Label-free capacitive immunosensors for ultra-trace detection based on the increase of immobilized antibodies on silver nanoparticles

Detection of ultra-trace amounts of antigens by label-free capacitive immunosensors was investigated using electrodes modified with silver nanoparticles (AgNPs) that allows for an increase in the amount of immobilized antibodies. The optimal amount of AgNPs that provided the highest immobilization yield was 48 pmol (in 2.0 mL). The performances of immunosensor electrodes for human serum albumin prepared with AgNPs, were compared to electrodes prepared with gold nanoparticles. The two systems provided the same linear range (1.0 × 10−18 to 1.0 × 10−10 M) and detection limit (1.0 × 10−18 M). The system with AgNPs was used to analyze albumin in urine samples and the results agreed well with the immunoturbidimetric assay (P > 0.05). Electrodes modified with AgNPs and appropriate antibodies were tested for their performances to detect analytes of different sizes. For a macromolecule (human serum albumin) the incorporation of AgNPs improved the detection limit from 100 to 1 aM. For small molecules, microcystin-LR and penicillin G, the detection limits were lowered from 100 and 10 fM to 10 and 0.7 fM, respectively. The high sensitivity and very low detection limits are potentially useful for the analysis of toxins or residues present in samples at ultra-trace levels and this method could easily be applied to other affinity pairs.

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► Label-free capacitive detection at ultra-trace level was achieved using electrode modified with nanoparticles.
► There is an optimal amount of AgNPs that provided the highest immobilization yield.
► AgNPs can enhance the sensitivity and LOD of the immunosensors.
► LOD can be reduced by 2 and 1 orders of magnitude for large and small molecules.
► Under the same conditions AuNPs and AgNPs provided the same performance.