Saliva analysis using metal-organic framework-coated miniaturized vials

In-vial microextraction is probably the simplest microextraction technique because it eliminates centrifugation and/or filtration steps while offering short extraction and desorption times. However, it has had limited applicability, mostly involving polydimethylsiloxane coatings and gas chromatography applications. Quite recently, one study introduced metal-organic framework (MOF)-coated glass vials for environmental analyses and liquid chromatography, thus combining the advantages of MOFs as adsorbents with the advantages of the in-vial approach, while not limiting the application to volatile analyses. Besides, a much higher exposure of the MOF to the sample due to the thin film coating available within the vial's inner walls is attained. Clearly, the applicability of this format for bioanalysis has not been evaluated, as there are not many stable and reusable sorbents useful for biological samples presenting high protein content. Besides, the in-vial technique must demonstrate to be valid for low-availability samples, such as saliva.

A vial with 2 mL-capacity and coated uniformly with a MOF has been developed to analyze saliva in a thin film solid-phase microextraction approach, while keeping an adequate analytical performance using only 50 μL of solvent for desorption. The procedure only requires 12.5 min of operation. Interestingly, the issues related to pore-blocking of the crystalline materials by proteins present in the saliva samples are solved with a simple cleaning protocol that also ensures a high reusability of the vials (more than 50 times). Seven bisphenols were determined in saliva with these devices, reaching limits of detection down to 0.10 μg L^-1, and with inter-vial and inter-day precision values as RSD (in %) lower than 15% at a low concentration level (2.0 μg L^-1).

A device is presented to analyze complex saliva samples with a novel miniaturized MOF-coated vial ensuring proper reusability, while addressing the challenge of protein clogging and, at the same time, keeping adequate analytical performance with short analysis times. This approach represents significant progress in the bioanalytical sample preparation field, particularly when using sorbent porous materials integrated within miniaturized devices.