A novel chemiresistor sensor for detection of organic analytes in high-conductivity aqueous electrolyte solution is reported. The chemiresistor sensor is based on thin films of gold nanoparticles capped with a 1-hexanethiol monolayer that is inkjet printed onto a microelectrode. In order for a change in nanoparticle film resistance to be measured, the electronic conduction must preferentially occur through the nanoparticle film rather than through the high-conductivity electrolyte solution. This was achieved by miniaturizing the chemiresistor device such that the double layer capacitance of the electrodes in contact with the electrolyte solution gives rise to a significantly larger impedance compared to the nanoparticle film resistance. This system was shown to be sensitive to simple organics dissolved in an aqueous electrolyte solution. The organic analytes, dissolved in the aqueous solution, partition into the hydrophobic nanoparticle film causing the nanoparticle film to swell, resulting in an increase in the low-frequency impedance of the sensor. An increase in the impedance, at 1 Hz, of the gold nanoparticle chemiresistor on exposure to toluene, dichloromethane, and ethanol dissolved in 1 M KCl solution was demonstrated with detection limits of 0.1, 10, and 3000 ppm, respectively. Titration curves over 3 orders of magnitude could be obtained for analytes such as toluene.

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Exposure of a Au(111) surface to ethynylbenzene in solution leads to the formation of a bound hydrocarbon monolayer. A chemisorption process occurs to give a stable layer consisting of oxygencontaining hydrocarbon species. Ethynylbenzene itself does not oxidize under the deposition conditions 2 indicating that the gold surface facilitates the oxidation process. Calculations show that ethynylbenzene and its oxidation products phenylacetic acid and phenyloxirane have positive binding energies to the gold surface. 1,4-diethynylbenzene also binds to Au(111) and anchors gold nanoparticles deposited from solution to form dense, semi-regular arrays.3

Chemiresistor sensors based on thin films of gold nanoparticles capped with hydrophobic hexanethiol or hydrophilic 6-hydroxyhexanethiol self-assembled monolayers are shown to respond to organic analytes in aqueous solution. Although considerable swelling of the 6-hydroxyhexanethiol-capped nanoparticle film by water occurred, the 6-hydroxyhexanethiol-capped nanoparticle film still responded toward the presence of organic analytes in aqueous solution. The response toward nonpolar analytes (toluene, hexane, dichloromethane) was reduced for the 6-hydroxyhexanethiol-capped chemiresistor compared to the hexanethiol-capped chemiresistor. However, for polar analytes such as ethanol the response sensitivity was reversed. A simple theoretical model describing the chemiresistor response in water is presented and was used to determine the partition coefficients between the nanoparticle film and water for ethanol and toluene.