Different approaches for increasing the sensitivity and selectivity of volt
ammetric probes for heavy metals have been examined. These have involved ad
sorbed monolayers of host molecules, functionalized self-assembled monolaye
rs and thin polymeric films. Two systems are presented that focus on the se
lective analysis of Hg(II) and Fe(II). The electrode for Hg(II) is based on
a macrocyclic ligand, i.e., Kryptofix-222, while that for Fe(LI) relies on
the selective complexation by ferroin ligands, such as 1,10-phenanthroline
, The monomeric and polymeric approaches were examined and compared for bot
h systems. The principal aim of this manuscript is to highlight the ability
of fine-tuning the selectivity characteristics of the solid-liquid interfa
ce as a result of considering and optimizing analyte-interface interactions
. We find that basically, an interface comprising a monolayer, which is cap
able of forming a strong and selective complex with the analyte, is likely
to exhibit sensitivity that is at least as good as a polymeric film. On the
other hand the stability and durability of the latter usually makes it a s
uperior interface for repetitive analysis and will therefore be the preferr
ed choice for flow analysis systems.