Electrochemical synthesis of 2D-silver nanodendrites functionalized with cyclodextrin for SERS-based detection of herbicide MCPA.

Surface enhanced Raman spectroscopy (SERS) is a powerful analytical technique that has found application in the trace detection of a wide range of contaminants. In this paper, we report on the fabrication of 2D silver nanodendrites, on silicon chips, synthesized by electrochemical reduction of AgNO3at microelectrodes. The formation of nanodendrites is tentatively explained in terms of electromigration and diffusion of silver ions. Electrochemical characterization suggests that the nanodendrites do not stay electrically connected to the microelectrode. The substrates show SERS activity with an enhancement factor on the order of 106. Density functional theory simulations were carried out to investigate the suitability of the fabricated substrate for pesticide monitoring. These substrates can be functionalized with cyclodextrin macro molecules to help with the detection of molecules with low affinity with silver surfaces. A proof of concept is demonstrated with the detection of the herbicide 2-methyl-4-chlorophenoxyacetic acid (MCPA).

Pen direct writing of SERRS-based lateral flow assays for detection of penicillin G in milk.

Direct pen writing offers versatile opportunities for development of low-cost tests for point-of-care applications. In this work a lateral flow immunoassay (LFIA) test was fabricated by hand "writing" immunoprobes onto hand-cut nitrocellulose strips with a commercial fountain pen. The qualitative capabilities of the test were extended by addition of a Raman reporter and consequent design and fabrication of a Surface Enhanced Resonant Raman Scattering (SERRS)-LFIA test. As proof-of-concept, dual detection of penicillin G was achieved in milk with a visual LOD of 20 ppm and a dynamic range of 0.03-97.5 ppm. Evaluation against equivalent tests performed with conventionally prepared LFIA strips showed comparable results, thus demonstrating the validity of the test. These results demonstrate the potential for further decrease in cost and consequent broader use of LFIA tests in remote regions and resource-limited environments.

Platinum-Based Interdigitated Micro-Electrode Arrays for Reagent-Free Detection of Copper.

Water is a precious resource that is under threat from a number of pressures, including, for example, release of toxic compounds, that can have damaging effect on ecology and human health. The current methods of water quality monitoring are based on sample collection and analysis at dedicated laboratories. Recently, electrochemical-based methods have attracted a lot of attention for environmental sensing owing to their versatility, sensitivity and their ease of integration with cost effective, smart and portable readout systems. In the present work, we report on the fabrication and characterization of platinum-based interdigitated microband electrodes arrays, and their application for trace detection of copper. Using square wave voltammetry after acidification with mineral acids, a limit of detection of 0.8 µg/L was achieved. Copper detection was also undertaken on river water samples and compared with standard analytical techniques. The possibility of controlling the pH at the surface of the sensors-thereby avoiding the necessity to add mineral acids-was investigated. By applying potentials to drive the water splitting reaction at one comb of the sensor's electrode (the protonator), it was possible to lower the pH in the vicinity of the sensing electrode. Detection of standard copper solutions down to 5 µg/L (ppb) using this technique is reported. This reagent free method of detection opens the way for autonomous, in situ monitoring of pollutants in water bodies.

Elimination of Oxygen Interference in the Electrochemical Detection of Monochloramine, Using In Situ pH Control at Interdigitated Electrodes.

Disinfection of water systems by chloramination is a method frequently used in North America as an alternative to chlorination. In such a case, monochloramine is used as the primary chlorine source for disinfection. Regular monitoring of the residual concentrations of this species is essential to ensure adequate disinfection. An amperometric sensor for monochloramine would provide fast, reagent-free analysis; however, the presence of dissolved oxygen in water complicates sensor development. In this work, we used in-situ pH control as a method to eliminate oxygen interference by conversion of monochloramine to dichloramine. Unlike monochloramine, the electrochemical reduction of dichloramine occurs outside the oxygen reduction potential window and is therefore not affected by the oxygen concentration. Potential sweep methods were used to investigate the conversion of monochloramine to dichloramine at pH 3. The pH control method was used to calibrate monochloramine concentrations between 1 and 10 ppm, with a detection limit of 0.03 ppm. Tests were carried out in high alkalinity samples, wherein it was found that the sensitivity of this method effectively remained unchanged. Monochloramine was also quantified in the presence of common interferents (copper, phosphate, and iron) which also had no significant impact on the analysis.

Highly Sensitive SERS Detection of Neonicotinoid Pesticides. Complete Raman Spectral Assignment of Clothianidin and Imidacloprid.

The use of surface enhanced Raman spectroscopy in the development of low cost, portable sensor devices that can be used in the field for nitroguanidine neonicotinoid insecticide detection is appealing. However, a key challenge to achieving this goal is the lack of detailed analysis and vibrational assignment for the most popular neonicotinoids. To make progress toward this goal, this paper presents an analysis of the bulk Raman and SERS spectra of two neonicotinoids, namely clothianidin and imidacloprid. Combined with first-principles simulations, this allowed assignment of all Raman spectral modes for both molecules. To our knowledge, this is the first report of SERS analysis and vibrational assignment of clothianidin, and a comprehensive assignment and analysis is provided for imidacloprid. Silver nanostructured surfaces were fabricated for qualitative SERS analysis, which provides the characteristic spectra of the target molecules and demonstrates the ability of SERS to sense these molecules at concentrations of 1 ng/mL. These concentrations are on par with high-end chromatographic-mass spectroscopy laboratory methods. These SERS sensors thus allow for the selective and sensitive detection of neonicotinoids and provide complementary qualitative data for the molecules. Furthermore, this technique can be adapted to portable devices for remote sensing applications. Further work focuses on integrating our device with an electronics platform for truly portable residue detection.

Structure, stability and water adsorption on ultra-thin TiO2 supported on TiN.

Interfacial metal-oxide systems with ultra-thin oxide layers are of high interest for their use in catalysis. The chemical activity of ultra-thin metal-oxide layers can be substantially enhanced compared to interfacial models with thicker oxide. In this study, we present a Density Functional Theory (DFT) investigation of the structure of ultra-thin rutile layers (one and two TiO2 layers) supported on TiN and the stability of water on these interfacial structures. The rutile layers are stabilized on the TiN surface through the formation of interfacial Ti-O bonds. Charge transfer from the TiN substrate leads to the formation of reduced Ti3+ cations in TiO2. The concentration of Ti3+ is proportionally higher in the ultra-thin oxide, compared to interfacial models with thicker oxide layers. The structure of the one-layer oxide slab is strongly distorted at the interface while the thicker TiO2 layer preserves the rutile structure. The energy cost for the formation of a single O vacancy in the one-layer oxide slab is only 0.5 eV with respect to the ideal interface. For the two-layer oxide slab, the introduction of several vacancies in an already non-stoichiometric system becomes progressively more favourable, which indicates the stability of the highly defective interfaces. Isolated water molecules dissociate when adsorbed at the TiO2 layers. At higher coverages, the preference is for molecular water adsorption. Our ab initio thermodynamics calculations show the fully water covered stoichiometric models as the most stable structure at typical ambient conditions. This behaviour is similar to that observed on thicker oxide in TiO2-TiN interfaces or pure TiO2 surfaces. In contrast, interfacial models with multiple vacancies are most stable at low (reducing) oxygen chemical potential values. The high concentration on reduced Ti3+ introduces significant distortions in the O-defective slab. Whereas, a water monolayer adsorbs dissociatively on the highly distorted 2-layer TiO1.75-TiN interface, where the Ti3+ states lying above the top of the valence band contribute to a significant reduction of the energy gap compared to the stoichiometric TiO2-TiN model. Our results provide a guide for the design of novel interfacial systems containing ultra-thin TiO2 with potential application as photocatalytic water splitting devices.

A potentiometric biosensor for rapid on-site disease diagnostics.

Quantitative point-of-care (POC) devices are the next generation for serological disease diagnosis. Whilst pathogen serology is typically performed by centralized laboratories using Enzyme-Linked ImmunoSorbent Assay (ELISA), faster on-site diagnosis would infer improved disease management and treatment decisions. Using the model pathogen Bovine Herpes Virus-1 (BHV-1) this study employs an extended-gate field-effect transistor (FET) for direct potentiometric serological diagnosis. BHV-1 is a major viral pathogen of Bovine Respiratory Disease (BRD), the leading cause of economic loss ($2 billion annually in the US only) to the cattle and dairy industry. To demonstrate the sensor capabilities as a diagnostic tool, BHV-1 viral protein gE was expressed and immobilized on the sensor surface to serve as a capture antigen for a BHV-1-specific antibody (anti-gE), produced in cattle in response to viral infection. The gE-coated immunosensor was shown to be highly sensitive and selective to anti-gE present in commercially available anti-BHV-1 antiserum and in real serum samples from cattle with results being in excellent agreement with Surface Plasmon Resonance (SPR) and ELISA. The FET sensor is significantly faster than ELISA (<10 min), a crucial factor for successful disease intervention. This sensor technology is versatile, amenable to multiplexing, easily integrated to POC devices, and has the potential to impact a wide range of human and animal diseases.

Luminescent optical detection of volatile electron deficient compounds by conjugated polymer nanofibers.

Optical detection of volatile electron deficient analytes via fluorescence quenching is demonstrated using ca. 200 nm diameter template-synthesized polyfluorene nanofibers as nanoscale detection elements. Observed trends in analyte quenching effectiveness suggest that, in addition to energetic factors, analyte vapor pressure and polymer/analyte solubility play an important role in the emission quenching process. Individual nanofibers successfully act as luminescent reporters of volatile nitroaromatics at sub-parts per million levels. Geometric factors, relating to the nanocylindrical geometry of the fibers and to low nanofiber substrate coverage, providing a less crowded environment around fibers, appear to play a role in providing access by electron deficient quencher molecules to the excited states within the fibers, thereby facilitating the pronounced fluorescence quenching response.

Dual resonance approach to decoupling surface and bulk attributes in photonic crystal biosensor.

A sub-wavelength grating-based photonic crystal sensor is designed to excite two spectrally and spatially different guided mode resonances that have distinctive electric field distributions. We present and validate the uni-polarized dual resonance approach to separating bulk index perturbations from surface-binding events in a single measurement by monitoring the resonance wavelength shifts. This self-referencing method will reduce errors in the measurement of biomolecule binding events on sensor surfaces in a perturbed environmental background.

High aspect ratio nano-fabrication of photonic crystal structures on glass wafers using chrome as hard mask.

Wafer-scale nano-fabrication of silicon nitride (Si x N y ) photonic crystal (PhC) structures on glass (quartz) substrates is demonstrated using a thin (30 nm) chromium (Cr) layer as the hard mask for transferring the electron beam lithography (EBL) defined resist patterns. The use of the thin Cr layer not only solves the charging effect during the EBL on the insulating substrate, but also facilitates high aspect ratio PhCs by acting as a hard mask while deep etching into the Si x N y . A very high aspect ratio of 10:1 on a 60 nm wide grating structure has been achieved while preserving the quality of the flat top of the narrow lines. The presented nano-fabrication method provides PhC structures necessary for a high quality optical response. Finally, we fabricated a refractive index based PhC sensor which shows a sensitivity of 185 nm per RIU.

Highly polarized luminescence from ß-phase-rich poly(9,9-dioctylfluorene) nanofibers.

Novel poly(9,9-dioctlylfluorene) (PFO) nanofibers were fabricated by solution template wetting of anodic aluminum oxide (AAO) templates with a pore diameter of 25 nm. Individual nanofibers displayed a pronounced axially polarized luminescence with a typical emission dichroic ratio of 15 and low spread of the emissive species angular distribution. The strong optical characteristics were ascribed to intrachain reorientation of amorphous PFO to a more planar and elongated ß-phase conformation induced by mechanical strain during polymer template pore infiltration. Absorption optical spectroscopy on nanofiber mats confirmed formation of 24% ß-phase emissive segments, which dominated the nanofiber luminescence characteristics. X-ray diffraction measurements were used to confirm and quantify the extent of nanofiber internal molecular alignment.

Low-cost silver capped polystyrene nanotube arrays as super-hydrophobic substrates for SERS applications.

In this paper, we describe the fabrication, simulation and characterization of dense arrays of freestanding silver capped polystyrene nanotubes, and demonstrate their suitability for surface enhanced Raman scattering (SERS) applications. Substrates are fabricated in a rapid, low-cost and scalable way by melt wetting of polystyrene (PS) in an anodized alumina (AAO) template, followed by silver evaporation. Scanning electron microscopy reveals that substrates are composed of a dense array of freestanding polystyrene nanotubes topped by silver nanocaps. SERS characterization of the substrates, employing a monolayer of 4-aminothiophenol (4-ABT) as a model molecule, exhibits an enhancement factor of ∼1.6 × 10(6), in agreement with 3D finite difference time domain simulations. Contact angle measurements of the substrates revealed super-hydrophobic properties, allowing pre-concentration of target analyte into a small volume. These super-hydrophobic properties of the samples are taken advantage of for sensitive detection of the organic pollutant crystal violet, with detection down to ∼400 ppt in a 2 µl aliquot demonstrated.

Colour-coded photoluminescence and chemiluminescence of fluorene polymer-based organic nanowires in random and organised arrangements.

Organic nanowires based on a fluorene homopolymer and a copolymer, i.e., poly(9,9-dioctylfluorene), F8, and poly(9,9-dioctylfluorene-co-benzothiadiazole), F8BT, respectively, were synthesised by solution assisted wetting of porous anodic alumina templates. Nanowires ranged between 3 microm and 50 microm in length, and were ca. 200 nm in diameter. Absorption and photoluminescence studies of F8BT nanowires yielded spectra characteristic of the parent material. By contrast, the well resolved spectra obtained for F8 nanowires indicated that, during synthesis, a fraction of the molecules within the wires underwent intra-chain re-orientation from the more random molecular conformations of the glassy phase to the more planar extended molecular conformation of the beta-phase. Importantly, both F8 and F8BT nanowires exhibited a distinct emission anisotropy, consistent with internal alignment of the emissive polymer chains along the long axes of the wires. This property was exploited by forming nanowire crossbar structures in which, by selecting either luminescence wavelength or polarisation state, spatial confinement and colour tuning of polarised light emission could be readily achieved. Finally, nanowire chemiluminescence was demonstrated. Characteristic blue and green-yellow luminescence was observed for F8 and F8BT wires, respectively, confirming that these novel nanostructures may act as nanoscale chemiluminescent light sources.

Polarization tunable transmission through plasmonic arrays of elliptical nanopores.

Polarization dependent transmission through thin gold films bearing arrays of elliptical nanopores and assembled at transparent substrates is explored. Far field transmission spectra with incident light polarized along the short and long axis of the ellipses show asymmetric peaks. Near-field finite difference time domain simulated electric field profiles suggest these features are related to Fano resonances between the (± 1, 0) Surface Plasmon Polariton mode and the ( ± 1, 0) Rayleigh Anomaly. The unique spectral signature of these samples makes them attractive for visible and near infrared tags for anti-counterfeiting applications.