Mass transport limitations for electrochemical sensing in low-flux excretory fluids

Despite non-invasive instant monitoring of sweat metabolites is becoming a general trend in early diagnostics and screening, the reliability and accuracy of the on-skin electrochemical biosensors in real-life scenarios still remain questionable. As a rule, mass transport effects in scantily excreted liquids are ignored, when considering the design of such wearable setups. Here we provide a comprehensive investigation of the disruption factors for commonly used Prussian Blue based (bio)sensors under different hydrodynamic conditions (2 × 10^-5 - 5 × 10⁰ mm s^-1 electrolyte velocity). A huge effect of flow on the (bio)sensors response has been revealed and explained with transport limitations for both analyte influx and reaction product outflux. It suggests no need for improving the sensor sensitivity, while minimizing analyte consumption and enhancing product withdrawal. Some strategies concerning measurement schemes and sensor design ensuring reliable sweat analysis have been discussed and illustrated for lactate and glucose on-skin monitoring.