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We present the flow synthesis of 4-(dimethylamino)pyridine (DMAP)-stabilised gold nanoparticles in a biphasic flow reactor system. In the first stage, the reduction of gold chloride using sodium borohydride took place via gas permeable tubing to minimise pressure build-up in the lines due to hydrogen gas liberation. The use of liquid–liquid membrane separators enabled automatic washing of the intermediate tetraoctylammonium bromide (TOAB)-stabilised gold nanoparticles and for subsequent phase transfer of the organic nanoparticles to the aqueous phase using DMAP. Through a systematic investigation of DMAP concentration and ratio, the amount of DMAP necessary for full transfer of the gold nanoparticles was elucidated. This semi-automated, scalable flow process enabled the production of gold nanoparticles in high yield, with good batch-to-batch reproducibility and improved monodispersity compared to conventional batch methods.

The analyte sensitivity of a chemical sensor is commonly tuned by the type of chemical recognition element. Here, it is shown that the solvent also plays a critical role in the sensing performance of thiol-capped gold nanoparticle film chemiresistors. Both the resistance change and speed of response of the chemiresistor can be optimised by adjusting the composition of methanol and water used for detection of the pesticide permethrin. It is shown that the resistance change is governed by the partitioning of the analyte between the thiol coating of the gold nanoparticles and the solvent. The partition coefficient, log P, has a strong influence on the response magnitude and is directly correlated to the response time. By varying the solvent, the log P of extremely high partitioning analytes such as permethrin in water can be lowered, and a much larger resistance change can be obtained in a shorter time period (5 min). A theoretical model is developed that correlates the experimental findings to changes in analyte partition coefficient with solvent type and composition. The results have significant implications for the design of chemical sensors and solvent conditions that can offer an enhanced signal within a practical timeframe.

Nanozymes are advanced nanomaterials which mimic natural enzymes by exhibiting enzyme-like properties. As nanozymes offer better structural stability over their respective natural enzymes, they are ideal candidates for real-time and/or remote environmental pollutant monitoring and remediation. In this review, we classify nanozymes into four types depending on their enzyme-mimicking behaviour (active metal centre mimic, functional mimic, nanocomposite or 3D structural mimic) and offer mechanistic insights into the nature of their catalytic activity. Following this, we discuss the current environmental translation of nanozymes into a powerful sensing or remediation tool through inventive nano-architectural design of nanozymes and their transduction methodologies. Here, we focus on recent developments in nanozymes for the detection of heavy metal ions, pesticides and other organic pollutants, emphasising optical methods and a few electrochemical techniques. Strategies to remediate persistent organic pollutants such as pesticides, phenols, antibiotics and textile dyes are included. We conclude with a discussion on the practical deployment of these nanozymes in terms of their effectiveness, reusability, real-time in-field application, commercial production and regulatory considerations.

Exposing a thiol-functionalised gold nanoparticle film chemiresistor to methanol in aqueous solution results in only a small electric current response as the thiol ligand/water partition coefficient of methanol is small, leading to only minor swelling of the chemiresistor film. Nevertheless, the current response to methanol can be enhanced if the chemiresistor becomes pre-exposed to a molecule with a large ligand/water partition coefficient P (e.g. octane with Po = 104.3). The large response enhancement is achieved because methanol, when added to an aqueous solution of octane, lowers the large initial partition coefficient of octane. Octane exiting the thiol ligands then leads to strong film shrinkage resulting in a relative current change much greater than the one otherwise induced by methanol alone. This was theoretically modelled for octane and heptane (Ph = 103.6). A strong response enhancement to methanol (>20 times) was observed experimentally by exposure to 2 ppm octane compared to direct testing of methanol in aqueous solution. Besides octane and heptane, molecules with P > 107 (e.g. permethrin) can theoretically be used to provide enhancement factors of several orders of magnitude. For practical reasons, heptane and octane saturate more quickly, thus enabling more rapid detection of methanol than higher P organic molecules.

The response time of chemiresistors consisting of gold nanoparticles coated with self-assembled monolayers (SAM) of 1-hexanethiol, exposed to different hydrocarbons dissolved in water, is investigated with respect to the analyte SAM/water partition coefficient, the analyte−water flow velocity, and the nanoparticle film thickness. We show experimentally that the response time is proportional to the analyte SAM/water partition coefficient and that for sufficiently large velocities the response time becomes flow velocity independent. The dependence of the response time on film thickness is found to be different in the two different flow velocity regimes examined. We outline in detail a theoretical model that explains our experimental data.

Gold nanoparticle films (Au(NPF)) functionalized with a range of hydrophobic and hydrophilic thiols were assembled in chemiresistor sensor arrays that were used to differentiate between complex mixtures of analytes in the aqueous phase. A chemiresistor array sampled a simple system of linear alcohols (methanol, ethanol, propan-1-ol, and butan-1-ol) dissolved in water over a range of concentrations. Discriminant analysis confirmed that the response patterns of the array could be used to successfully distinguish between the different alcohol solutions at concentrations above 20 mM for all of the alcohols except methanol, which was distinguished at concentrations above 200 mM. Alcohol solutions more dilute than these concentrations had response patterns that were not consistently recognizable and failed cross validation testing. This defined the approximate limit of discrimination for the system, which was close to the limits of detection for the majority of the individual sensors. Another Au(NPF) chemiresistor array was exposed to, and successfully identified crude oil, diesel, and three varieties of gasoline dissolved in artificial seawater at a fixed concentration. This work is a demonstration that the pattern of responses from an array of differently functionalized Au(NPF) sensors can be used to distinguish analytes in the aqueous phase.

Gold nanoparticles functionalized with mixtures of 1-hexanethiol and 4-mercaptophenol were investigated as chemiresistor sensors for use in aqueous solutions. X-ray photoelectron spectroscopy (XPS) studies confirmed that it was possible to form mixed ligand compositions on the surface of the nanoparticles. Nanoparticle films with a higher proportion of 1-hexanethiol as the ligand resulted in higher impedances than those with lower proportions. The electrical response of the chemiresistor to toluene, dichloromethane, hexane and ethanol dissolved in water was found to depend strongly on the composition of the organic ligand used to cap the gold nanoparticles. 1-Hexanethiol-coated gold nanoparticles were sensitive to non-polar analytes whereas the sensitivity was reduced upon increasing the composition of 4-mercaptophenol on the surface. It was also shown that the sensitivity to ethanol could be enhanced 3-fold by using a sensor that was functionalized with a mixture of 60% 1-hexanethiol and 40% 4-mercaptophenol compared to a sensor functionalized with pure thiols only.

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.

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.

Chemiresistor sensor arrays are a promising technology to replace current laboratory-based analysis instrumentation, with the advantage of facile integration into portable, low-cost devices for in-field use. To increase the performance of chemiresistor sensor arrays a high-throughput fabrication and screening methodology was developed to assess different organothiol-functionalized gold nanoparticle chemiresistors. This high-throughput fabrication and testing methodology was implemented to screen a library consisting of 132 different organothiol compounds as capping agents for functionalized gold nanoparticle chemiresistor sensors. The methodology utilized an automated liquid handling workstation for the in situ functionalization of gold nanoparticle films and subsequent automated analyte testing of sensor arrays using a flow-injection analysis system. To test the methodology we focused on the discrimination and quantitation of benzene, toluene, ethylbenzene, p-xylene, and naphthalene (BTEXN) mixtures in water at low microgram per liter concentration levels. The high-throughput methodology identified a sensor array configuration consisting of a subset of organothiol-functionalized chemiresistors which in combination with random forests analysis was able to predict individual analyte concentrations with overall root-mean-square errors ranging between 8-17 μg/L for mixtures of BTEXN in water at the 100 μg/L concentration. The ability to use a simple sensor array system to quantitate BTEXN mixtures in water at the low μg/L concentration range has direct and significant implications to future environmental monitoring and reporting strategies. In addition, these results demonstrate the advantages of high-throughput screening to improve the performance of gold nanoparticle based chemiresistors for both new and existing applications.

The performance of chemiresistor sensors made from thin film assemblies of single-wall carbon nanotubes, multiwall carbon nanotubes, reduced graphene oxide nanosheets (RGON), and gold nanoparticles (AuNP) was assessed with an immersible microelectrode array. Carbon nanotube and RGON chemiresistors were functionalized with octadecyl-1-amine and the AuNP chemiresistors were functionalized with 1-hexanethiol. The analytes examined were aqueous solutions of petroleum hydrocarbons: cyclohexane, naphthalene, benzene, toluene, ethylbenzene, and the three isomers of xylene (BTEX analytes). Titrations were performed to determine the detection limits of the different chemiresistors. The AuNP chemiresistor was the most sensitive to all the analytes with limits of detection between 0.2 and 0.6 ppm in water. In contrast, the multiwall carbon nanotube chemiresistor was the least sensitive to the analytes with limits of detection between 20 and 200 ppm. These sensitivities show that these nanomaterials have the potential, with further optimization, of being incorporated into devices that would respond to hydrocarbons in water at concentrations relevant to the regulations of the US Environmental Protection Agency. The stability of the sensors over 26 days was also assessed. Remarkably, there was a negligible change in the electrical resistance of the RGON sensors over this time. The nanotube sensors increased in resistance and the AuNP decreased in resistance over the same period. The drifting resistances did not affect the sensitivity of the nanomaterials, which remained constant with time.

The porosity of 1-hexanethiol-functionalised gold nanoparticle films was assessed and utilised as chemiresistor sensors. Electrochemical capacitance measurements showed that the accessibility of electrolytes of different ionic strengths into the pores depended on the thickness of the electric double layer formed. A large variation in capacitance was measured in 0.01–1000 mM NaClO4, implying a wide pore size distribution. The change in morphology of the nanoparticle films upon storage in air, water and ethanol for two weeks was investigated. There was a significant decrease in the electrochemical capacitance at high electrolyte concentrations for the ethanol-stored films compared to the freshly-prepared films suggesting a decrease in the number of small pores of radii in the range of 0.3–3 nm. This was further supported by optical topographical measurements where a decrease in the thickness of ethanol-stored films was observed relative to the freshly-prepared films. The porous nature of the nanoparticle films was found to have an effect on the chemical sensing behaviour. When used as chemiresistor sensors, for the detection of heptane in water, the ethanol-stored films provided larger resistance changes and longer response times. This suggests that the more densely packed ethanol-stored films provided more sites that enabled film swelling, and that diffusion of the analyte occurred through the narrower water-filled pores. This demonstrates the effect of different storage conditions on film morphology and subsequently sensor response.

Functionalised gold nanoparticle (Au(NP)) chemiresistors are investigated for direct sensing of small organic molecules in biological fluids. The principle reason that Au(NP) chemiresistors, and many other sensing devices, have limited operation in biological fluids is due to protein and lipid fouling deactivating the sensing mechanism. In order to extend the capability of such chemiresistor sensors to operate directly in biofluids, it is essential to minimise undesirable matrix effects due to protein and lipidic components. Ultrafiltration membranes were investigated as semi-permeable size-selective barriers to prevent large biomolecule interactions with Au(NP) chemiresistors operating in protein-loaded biofluids. All of the ultrafiltration membranes protected the Au(NP) chemiresistors from fouling by the globular biomolecules, with the 10 kDa molecular weight cut-off size being optimum for operation in biofluids. Titrations of toluene in different protein-loaded fluids indicated that small molecule detection was possible. A sensor array consisting of six different thiolate-functionalised Au(NP) chemiresistors protected with a size-selective ultrafiltration membrane successfully identified, and discriminated the spoilage of pasteurised bovine milk. This proof-of-principle study demonstrates the on-chip protein separation and small metabolite detection capability, illustrating the potential for this technology in the field of microbial metabolomics. Overall, these results demonstrate that a sensor array can be protected from protein fouling with the use of a membrane, significantly increasing the possible application areas of Au(NP) chemiresistors ranging from the food industry to health services.

We investigate the response dynamics of 1-hexanethiol-functionalized gold nanoparticle chemiresistors exposed to the analyte octane in aqueous solution. The dynamic response is studied as a function of the analyte-water flow velocity, the thickness of the gold nanoparticle film and the analyte concentration. A theoretical model for analyte limited mass-transport is used to model the analyte diffusion into the film, the partitioning of the analyte into the 1-hexanethiol capping layers and the subsequent swelling of the film. The degree of swelling is then used to calculate the increase of the electron tunnel resistance between adjacent nanoparticles which determines the resistance change of the film. In particular, the effect of the nonlinear relationship between resistance and swelling on the dynamic response is investigated at high analyte concentration. Good agreement between experiment and the theoretical model is achieved.

A sensor array of gold nanoparticle chemiresistors, functionalized with a variety of thiolate ligands, was used to detect different hydrocarbons dissolved in water. Discriminant analysis of the sensor responses showed that the diluted saturated solutions of kerosene, turpentine, two types of oil and three types of petrol could be clearly identified across a range of concentrations.

This study was conducted to assess and characterize the intrinsic electrical noise associated with thiolate functionalized gold nanoparticle films utilized as chemiresistor sensors. Recently, this sensor type has been demonstrated to have liquid-based sensing capabilities. Differences in the thermal noise component of the different thiolate functionalized nanoparticle films in ambient air and in deionized water are detailed. Comparable values are found between real impedance values and resistance values derived from the Nyquist equation, in the frequency domain, for differing chemical measurement environments. Voltage-biased studies in aqueous media demonstrate the device's retention of the intrinsic 1/f noise, known to exist in gold nanoparticle chemiresistors operating in ambient air. These results have implications on the ultimate sensitivity of devices utilized for liquid-based analyte detection.

The electrical impedance change and response time of chemiresistor sensors based on gold nanoparticles capped with 1-hexanethiolate ligands were investigated for several organic analytes dissolved in aqueous solution. Analytes that partitioned strongly into the nanoparticle film resulted in greater impedance changes and longer response times than analytes which had a smaller partition coefficient.

The influence of film morphology on the performance of inkjet-printed gold nanoparticle chemiresistors has been investigated. Nanoparticles deposited from a single-solvent system resulted in a "coffee ring"-like structure with most of the materials deposited at the edge. It was shown that the uniformity of the film could be improved if the nanoparticles were deposited from a mixture of solvents comprising N-methyl-2-pyrrolidone and water. Electrical conductivity measurements showed that both "coffee ring" and "flat" films were qualitatively similar suggesting that the films have similar nanoscale structures. To form the functional chemiresistor device, the 4-(dimethylamino)pyridine coating on the nanoparticle was exchanged with 1-hexanethiol to provide a hydrophobic sensing layer. The performance of 1-hexanethiol coated gold nanoparticle chemiresistors to small organic molecules, toluene, dichloromethane and ethanol dissolved in 1 M KCl in regard to changes in impedance and response times was unaffected by the film morphology. For larger hydrocarbons such as octane, the rate of uptake of the analyte into the film was significantly faster when the flatter nanoparticle film was used as opposed to the "coffee ring" film which has a thicker edge. Furthermore, the presence of potassium and chloride ions in the solution media does not significantly affect the impedance of the nanoparticle film at 1 Hz (

A simple and economical process for fabricating gold electrodes on paper is presented. Gold nanoparticles stabilised with 4-(dimethylamino)pyridine were applied to nail-polish coated filter paper and made conductive using a camera flash sintering step. To test the ability of the sintered gold nanoparticle film to function as a sensing platform, cysteine was self-assembled on gold and used for the electrochemical determination of copper ions. The cysteine-sintered gold nanoparticle film was able to successfully complex copper ions, with only minor differences in performance compared with a standard cysteine-modified solid-state gold disk electrode. Investigations by Raman spectroscopy revealed the successful removal of the 4-(dimethylamino)pyridine coating during sintering, whereas electrochemical impedance spectroscopy and scanning electron microscopy suggested that differences in the sensing performance could be attributed to the rougher morphology of the sintered gold nanoparticle electrode.