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Recent work using plasmonic nanosensors in a clinically relevant detectionassay reports extreme sensitivity based upon a mechanism termed 'inversesensitivity', whereby reduction of substrate concentration increases reactionrate, even at the single-molecule limit. This near-homoeopathic mechanismcontradicts the law of mass action. The assay involves deposition of silveratoms upon gold nanostars, changing their absorption spectrum. Multipleadditional aspects of the assay appear to be incompatible with settled chemicalknowledge, in particular the detection of tiny numbers of silver atoms on abackground of the classic 'silver mirror reaction'. Finally, it is estimatedhere that the reported spectral changes require some 2.5E11 times more silveratoms than are likely to be produced. It is suggested that alternativeexplanations must be sought for the original observations.

Inverse sensitivity of plasmonic nanosensors at the single-molecule limit