Edith Chow

Recent Advances in Paper-Based Sensors

Paper-based sensors are a new alternative technology for fabricating simple, low-cost, portable and disposable analytical devices for many application areas including clinical diagnosis, food quality control and environmental monitoring. The unique properties of paper which allow passive liquid transport and compatibility with chemicals/biochemicals are the main advantages of using paper as a sensing platform. Depending on the main goal to be achieved in paper-based sensors, the fabrication methods and the analysis techniques can be tuned to fulfill the needs of the end-user. Current paper-based sensors are focused on microfluidic delivery of solution to the detection site whereas more advanced designs involve complex 3-D geometries based on the same microfluidic principles. Although paper-based sensors are very promising, they still suffer from certain limitations such as accuracy and sensitivity. However, it is anticipated that in the future, with advances in fabrication and analytical techniques, that there will be more new and innovative developments in paper-based sensors. These sensors could better meet the current objectives of a viable low-cost and portable device in addition to offering high sensitivity and selectivity, and multiple analyte discrimination. This paper is a review of recent advances in paper-based sensors and covers the following topics: existing fabrication techniques, analytical methods and application areas. Finally, the present challenges and future outlooks are discussed.

Exploring the use of the tripeptide Gly–Gly–His as a selective recognition element for the fabrication of electrochemical copper sensors

The modification of electrodes with the tripeptide Gly-Gly-His for the detection of copper in water samples is described in detail. The tripeptide modified electrode was prepared by first self-assembling 3-mercaptopropionic acid (MPA) onto the gold electrode followed by covalent attachment of the tripeptide to the self-assembled monolayer using carbodiimide coupling. The electrodes were characterized using electrochemistry, a newly developed mass-spectrometry method and quantum mechanical calculations. The mass spectrometry confirmed the modification to proceed as expected with peptide bonds formed between the carboxylic acids of the MPA and the terminal amine of the peptide. Electrochemical measurements indicated that approximately half the MPA molecules in a SAM are modified with the peptide. The peptide modified electrodes exhibited high sensitivity to copper which is attributed to the stable 4N coordinate complex the peptide formed around the metal ion to give copper the preferred tetragonal coordination. The formation of a 4 coordinate complex was predicted using quantum mechanical calculation and confirmed using mass spectrometry. The adsorption of the copper to the peptide modified electrode was consistent with a Langmuir isotherm with a binding constant of (8.1 +/- 0.4) 10(10) M(-1) at 25 degrees C.

Voltammetric detection of cadmium ions at glutathione-modified gold electrodes

An electrochemical sensor for the detection of cadmium ions is described using immobilized glutathione as a selective ligand. First, a self-assembled monolayer of 3-mercaptopropionic acid (MPA) was formed on a gold electrode. The carboxyl terminus then allowed attachment of glutathione (GSH)via carbodiimide coupling to give the MPA-GSH modified electrode. A cadmium ion forms a complex with glutathione via the free sulfhydryl group and also to the carboxyl groups. The complexed ion is reduced by linear and Osteryoung square wave voltammetry with a detection limit of 5 nM. The effect of the kinetics of accumulation of cadmium on the measured current was investigated and modeled. Increasing the temperature of accumulation and electrochemical analysis caused an increase in the voltammetric peak of approximately 4% per degrees C around room temperature. The modified electrode could be regenerated, being stable for more than 16 repeated uses and more than two weeks if used once a day. Some interference from Pb(2+) and Cu(2+) was observed but the effects of Zn(2+), Ni(2+), Cr(3+) and Ba(2+) were insignificant.

Gold nanoparticle chemiresistor sensor array that differentiates between hydrocarbon fuels dissolved in artificial seawater.

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.

Sintered gold nanoparticles as an electrode material for paper-based electrochemical sensors

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.

Biosensors for Detecting Metal Ions: New Trends

The toxicity of metal ions to flora and fauna makes the monitoring of metals in the environment vital. Current methods of metal ion monitoring involve using classical elemental analysis techniques such as atomic absorption spectroscopy (AAS), inductively coupled plasma mass spectroscopy (ICPMS), and anodic stripping voltammetry (ASV). These classical analytical techniques are reliable and fast but suffer from two key problems. Firstly, they require the sample to be transported from the site of collection to a laboratory; secondly, they monitor either the total metal ion concentration or a labile concentration. The true toxicity of metal ions in the environment, however, is related to the amount of bioavailable metal rather than total metal.[1] Bioavailability is a somewhat loosely defined term as what is regarded as a bioavailable metal may vary from one species to the next.[2] As the water safety guidelines can only reflect the reliable measurement techniques available, the current guidelines attempt to assess bioavailability using a combination of techniques including filtration, ion exchange, ASV, chemical modeling of toxicity; and, if necessary, the effect on the target organism.[3] Such analyses are complicated and certainly not particularly compatible with monitoring in the field. So the challenges to the analytical community are to develop methods for on-site measurement of metal ion levels which may give an indication of the bioavailability of at least some metals. For any new analytical method to be competitive with AAS, ICP-MS, and ASV it is essential that it is reliable, robust, easy to use, and able to measure a suite of metals (all criteria met by these classical methods). The ability to undertake analyses in the field, cheaply and easily, is also desirable. These essential and desired criteria for a new analytical method are compatible with what biosensors are claimed to be able to achieve.[4] Biosensors have most frequently been applied to the detection of organic and biological molecules.[4–8] Thus far there has been little research into the detection of metals using biosensors. In the quest to have analytical methods which measure metals in the field, biosensors appear to be ideal as the recognition molecule is a biological molecule and hence could provide an indication of how the metal ions interact with a particular organism. The possibilities of detecting metal ions using biosensors and biological molecules have begun to attract more interest recently. The purpose of this article is to outline what has been achieved thus far in the detection of metal ions using biosensors. Initially we will discuss more mature biosensor technologies for monitoring metals which use enzymes and bacteria whereupon attention will turn to some new approaches which have recently been described. It is important to emphasize that selectivity in metal ion sensing is often more important than sensitivity because trace levels of heavy metals are present in a sample containing other ionic species which are often a million-fold more concentrated.[9]

Toward Paper-Based Sensors: Turning Electrical Signals into an Optical Readout System

Paper-based sensors are gaining increasing attention for their potential applications in resource-limited settings and for point-of-care analysis. However, chemical analysis of paper-based electronic sensors is frequently interpreted using complex software and electronic displays which compromise the advantages of using paper. In this work, we present two semiquantitative paper-based readout systems that can visually measure a change in resistance of a resistive-based sensor. The readout systems use electrochromic Prussian blue/polyaniline as an electrochromic indicator on a resistive gold nanoparticle film that is fabricated on paper. When the readout system is integrated with a resistive sensor in an electrical circuit, and a voltage is applied, the voltage drop along the readout system varies depending on the sensors resistance. Due to the voltage gradient formed along the gold nanoparticle film, the overlaying Prussian blue/polyaniline will change color at voltages greater than its reduction voltage (green/blue for oxidized state and transparent for reduced state). Thus, the changes in resistances of a sensor can be semiquantified through color visualization by either measuring the length of the transparent film (analog readout system) or by counting the number of transparent segments (digital readout system). The work presented herein can potentially serve as an alternative paper-based display system for resistive sensors in instances where cost and weight is a premium.

High-throughput fabrication and screening improves gold nanoparticle chemiresistor sensor performance.

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.

Dynamic response of gold nanoparticle chemiresistors to organic analytes in aqueous solution

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.

Electrochemical Detection of Heavy Metal Ions Using Amino Acids and Oligopeptides as Complexing Ligands

Using biological components to provide selectivity for monitoring heavy metal ions in sensory devices are attractive due to the natural occurrence of metal-binding peptides and proteins. They have advantages over conventional analytical techniques such as atomic absorption spectroscopy, inductively coupled plasma mass spectrometry and anodic stripping voltammetry, because they have the potential to give an estimate of the bioavailability of heavy metals as opposed to measuring total metal concentrations. The metal-binding properties of peptides have been studied extensively [ 1 ] but research into using amino acids and peptides as biosensors for the detection of heavy metal ions is relatively new. Apart from the selectivity imparted from using different peptide ligands, an additional level of selectivity can be achieved by exploiting the different redox potentials of different metals. As a consequence, the following work describes the use of peptide-modified electrodes as highly selective and sensitive metal ion biosensors. [ 2 ]