Development of Agricultural Sensors Based on Conductive Polymers
Authors: Bendikov Michael , Harmon Thomas C. 
Published: December 2021

In this 1-year feasibility study, we tried polymerization of several different monomers, commercial as well as novel, specially designed and synthesized for this project in the presence of the nitrate ion to produce imprinted conductive polymers. Polymers 1 and 2 (shown below) produced a response to nitrate, but one inferior to that produced by a polypyrrole (Ppy)-based sensor (which we demonstrated prior to this study). Thus, we elected to proceed with improving the stability of the Ppy-based sensor.  In order to improve stability of the Ppy-based sensor, we created a two-layer design which includes nitrate-doped Ppy as an inner layer, and nitrate-doped PEDOT as the outer layer. PEDOT is known for its high environmental stability and conductivity. This design has demonstrated promise, but is still undergoing optimization and stability testing. Previously we had failed to create nitrate-doped PEDOT in the absence of a Ppy layer. Nitrate-doped PEDOT should be very promising for sensor applications due to its high stability and exceptional sensing properties as we showed previously for sensing of perchlorate ions (by perchlorate-doped PEDOT). During this year, we have succeeded in preparing nitrate-doped PEDOT (4 below) by designing a new starting monomer (compound 3 below) for polymerization. We are currently testing this design for nitrate sensing. In parallel with the fabrication design studies, we fabricated and tested nitrate-doped Ppy sensors in a series of flow studies under laboratory and field conditions. Nitrate-doped Ppy sensors are less stable than is desirable but provide excellent nitrate sensing characteristics for the short-term experiments focusing on packaging and deployment strategies. The fabricated sensors were successfully interfaced with a commercial battery-powered self-logging (Onset Computer Hobo Datalogger) and a wireless data acquisition and transmission system (Crossbow Technologies MDA300 sensor interface and Mica2 wireless mote). In a series of flow-through experiments with water, the nitrate-doped Ppy sensors were exposed to pulses of dissolved nitrate and compared favorably with an expensive commercial sensor. In 24-hour field tests in both Merced and in Palmdale, CA agricultural soils, the sensors responded to introduced nitrate pulses, but with different dynamics relative to the larger commercial sensors. These experiments are on-going but suggest a form factor (size, shape) effect of the sensor when deployed in a porous medium such as soil. To fill the need for a miniature reference electrode, we identified and tested one commercial version (Cypress Systems, ESA Mini-reference electrode) which works well but is expensive ($190). To create an inexpensive miniature reference electrode, we are exploring the use of AgCl-coated silver wire. This electrode is not a “true” reference electrode; however, it can calibrated once versus a commercial reference electrode at the time of deployment in soil. Thus, only one commercial reference electrode would suffice to support a multiple sensor deployment.