We report a simple, fast and selective colorimetric assay of adenosine triphosphate (ATP) using unmodified gold nanoparticles (AuNPs) as probes and metal ions as cross-linkers. ATP can be assembled onto the surface of AuNPs through interaction between the electron-rich nitrogen atoms and the electron-deficient surface of AuNPs. Accordingly, Cu2+ ions induce a change in the color and UV/Vis absorbance of AuNPs by coordinating to the triphosphate groups and a ring nitrogen of ATP. A detection limit of 50 nM was achieved, which is comparable to or lower than that achievable by the currently used electrochemical, spectroscopic or chromatographic methods. The theoretical simplicity and high selectivity reported herein demonstrated that AuNPs-based colorimetric assay could be applied in a wide variety of fields by rationally designing the surface chemistry of AuNPs. In addition, our results indicate that ATP-modified AuNPs are less stable in Cu2+, Cd2+ or Zn2+-containing solutions due to the formation of the corresponding dimeric metal-ATP complexes.
1 March 2014 in Journal of Electroanalytical Chemistry
Covalent organic frameworks (COFs) are a new type of metal-free porous architecture with a well-designed pore structure and high stability. Here an efficient electrochemical sensing platform was demonstrated based on COFs TpPa-1 constructed by 1,3,5-triformylphloroglucinol (Tp) with p-phenylenediamine (Pa-1), which possesses abundant nitrogen and oxo-functionalities. COFs TpPa-1 exhibited good water dispersibility and strong adsorption affinities for Pd2+ and thus was used as loading support to modify Pd2+. The Pd2+-modified COFs TpPa-1 electrode (Pd2+/COFs) showed high electrocatalytic activity for both hydrazine oxidation reaction and nitrophenol reduction reaction. In addition, TpPa-1-derived nitrogen-doped carbon presented high activity for the electro-oxidation of reduced glutathione (GSH), and sensitive electrochemical detection of GSH was achieved. The presented COFs TpPa-1 can be utilized as a precursor as well as support for anchoring electro-active molecules and nanoparticles, which will be useful for electrochemical sensing and electrocatalysis.
Electrode interfaces with both antibiofouling properties and electrocatalytic activity can promote the practical application of nonenzymatic electrochemical sensors in biological fluids. Compared with graphene, graphene oxide (GO) possesses unique properties such as superior solubility (hydrophilicity) in water, negative charge, and abundant oxygenated groups (oxo functionalities) in the plane and edge sites, which play an essential role in electrocatalysis and functionalization. In this work, a micro electrochemical sensor consisting of GO-modified screen-printed electrode and PDMS micro-cell was designed to achieve multi-analyte detection with excellent selectivity and anti-biofouling properties by electrochemically tuning the oxygen-containing functional species, hydrophilicity/hydrophobicity, and electrical conductivity. In particular, the presented electrodes demonstrated the potential in the analysis of biological samples in which electrodes often suffer from serious biofouling. The interaction of proteins with electrodes as well as uric acid was investigated and discussed.