Tip-porous microneedle: A highly stable sensing platform for direct determination of labile metals in natural seawater.

Nanomaterial-functionalized voltammetric microsensors are promising tools for detecting trace metals at low concentrations in the complex environment of natural seawater. However, the sensitivity reduction caused by the loss of modified nanomaterials in the detection process has always been a major problem. Herein, to fabricate a highly stable sensing platform, a microneedle electrode with a hierarchical porous tip was prepared through electrochemical etching technology to firmly embed nanoparticles. Using copper (Cu) as a model trace metal, a micro-cluster needle sensor based on a gold nanoparticle (AuNP)-embedded tip-porous microneedle electrode (P-MNE) was fabricated for the direct voltammetric determination of labile Cu in natural seawater. The porous structure of P-MNE not only provided a larger specific surface area and active sites for AuNPs which had excellent electrocatalytic performance for Cu2+ determination, but also protected from their loss during the detection process in seawater. Therefore, this novel micro-cluster needle sensor exhibited significantly improved stability with a relative standard deviation (RSD) of 1.5% for 30 detections. The linear range of Cu2+ on this micro-cluster needle sensor was from 0.1 to 1000 nM with a detection limit of 0.03 nM. More importantly, this micro-cluster needle sensor was successfully used for directly detecting labile Cu in natural seawater samples without any preaccumulation treatment or reagent addition to obtain the contribution proportions of the labile fraction in total dissolved Cu. Furthermore, this sensing platform might also be extended to the reliable determination of other labile metals in seawater by changing the functional nanoparticles embedded in the nanopores.