Nalophan, Tedlar and Cali-5-Bond polymeric bags were compared to determine the most suitable type for breath sampling and storage when volatile organic compounds are to be determined. Analyses were performed by thermal desorption gas chromatography mass spectrometry. For each bag, the release of contaminants and the chemical stability of a gaseous standard mixture containing eighteen organic compounds, as well as the CO2 partial pressure were assessed. The selected compounds were representative of breath constituents and belonged to different chemical classes (i.e. hydrocarbons, ketones, aldehydes, aromatics, sulfurs and esters). In the case of Nalophan, the influence of the surface-to-volume ratio, related to the bag's filling degree, on the chemical stability was also evaluated. Nalophan bags were found to be the most suitable in terms of contaminants released during storage (only 2-methyl-1,3-dioxalane), good sample stability (up to 24 h for both dry and humid samples), and very limited costs (about 1 € for a 20 liter bag). The (film) surface-to-(sample) volume ratio was found to be an important factor affecting the stability of selected compounds, and therefore we recommended to fill the bag completely.

Tumor necrosis factor-α (TNF-α) is a biomarker of inflammation that occurs in patients suffering from heart failure (HF). Saliva can be sampled in a non-invasive way, and it is currently gaining importance as matrix alternative to blood in diagnostic and therapy monitoring. This work presents the development of an immunosensor array based on eight screen-printed gold electrodes to detect TNF-α in saliva samples. Two different functionalization strategies of electrodes were compared. In the first, anti-TNF-α antibodies were chemically bonded onto the electrode by functionalization with 4-carboxymethylaniline. The other functionalization procedure involved the binding of antibodies onto polymer-coated magnetic microparticles, which were then deposited onto the electrode by pulsed chronoamperometry. Finally, the chronoamperometry technique was applied to characterize the modified SPEAu. The use of a secondary antibody anti-TNF-α (Ab-TNF-α-HRP) labelled with horseradish peroxidase (HRP, 2 µg·mL⁻¹) was investigated using tetramethylbenzidine (TMB, pH = 3.75) as electrochemical substrate containing 0.2 mM of H₂O₂. A sandwich-type detection strategy with a secondary antibody anti-TNF-α provided chronoamperometric analyses in 10 s for each sample. Linearity, precision, limit of detection, and selectivity of devices were investigated. Interferences were evaluated by analyzing solutions containing other cytokine produced during the acute stage of inflammation. The immunosensor showed good performance within the clinically relevant concentration range, with a precision of 8%, and a limit of detection of 0.3 pg/mL. Therefore, it may represent a promising tool for monitoring HF in a non-invasive way.