Boronic acid dendrimer receptor modified nanofibrillar cellulose membranes

Cellulose nanofibrils from sisal of typically 4–5 nm diameter and ca. 250 ± 100 nm length are reconstituted into thin films of ca. 6 µm thickness (or thicker freestanding films). Pure cellulose and cellulose composite films are obtained in a solvent evaporation process. A boronic acid appended dendrimer is embedded as a receptor in the nanofibrillar cellulose membrane. The number of boronic acid binding sites is controlled by varying the dendrimer content. The electrochemical and spectrophotometric properties of the nanocomposite membrane are investigated using the probe molecule alizarin red S. Pure cellulose membranes inhibit access to the electrode. However, the presence of boronic acid receptor sites allows accumulation of alizarin red S with a Langmuirian binding constant of ca. 6000 ± 1000 M⁻¹. The 2-electron 2-proton reduction of immobilized alizarin red S is shown to occur in a ca. 60 nm zone close to the electrode surface. With a boronic acid dendrimer modified nanofibrillar cellulose composition of 96 wt% cellulose and 4 wt% boronic acid dendrimer, the analytical range for alizarin red S in aqueous acetate buffer pH 3 is approximately 10 µM to 1 mM.