Bacterial cellulose composite hydrogel for pre-concentration and mass spectrometric detection of thiol-containing biomarker

Simple soaking of bacterial cellulose (BC) membrane in carboxymethyl cellulose (CMC) solution yielded BC/CMC hydrogel having re-swellable property. Then, gold nanoparticles (AuNPs) were embedded in the BC/CMC hydrogel via in situ chemical reduction to form BC/CMC/AuNPs composite hydrogel. It was found that the composite hydrogel exhibited physical/chemical characteristics similar to those of BC. The AuNPs with an average diameter of 13 nm distributed uniformly within the BC/CMC matrix as verified by transmission electron microscopy. The novelty of this work is the application of the BC/CMC/AuNPs composite hydrogel for selective adsorption of an important thiol-containing biomarker of Alzheimer's disease, glutathione (GSH), prior to direct laser desorption/ionization mass spectrometric (LDI-MS) detection. GSH adsorbed in the BC/CMC/AuNPs composite hydrogel showed the high ionization signal in LDI-MS providing a linear range of 50-10,000 nM with a limit of detection as low as 54.1 nM, which is a cut-off level for distinguishing between normal individuals and Alzheimer's patients. It should be emphasized that an additional matrix was not necessary as AuNPs can act as self-matrix for LDI-MS analysis. Furthermore, the BC/CMC/AuNPs composite hydrogel can effectively preconcentrate GSH approximately 10 times upon adsorption allowing for ultrasensitive detection of GSH required for disease diagnosis.