In vivo monitoring of extracellular
calcium ion (Ca2+) is of great importance due to its significant
contributions in
different (patho)physiological processes. In this study, we develop
a potentiometric method with solid-state ion-selective electrodes
(ISEs) for in vivo monitoring of the dynamics of the extracellular
Ca2+ by using hollow carbon nanospheres (HCNs) as a transducing
layer and solid contact to efficiently promote the ion-to-electron
transduction between an ionophore-doped solvated polymeric membrane
and a conducting substrate. We find that the use of HCNs essentially
improves the stability of the signal response and minimizes the potential
drift of the as-prepared ISEs. With three-shelled HCNs (3s-HCNs) as
the transducing layer, we fabricate a solid-state Ca2+-selective
microelectrode by forming a Ca2+-selective membrane with
calcium ionophore II as the recognition unit, 2-nitrophenyl octyl
ether as the plasticizer, sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]
borate as the ion exchanger, and polyvinyl chloride polymeric as the
matrix onto the 3s-HCN-modified carbon fiber electrodes. The as-prepared
electrode shows a high stability and a near Nernst response of 28
mV/decade toward Ca2+ over a concentration range from 10–5 to 0.05 M as well as a good selectivity against species
endogenously existing in the central nervous system. With these properties,
the electrode is used for real-time recording of the dynamics of extracellular
Ca2+ during spreading depression induced by electrical
stimulation, in which the extracellular Ca2+ in rat cortex
is found to decrease by 50.0 ± 7.5% (n = 5)
during spreading depression. This study essentially offers a new platform
to develop solid-state ISEs, which is particularly useful for in vivo
measurements of metal ions and pH in live rat brain.