Lech Wieczorek

Mie and Bragg Plasmons in Subwavelength Silver Semi-Shells

2D arrays of silver semi-shells of 100 and 200 nm diameter display complex reflection and transmission spectra in the visible and near-IR. Here these spectral features are deconstructed and it is demonstrated that they result from the coupling of incident light into a delocalized Bragg plasmon, and the latters induction of localized Mie plasmons in the arrays. These phenomena permit the excitation of transverse dipolar plasmon resonances in the semi-shells despite an ostensibly unfavorable orientation with respect to normally incident light. The resulting spectral feature in the mid-visible is strong and tunable.

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.

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.

Molecular Engineering of G Protein-Coupled Receptors and G Proteins for Cell-Free Biosensing

The ability to express and purify modified recombinant proteins, so they retain their biological function in a cell-free format, has provided a basis for development of molecular biosensors. Here we utilize recombinant G Protein-coupled receptors (GPCRs) and their G proteins for cell-free detection of various binding partners. Fusion peptides were used to improve surface-attachment and fluorescent-labelling capabilities. A novel homogeneous fluorescence resonance energy transfer (FRET)-based assay was developed to detect rearrangements in the G protein heterotrimer. By using this heterotrimeric ‘molecular switch’, we are developing a generic technology such that multiple GPCRs could be assayed for ligand-mediated activation while tethered to surfaces or in solution, with increased throughput compared to current assay platforms.

Electrical noise in gold nanoparticle chemiresistors: Effects of measurement environment and organic linker properties

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 devices 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.

Contact effects in single-molecule conduction

Electronic components based on single organic molecules hold great promise for applications in sensing and information processing. To make progress in this area, a good understanding of the conduction process at the single-molecule level is required. The authors present results of our investigations of single-molecule conduction. Theoretical modeling reveals that small variations in the atomic contact configuration can have a pronounced effect on the conduction through a molecular junction. This is reflected in experimental results for the single-molecule conduction of alkanes that are bound to gold electrodes via end groups with different bond strength.

Electron transport in nanoparticle assemblies

The electrical resistance of nanoparticle assemblies in the form of thin films shows semiconductor-like behavior at low temperatures and metal-like behaviour at high temperatures. We show that this resistance behavior is due to the interplay between Coulomb blockade reduced tunneling of electrons between nanoparticles and the thermal expansion of the nanoparticle assembly. We develop a detailed theoretical model that describes the electron transport process and show that the model agrees well with experimental data.

Determination of alkanes in aqueous solution using gold nanoparticle chemiresistors: Dynamic response characteristics

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.