Voltammetric pH Measurements in Unadulterated Foodstuffs, Urine, and Serum with 3D-Printed Graphene/Poly(Lactic Acid) Electrodes

The pH of a system is a critical descriptor of its chemistry - impacting reaction rates, solubility, chemical speciation, and homeostasis. As a result, pH is one of the most commonly measured parameters in food safety, clinical, and environmental laboratories. Glass pH probes are the gold standard for pH measurements but suffer drawbacks including frequent recalibration, wet storage of the glass membrane, difficulty in miniaturization, and interferences from alkali metals. In this work, we describe a voltammetric pH sensor that uses a three-dimensional (3D)-printed graphene/poly(lactic acid) filament electrode that is pretreated to introduce quinone functional groups to the graphene surface. After thoroughly characterizing the pretreatment parameters using outer-sphere and inner-sphere redox couples, we measured pH by reducing the surface-bound quinones, which undergo a pH-dependent 2e-/2H+ reduction. The position of the redox peak was found to shift -60 ± 2 mV pH-1 at 25 °C, which is in excellent agreement with the theoretical value predicted by the Nernst Equation (-59.2 mV pH-1). Importantly, the sensors did not require the removal of dissolved oxygen prior to successful pH measurements. We investigated the impact of common interfering species (Pb2+ and Cu2+) and found that there was no impact on the measured pH. We subsequently challenged the sensors to measure the pH of unadulterated complex samples, including cola, vinegar, an antacid tablet slurry, serum, and urine, and obtained excellent agreement compared to a glass pH electrode. In addition to the positive analytical characteristics, the sensors are extremely cheap and easy to fabricate, making them highly accessible to a wide range of researchers. These results pave the way for customizable pH sensors that can be fabricated in (nearly) any geometry for targeted applications using 3D printing.