Determination of 3-nitrotyrosine in human urine samples by surface plasmon resonance immunoassay

This paper describes the detection of a low-molecular weight molecule, 3-nitrotyrosine (3-NT) (∼226 Da), in human urine by coupling indirect inhibition assay with a surface plasmon resonance (SPR) sensor. 3-NT antibody (anti-3-NT Ab, mouse IgG) was used in this assay. An optimal antibody concentration has been measured at 27.9 μg/mL in order to obtain the best performance of the sensor surface. The lowest detection limit for 3-NT with this method is 4.7 ng/mL (S/N = 3). Sensor reliability was demonstrated by good specificity, intra-assay and inter-assay relative standard deviations <8%, average recovery of 107.68 ± 19.4% and sensor surface (self-assembled monolayer) stability through more than 200 regeneration cycles and 15 days of repeated measurement. This is the first SPR biosensor assay of 3-NT in human urine. The high stability of the SPR sensor surface underlies the potential of the SPR method as a low cost diagnostic tool for clinical detection of 3-NT.     

ZnO modified gold disc: A new route to efficient glucose sensing

Surface of a gold disc was modified by depositing ZnO film electrochemically. AFM analysis of the film shows c-axis oriented pillar like structures grown normal to the surface. Sensor surface was prepared by immobilizing glucose oxidase (GOD) on the ZnO modified gold disc. Different concentrations of glucose (50-1000 ng/ml) were taken to monitor the sensor response. Sensor was found to be highly sensitive to low concentrations of glucose and sensitivity increases linearly in the range of 50-250 ng/ml. The high sensitivity of the ZnO modified gold disc may be attributed to the SPR induced electron transfer between the two systems (i.e. Au and ZnO). The work indicates promising application of the system as a tool for studying sensitive bio-specific interactions, with further development of highly sensitive and selective bio-molecular and chemical SPR based optical sensors.     

Full-field surface plasmon resonance sensor for high resolution refractive index measurement using common-path heterodyne interferometer

This study presents a full-field surface plasmon resonance (SPR) sensor induced by attenuated total reflection (ATR)-couple for liquid refractive index measurement. The system adopts a common-path heterodyne interferometer to measure the phase difference between P- and S-wave after passing through the SPR sensor. In order to realize the full-field measurement, it adopts a three-frame integrating-bucket method. The experimental results show great consistency profile between single point and full-field liquid refractive index measurement from 1.330 to 1.340 RIU. It shows that the best sensitivity and resolution of a single pixel in charge couple device (CCD) for liquid refractive measurement are 3.3 × 10⁴ (deg/RIU) and 3.53 × 10⁻⁶ (RIU), respectively. As compared with traditional single-point method, the proposed method with a regular CCD has no degradation. Therefore, the system has many applications in chemistry and biology.     

Surface plasmon resonance immunosensor using Au nanoparticle for detection of TNT

In order to develop the fully integrated portable surface plasmon resonance (SPR) system for detection of explosives, the amplification strategy of SPR signal was investigated. Indirect competitive inhibition method allowed the middle-sized SPR sensor to detect trinitrotoluene (TNT) at ppt level. However, this enhanced SPR signal was not high enough to detect TNT at ppt level by a miniaturized SPR sensor. Therefore, localized surface plasmon resonance (LSPR) effect using Au nanoparticle as further signal amplification approach was used. The amplification method of indirect competitive inhibition and LSPR were combined together for fabrication of the immunosurface using Au nanoparticle. TNT detectable range of this immunosurface was from 10 ppt (10 pg/ml) to 100 ppb (100 ng/ml), which was almost comparable to that without Au nanoparticle. The observed resonance angle change due to binding monoclonal TNT antibody (M-TNT Ab) with the immunosurface modified with Au nanoparticle was amplified to four times higher than that in absence of Au nanoparticle.     

Tethered DNA scaffolds on optical sensor platforms for detection of hipO gene from Campylobacter jejuni

DNA biosensors have gained increased attention over traditional diagnostic methods due to their fast and responsive operation and cost-effective design. The specificity of DNA biosensors relies on single-stranded oligonucleotide probes immobilized to a transduction platform. Here, we report the development of biosensors to detect the hippuricase gene (hipO) from Campylobacter jejuni using direct covalent coupling of thiol- and biotin-labeled single-stranded DNA (ssDNA) on both surface plasmon resonance (SPR) and diffraction optics technology (DOT, dotLab) transduction platforms. This is the first known report of the dotLab to detect targeted DNA. Application of 6-mercapto-1-hexanol as a spacer thiol for SPR gold surface created a self-assembled monolayer that removed unbound ssDNA and minimized non-specific detection. The detection limit of SPR sensors was shown to be 2.5 nM DNA while dotLab sensors demonstrated a slightly decreased detection limit of 5.0 nM (0.005 μM). It was possible to reuse the SPR sensor due to the negligible changes in sensor sensitivity (∼9.7 × 10⁻⁷ ΔRU) and minimal damage to immobilized probes following use, whereas dotLab sensors could not be reused. Results indicated feasibility of optical biosensors for rapid and sensitive detection of the hipO gene of Campylobacter jejuni using specific ssDNA as a probe.     

A silicon-glass-based microfabricated wide range thermal distribution gas flow meter

Recently, there has been high demand on miniaturizations of bio-instruments and wide range gas flux measurement in the field of chemistry and mechanics. This paper presents the design, fabrication, and characterization of a silicon-glass-based thermal distribution gas flow meter (20 mm × 10 mm × 1.6 mm) with a wide detection range. To facilitate the fabrication and maintain the stability of the sensor, a platinum (Pt) thin film was adopted as the heater and thermometers. Both the thermal property and temperature sensitivity of Pt thin film were characterized. SiO₂ passivation layers were deposited on top of the Pt film to prevent thermal and electrical shift of sensitive elements. Three pairs of thermometers were constructed beside the heater. Sensitivity and gas flux range of the gas flow meter can be increased by alternate use of these three sensor pairs. We also introduced a specific hardware control circuit system for real-time gas flux monitoring through the connection with a computer interface. The proposed gas flow sensor device was capable of measuring gas flux within the range of 0.8-2800 ml/min, thus demonstrating the potential for a wide range of applications.     

Highly sensitive label-free immunosensor for ochratoxin A based on functionalized magnetic nanoparticles and EIS/SPR detection

A label-free immunosensor for the detection of ochratoxin A (OTA) based on use of magnetic nanoparticles (MNPs) was developed. A gold electrode was modified using bovine serum albumin conjugate with a glutaraldehyde-thiolamine linker, creating a layer that prevents non-specific binding of OTA on gold. The OTA antibodies were attached to MNPs using the carbodiimide chemistry and afterwards were immobilized on the modified gold electrode using a strong magnetic field. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and surface plasmon resonance (SPR) were used to characterize each step in immunosensor development. The impedance variation due to the specific antibody-OTA interaction was correlated with the OTA concentration in the samples. The increase in electron-transfer resistance values was proportional to the concentration of OTA on a linear range between 0.01 and 5 ng/mL, with a detection limit of 0.01 ng/mL. SPR measurements showed a larger response range (1-50 ng/mL) with a detection limit of 0.94 ng/mL. Analytical results were in accordance with standard ELISA test kit.     

Highly accurate and sensitive surface plasmon resonance sensor based on channel photonic crystal waveguides

A highly sensitive surface plasmon resonance (SPR) sensor based on channel photonic crystal waveguide (PCW) is proposed. The PCW is based on widely used lithographic and nano-fabrication compatible materials like TiO₂ and SiO₂. Gold has been used as a SPR active metal. By rigorously optimizing the different waveguide parameters, we have shown that there is significant transfer of modal power around phase-matching or resonance wavelength which has been utilized to design a compact and highly sensitive sensor for lab on chip. The ultra narrow width (∼765 pm for an interaction length of 10 mm) of surface plasmon resonance curve and sensitivity as high as 7500 nm-RIU⁻¹ will open a new window for bio-chemical sensing applications.     

Gas sensing properties at room temperature of a quartz crystal microbalance coated with ZnO nanorods

Gas sensors based on a quartz crystal microbalance (QCM) coated with ZnO nanorods were developed for detection of NH₃ at room temperature. Vertically well-aligned ZnO nanorods were synthesized by a novel wet chemical route at a low temperature of 90 °C, which was used to grow the ZnO nanorods directly on the QCM for the gas sensor application. The morphology of the ZnO nanorods was examined by field-emission scanning electron microscopy (FE-SEM). The diameter and length of the nanorods were 100 nm and 3 μm, respectively. The QCM coated with the ZnO nanorods gas sensor showed excellent performance to NH₃ gas. The frequency shift (Δf) to 50 ppm NH₃ at room temperature was about 9.1 Hz. It was found that the response and recovery times were varied with the ammonia concentration. The fabricated gas sensors showed good reproducibility and high stability. Moreover, the sensor showed a high selectivity to ammoniac gas over liquefied petroleum gas (LPG), nitrous oxide (N₂O), carbon monoxide (CO), nitrogen dioxide (NO₂), and carbon dioxide (CO₂).     

Ochratoxin A immunoassay with surface plasmon resonance registration: Lowering limit of detection by the use of colloidal gold immunoconjugates

An immunoanalytical system was developed for the determination of ochratoxin A with the use of a surface plasmon resonance (SPR) sensor amplified by the anti-species antibody-colloidal gold particle (CGP) conjugate. The use of the binding of immune complexes to the CGP-anti-species antibody conjugate leads to the SPR signal amplification by a factor of more than 10 and results in the 60 pg/mL limit of detection of ochratoxin A with an assay time of 30 min. These characteristics are superior to those obtained both in the conventional enzyme immunoassay with the use of the same reagents and the SPR assay with unmodified antibodies and specific antibodies conjugated to colloidal gold.     

Optical parameters of calix[4]arene films and their response to volatile organic vapors

The Langmuir-Blodgett (LB) technique was employed to produce thin LB films using an amphiphilic calix-4-resorcinarene onto different substrates such as quartz, gold coated glass and quartz crystals. The characteristics of the calix LB films are assessed by UV-visible, quartz crystal microbalance (QCM) and surface plasmon resonance (SPR) measurements. UV-vis and QCM measurements indicated that this material deposited very well onto the solid substrates with a transfer ratio of >0.95. Using SPR data, the thickness and refractive index of this LB film are determined to be 1.14 nm/deposited layer and 1.6 respectively. The sensing application of calixarene LB films towards volatile organic vapors such as chloroform, benzene, toluene and ethanol vapors is studied by the SPR technique. The response of this LB film to saturated chloroform vapor is much larger than for the other vapors. The response is fast and fully recoverable. It can be proposed that this sensing material deposited onto gold coated glass substrates has a good sensitivity and selectivity for chloroform vapor. This material may also find potential applications in the development of room temperature organic vapor sensing devices.     

Ultrasensitive immunosensing of tuberculosis CFP-10 based on SPR spectroscopy

An antigen (Ag), CFP-10, found in tissue fluids of tuberculosis (TB) patients may be an ultimate candidate for use as a sensitive TB marker with a sensing method for early simplified diagnosis of TB. In this study, chemical and optical optimizations were carried out using novel immuno-materials for establishment of a self-assembled surface plasmon resonance (SPR) optical immunosensor system for detection of CFP-10, which is valuable for pre-clinical work, prior to conduct of massive clinical observations. For creation of a simple sensing interface, a monoclonal antibody (anti-CFP-10) was immobilized directly on a gold surface, followed by blocking with cystamine. Orientation and accessibility of anti-CFP-10 were assessed by the selective binding of CFP-10. Recent results indicate that the reusability of the sensor chip adopting the cystamine method was found to be preferable to other immobilization methods. A linear relationship was well correlated between SPR angle shift and CFP concentrations in the range from 100 ng mL⁻¹ to 1 μg mL⁻¹. Modification of the SPR chip with antibody provides a simple experimental platform for investigation of isolated proteins under experimental conditions resembling those of their native environment.     

Fabrication of ultraviolet photoconductive sensor using a novel aluminium-doped zinc oxide nanorod-nanoflake network thin film prepared via ultrasonic-assisted sol-gel and immersion methods

Unique and novel thin films with aluminium (Al)-doped zinc oxide (ZnO) nanostructures consisting of nanorod-nanoflake networks were prepared for metal-semiconductor-metal (MSM)-type ultraviolet (UV) photoconductive sensor applications. These nanostructures were grown on a glass substrate coated with a seed layer using a combination of ultrasonic-assisted sol-gel and immersion methods. The synthesised ZnO nanorods had diameters varying from 10 to 40 nm. Very thin nanoflake structures were grown vertically and horizontally on top of the nanorod array. The thin film had good ZnO crystallinity with a root mean square roughness of approximately 13.59 nm. The photocurrent properties for the Al-doped ZnO nanorod-nanoflake thin films were more than 1.5 times greater than those of the seed layer when the sensor was illuminated with 365 nm UV light at a density of 5 mA/cm². The responsivity of the device was found to be dependent on the bias voltage. We found that similar photocurrent curves were produced over eight cycles, which indicated that the UV sensing capability of the fabricated sensor was highly reproducible. Our results provide a new approach for utilising the novel structure of Al-doped ZnO thin films with a nanorod-nanoflake network for UV sensor applications. To the best of our knowledge, UV photoconductive sensors using Al-doped ZnO thin films with a nanorod-nanoflake network have not yet been reported.     

Nano particulate SnO2 based resistive films as a hydrogen and acetone vapour sensor

SnCl₂ (solution) was spin coated on soda lime glass and Al₂O₃ substrate to obtain nano-particulate tin oxide film, directly by sintering at 550 °C for 40 minutes (min). The surface morphology and crystal structure of the tin oxide films were analyzed using atomic force microscopy (AFM) and X-ray diffraction (XRD). The size of SnO₂ nanostructure was determined from UV-vis and found to be ?3 nm. These films were tested for sensing H₂ concentration of 0.1-1000 ppm at optimized operating temperature of 265 °C. The results showed that sensitivity (R_air/R_gas per ppm) goes on increasing with decreasing concentration of test gas, giving concentration dependent changes. Special studies carried out at low concentration levels (0.1-1 and 1-10 ppm) of H₂, give high sensitivity (200 × 10⁻³/ppm) for lowest concentration (0.1-1 ppm) of H₂. The selectivity for H₂ against relative humidity (RH), CO₂, CO and LPG gases is also good. The sensor, at operating temperature of 200 °C, is showing nearly zero response to 300 ppm of H₂, and offering response to acetone vapour of 11 ppm. Selectivity for acetone against RH% and CO₂ was also studied. These sensors can be used as H₂ sensor at an operating temperature of 265 °C, and as an acetone sensor at the operating temperature of 200 °C.     

Formaldehyde sensors based on nanofibrous polyethyleneimine/bacterial cellulose membranes coated quartz crystal microbalance

A novel formaldehyde sensor based on nanofibrous polyethyleneimine (PEI)/bacterial cellulose (BC) membranes coated quartz crystal microbalance (QCM) has been successfully fabricated. The nanoporous three-dimensional PEI/BC membranes are composed of nanofibers with diameter of 30-60 nm. The sensor showed high sensitivity with good linearity and exhibited a good reversibility and repeatability towards formaldehyde in the concentration range of 1-100 ppm at room temperature. Moreover, the results showed that the sensing properties were mainly affected by the content of PEI component in nanofibrous membranes, concentration of formaldehyde and relative humidity. Additionally, the nanofibrous PEI/BC membrane coated QCM sensors exhibited a good selectivity to formaldehyde when tested with competing vapors. The simple and feasible method to prepare and coat the PEI/BC sensing membranes on QCM makes it promising for mass production at a low cost.     

Comparison of surface plasmon resonance spectroscopy and quartz crystal microbalance for human IgE quantification

Surface plasmon resonance (SPR) and quartz crystal microbalance (QCM) have been known independently as surface sensitive analytical devices capable of label-free and in situ bioassays. In this study a SPR device and a 10 MHz QCM sensor are employed for the study of human IgE and anti-human IgE-binding reactions upon immobilizing the latter on the gold electrodes. The SPR and QCM response curves to the antibody immobilization and antigen binding are similar in shape but different in time scale, reflecting different resonation principles. Through optimization of the anti-human IgE coating, both the SPR and QCM sensors could detect IgE in a linear range from 5 to 300 IU/ml. Although the intrinsic sensitivity of the SPR device is five times of the 10 MHz QCM, the IgE detection sensitivity of the two methods is, however, different only in a factor of 2. The acceptable QCM sensitivity for the IgE detection is attributed to the fact that QCM measures the sum of molar mass of a protein layer and the entrapped water. Although both the devices use open, stand still liquid cell, and all the measurements are performed at room temperature, the SPR reproducibility and reliability are better than QCM, as the QCM frequency is more sensitive to temperature fluctuations, press changes and mechanical disturbances.     

Potential of 5,10,15,20-Tetrakis(3′,5′-di-tertbutylphenyl)porphyrinatocopper(II) for a multifunctional sensor

An organic compound 5,10,15,20-Tetrakis(3′,5′-di-tertbutylphenyl)porphyrinatocopper(II) (TDTPPCu) is synthesized and studied as an active material for multifunctional capacitive sensor. The capacitance of the device as a function of illumination, humidity and temperature has been investigated. It is observed that the capacitance increases by 4.7 times from the dark condition under an illumination of 3850 lx. The capacitance is also changed 9.5 times with the increase in relative humidity (RH) from 30% to 95%. No change in capacitance appeared below critical temperature 120 °C. Based on the experimental results for the multifunctional sensor a mathematical model has been developed. The model is mainly based on the assumption that the capacitive response of the sensor is associated with dielectric polarization. The sensors are simulated using this model. The simulated results match well with experimental results.     

The experimental investigation of the effects of uncoated,PVD- and CVD-coated cemented carbide inserts and cutting parameters on surface roughness in CNC turning and its prediction using artificial neural networks

In this study the machining of AISI 1030 steel (i.e. orthogonal cutting) uncoated, PVD- and CVD-coated cemented carbide insert with different feed rates of 0.25, 0.30, 0.35, 0.40 and 0.45 mm/rev with the cutting speeds of 100, 200 and 300 m/min by keeping depth of cuts constant (i.e. 2 mm), without using cooling liquids has been accomplished. The surface roughness effects of coating method, coating material, cutting speed and feed rate on the workpiece have been investigated. Among the cutting tools—with 200 mm/min cutting speed and 0.25 mm/rev feed rate—the TiN coated with PVD method has provided 2.16 μm, TiAlN coated with PVD method has provided 2.3 μm, AlTiN coated with PVD method has provided 2.46 μm surface roughness values, respectively. While the uncoated cutting tool with the cutting speed of 100 m/min and 0.25 mm/rev feed rate has yielded the surface roughness value of 2.45 μm. Afterwards, these experimental studies were executed on artificial neural networks (ANN). The training and test data of the ANNs have been prepared using experimental patterns for the surface roughness. In the input layer of the ANNs, the coating tools, feed rate (f) and cutting speed (V) values are used while at the output layer the surface roughness values are used. They are used to train and test multilayered, hierarchically connected and directed networks with varying numbers of the hidden layers using back-propagation scaled conjugate gradient (SCG) and Levenberg–Marquardt (LM) algorithms with the logistic sigmoid transfer function. The experimental values and ANN predictions are compared by statistical error analyzing methods. It is shown that the SCG model with nine neurons in the hidden layer has produced absolute fraction of variance (R²) values about 0.99985 for the training data, and 0.99983 for the test data; root mean square error (RMSE) values are smaller than 0.00265; and mean error percentage (MEP) are about 1.13458 and 1.88698 for the training and test data, respectively. Therefore, the surface roughness value has been determined by the ANN with an acceptable accuracy.     

Large area Ag-TiO2 UV radiation sensor fabricated on a thermally oxidized titanium chip

A Schottky-type ultraviolet (UV) light sensor is fabricated on a thermally oxidized titanium chip. The device is of Ag-TiO₂-Ti structure, and the Schottky junction between silver and rutile is formed subsequent to the vacuum deposition of silver on the thermally grown rutile layer by a controlled thermal annealing in air. The device operates at −300 mV biasing established between silver and titanium electrodes. The dark reverse current of this diode increases four orders of magnitude when illuminated with UV light (355 nm) of 10 μW/mm² intensity. The device is almost insensitive to visible light and requires no filtering when used for ambient UV level detection. The operation mechanism of the device is described by photonic electron-hole pair generation in the carrier depleted titanium dioxide layer adjacent to the silver electrode. The electrode-to-electrode distance is 1 μm only affording much faster performance compared to photoconductive UV detectors fabricated based on titanium dioxide; the response and recovery times of the device are 10 ms and 17 ms, respectively. At its standby mode, a 1 mm² active area device consumes less than 10 pW of electric power. Sensors with sensitive areas as large as ∼10 mm² are easy to fabricate. The fabricated devices are rugged, resistant to UV degradation, and cost effective.     

Selective potentiometric determination of uric acid with uricase immobilized on ZnO nanowires

In this study, a potentiometric uric acid biosensor was fabricated by immobilization of uricase onto zinc oxide (ZnO) nanowires. Zinc oxide nanowires with 80-150 nm in diameter and 900 nm to 1.5 μm in lengths were grown on the surface of a gold coated flexible plastic substrate. Uricase was electrostatically immobilized on the surface of well aligned ZnO nanowires resulting in a sensitive, selective, stable and reproducible uric acid biosensor. The potentiometric response of the ZnO sensor vs Ag/AgCl reference electrode was found to be linear over a relatively wide logarithmic concentration range (1-650 μM) suitable for human blood serum. By applying a Nafion^® membrane on the sensor the linear range could be extended to 1-1000 μM at the expense of an increased response time from 6.25 s to less than 9 s. On the other hand the membrane increased the sensor durability considerably. The sensor response was unaffected by normal concentrations of common interferents such as ascorbic acid, glucose, and urea.