Maintaining
the concentrations of various ions in body fluids is
critical to all living organisms. In this contribution, we designed
a flexible microneedle patch coupled electrode array (MNP-EA) for
the in situ multiplexed detection of ion species (Na+,
K+, Ca2+, and H+) in tissue interstitial
fluid (ISF). The microneedles (MNs) are mechanically robust for skin
or cuticle penetration (0.21 N/needle) and highly swellable to quickly
extract sufficient ISF onto the ion-selective electrochemical electrodes
(∼6.87 μL/needle in 5 min). The potentiometric sensor
can simultaneously detect these ion species with nearly Nernstian
response in the ranges wider enough for diagnosis purposes (Na+: 0.75–200 mM, K+: 1–128 mM, Ca2+: 0.25–4.25 mM, pH: 5.5–8.5). The in vivo experiments
on mice, humans, and plants demonstrate the feasibility of MNP-EA
for timely and convenient diagnosis of ion imbalances with minimal
invasiveness. This transdermal sensing platform shall be instrumental
to home-based diagnosis and health monitoring of chronic diseases
and is also promising for smart agriculture and the study of plant
biology.