Polyelectrolyte-functionalized reduced graphene oxide wrapped helical POMOF nanocomposites for bioenzyme-free colorimetric biosensing

For the sake of effective colorimetric sensing-pattern, a sensitive colorimetric sensor was conceived based on polyoxometalates based metal-organic frameworks (POMOFs) and polydiallyldimethylammonium chloride functionalized reduced graphene oxide (PDDA-rGO) for the first time, in which PDDA as a “glue” molecule turns rGO nanosheets into general platforms for bonding POMOFs nanoparticles. Herein, a new POMOF compound with fascinating helices-on-helices feature, [Ni4(Trz)6(H2O)2][SiW12O40].4H2O (Trz = 1,2,4-triazole) (abbreviated as Ni4SiW12), was synthesized and characterized, then PDDA-rGO sheet as dispersive and conductive material was successfully introduced to Ni4SiW12 fabricating new PDDA-rGO/Ni4SiW12-n nanocomposites, (abbreviated as PMPG-n). The resulting PMPG-n nanocomposites as peroxidase mimetic show excellent catalytic activities under extreme condition (pH value 2.5), attributed to the nature and synergies from POMs, MOFs and PDDA-rGOs. Note that the peroxidase-like activity of PMPG-1 (the mass ratio of Ni4SiW12 to PDDA-rGO is 1:1) exhibits higher sensitivity (1–60 μM), faster response (10 min) and the lowest limit of detection (2.07 μM) among all reported materials to citric acid (CA) to date. This work opens up new application prospects in colorimetric sensing system for food quality control and safety, biotechnology and clinical diagnosis.