypes associated with TRP in other populations.