Adsorption studies of carbowax and poly dimethyl siloxane to use as chemical array for nitro aromatic vapour sensing

Trinitro toluene (TNT)-based explosives contain 2,4-dinitro toluene (DNT) and 1,4-dinitro benzene (DNB) as a manufacturing impurity, which form more vapour in the vicinity than TNT itself, and hence form a distinctive ‘chemical signature’ indicative of explosive. The concentration of these compounds over landmines is extremely low and well below the minimum detection limits of most field-portable chemical sensors. Carbowax was found to give good adsorption for 2,4-DNT vapour at higher temperature and reverse was in case of 2,6-DNT vapour. On the other hand, the same polymer film gives reasonably good adsorption for 1,4-DNB, more than 33% adsorption and poor response for 1,3-DNB, which is around only 20%. The adsorption rate was specific for all the four isomers as observed 0.81 ng/(cm² min) for 2,4-DNT, 0.14 ng/(cm² min) for 1,3-DNB, 0.07 ng/(cm² min) for 2,6-DNT, and 0.04 ng/(cm² min) for 1,4-DNB. This polymer was found to give different relative response to these nitro aromatic isomers. PDMS gives very good response for 2,4-DNT (98–100%) at 50 °C appears to be a distinguishing performance. The results of carbowax-1000 and poly dimethyl siloxane (PDMS) indicated that these two polymers could be more suitable for the realisation of polymer-based chemical sensor.     

The effect of hydrodynamic conditions on the detection of aqueous solutions of toluene by means of an inverted graded-index fiber

This paper deals with the effect of hydrodynamic conditions on the detection of toluene dissolved in water by means of fibers with a truncated parabolic inverted-graded index (IGI) profile. The detection is based on refractive-index changes of a detection layer of polydimethylsiloxane (PDMS) applied on the fiber which are induced by penetration of toluene into the layer. The dependence of the response of the sensing fiber placed in a flow cell on the flow velocity of the detected aqueous solution of toluene has been investigated. The sensing fiber was successively exposed to flows of distilled water and aqueous solutions of toluene. The fiber responses were measured for three chosen concentrations of the toluene solutions and for five flow velocities of the solutions. From these results the dependence of the relative decrease of the output signal on the flow velocity was determined. It has been found that the magnitude of output signal changes is approximately proportional to the solution concentration and the rate of the signal changes in the tested concentration range depends approximately linearly on the solution flow velocity.     

Interfacial hybridization kinetics of oligonucleotides immobilized onto fused silica surfaces

Fused silica optical fibers have been used in an intrinsic mode optical configuration as biosensors for fluorescence based detection of hybridization of nucleic acids. In this work, the kinetics of hybridization of single-stranded oligonucleotides that were covalently immobilized were studied. The probe DNA was dT₂₀, and the target was Fluorescein-labeled non-complementary (dT₂₀) or complementary (dA₂₀) oligonucleotide. Chronofluorimetric monitoring of the adsorption and hybridization processes was used to investigate oligonucleotide films of different density, in different salt concentrations, at temperatures of 25 and 40 °C, with the concentration of the target DNA being 0.005–0.1 μM. Mathematical models based on first- and second-order Langmuir adsorption have been examined to describe both the adsorption and the hybridization processes. Experimental data were processed using the models, and the hybridization kinetics were calculated. Hybridization kinetics on these optical fiber DNA sensors was found to be up to three orders faster than results presented for a number of other experiments using different immobilization chemistries.     

Label-free detection of DNA hybridization using gold-coated tapered fiber optic biosensors (TFOBS) in a flow cell at 1310 nm and 1550 nm

We had previously reported the detection of a model protein bovine serum albumin (BSA) using antibody-immobilized tapered fiber optic biosensors (TFOBS) at 1310 nm and 1550 nm under stagnant and flow conditions. Because of recent interest in pathogen detection based on DNA, in this work we explore the application of these sensors for the detection of single stranded DNA (ssDNA). We show that it is feasible to directly detect the hybridization of a 10-mer ssDNA to its complementary strand immobilized on the sensor surface. Detection was performed under flow conditions because flow reduces non-specific binding to sensor surface, eliminates optical transmission changes due to mechanical movements, and allows for instantaneous switching of samples when needed.

TFOBS were fabricated with waist diameters of 5–10 μm and total lengths of 1000–1200 μm. The taper regions were coated with 50 nm of gold and housed in a specially constructed holder which served as a flow cell. The TFOBS was immobilized with 15-mer ssDNA with a C₆ extension and a thiol group, which attaches to Au1 1 1 sites. Then, the complementary 10-mer ssDNA samples were allowed to flow in from low to high concentration (750 fM to 7.5 nM) and the resulting transmission changes were recorded. It is shown that 750 fM of complementary DNA can be detected. This sensor was able to distinguish between complementary DNA from DNA with a single nucleotide mismatch in the middle position.     

UV-LIGA interferometer biosensor based on the SU-8 optical waveguide

SU-8 resist was used as a core/cladding waveguide material to fabricate a Mach–Zehnder interferometer (MZI) for biochemical sensing. The refractive index of the SU-8 resist was fine-tuned with a Δn of 0.004 for single-mode transmission. The UV lithography processes of the SU-8 resist were also optimized to pattern the high resolution (1 μm) and high aspect ratio (A_R = 6) Y-branch structure of the optical interferometer. Optical measurements reveal that the SU-8 MZI chip can efficiently transmit the NIR laser (λ = 1310 nm) with a total loss less than 6 dB. When one branch of the MZI is in contact with the analyte, the interfered intensity stabilizes after the soaking time exceeds 5 min. NaCl solution with a concentration of 10⁻⁹ g/l can be detected using the SU-8 MZI chip. In the future, the polymer MZI chip can be mass-produced by molding process (or the LIGA process). The low-cost, label-free, real-time and high-sensitivity MZI chip will benefit many applications related to biological, environmental and industrial detection.     

Evaluation of the selective detection of 4,6-dinitro-o-cresol by a molecularly imprinted polymer based microsensor electrosynthesized in a semiorganic media

A carbon fiber microelectrode (CFME) was coated with a polymeric film, in order to synthesize an MIP based voltammetric microsensor for the selective determination of DNOC. The polymeric synthesis was carried out by electrocopolymerization of aniline and o-phenylenediamine (o-PD) in a water:methanol (1:1) media. The response of the MIP-sensor synthesized to the target analyte, was linear in a range from 8 × 10⁻⁷ to 10⁻⁴ M with a sensitivity of 1.6 × 10³ nA M⁻¹ and good stability and repeatability (<14%). Different rebinding experiments were carried out in order to evaluate the binding properties of the MIP-sensor. The experimental adsorption isotherms were fitted to Langmuir, Bi-Langmuir and Freundlich–Langmuir isotherms and the Langmuir model was chosen as the best fitting model. Under the optimized experimental conditions, the voltammetric microsensor was able to differentiate between DNOC and other closely related compounds such as other dinitrophenolic pesticides like binapacryl or dinobuton.     

Characterization of protective coatings for planar automotive gas sensors

Alumina support material suitable for use as a planar automotive gas sensor support was coated in thin films of yttria-stabilised zirconia (YSZ) and titania. The morphology, composition, thickness and homogeneity of the coating was measured. The coating was applied to the ‘green’ form of a tape cast alumina substrate which was subsequently fired at 1500 °C to produce the final form of the coated alumina. The YSZ coating gave a continuous 5 μm thick coating with no evidence of mixed oxide formation between the YSZ and the alumina substrate. XRD indicated a face centred cubic Y doped ZrO₂ or primitive tetragonal Zr_0.9Y_0.1O_1.95 phase. The titania coatings were much thinner (<1 μm) with signs of trace amounts of aluminium titanium oxide (Al₂TiO₅) as well as rutile titania in XRD. Spot analysis using X-ray photoelectron spectroscopy showed a fairly regular titania coverage. Atomic force microscopy analysis showed a particle size of 1–3 μm for the YSZ coating and 0.5 μm for titania.     

Remote detection of gaseous ammonia using the near infrared transmission properties of polyaniline

Ammonia is a key component of many industrial processes where it is used in very high concentrations. The applications range from high quality steel production and fertiliser manufacture, to the refrigeration of food products and ice ring leisure facilities. Ammonia escapes have been identified as a large and serious problem by both government and industry. Simple and robust ammonia sensors for remote monitoring applications remain an area of continuous interest.

Polyaniline is a conducting polymer used in ‘electronic nose’ instrumentation and has been shown to be electronically sensitive to ammonia. In this paper, we report on the application of electrochemically-prepared polyaniline films for the measurement of gaseous ammonia at 1300 nm. This wavelength corresponds to a region of high optical transmission for optical fibres and is also compatible with telecom devices and technology. A simple and robust measurement system based on a standard telecom 1300 nm LED is described and remote sensing using 100 m of duplex multimode fibre is demonstrated.

Typically, the transmission of the polyaniline films at 1300 nm increases by approximately 1% in response to gaseous ammonia levels of 6 ppm in 50% RH. This represents the lower limit of detection in our study. Although initially the sensors react to the presence of ammonia very fast it takes over several hours for the output to reach the equilibrium. Clearly this is impractical however, it is possible to differentiate between different concentrations of ammonia by taking two readings at fixed intervals. A calibration curve for the sensors was obtained using two readings 15 s apart. The response time of the polyanaline films was found to be insensitive to the humidity variations in the range of 30–70% RH, however, over the 10–90% variation the changes were of the same order of magnitude as those induced by 6 ppm of ammonia.     

The application of a light guiding flexible tubular waveguide in evanescent wave absorption optical sensing

A light guiding flexible fused silica (FFS) capillary has been used in designing evanescent wave (EW) absorption based chemical sensors. The FFS capillary is similar to a conventional silica optical fiber in that it can guide light in the wavelength region from UV to near infrared, but different from a conventional optical fiber in that it is a tubular waveguide. The inner surface of the FFS capillary is fused silica, which was coated with a reagent doped polymer in order to design an optical fiber chemical sensor. The FFS capillary has a cladding layer plus a protection polymer coating on its outside surface. The cladding layer ensured the capability of the FFS capillary for guiding light. The protection coating increases the FFS capillary's mechanical strength and makes it robust in practical applications. This makes the FFS capillary very useful in designing an EW based optical chemical sensor of a long path length. Techniques for activating the inner surface of an FFS capillary, coating the inner surface of the capillary with a polymer, connecting the coated capillary to a light source and a photodetector, and delivering a sample through the capillary have been developed in this work. Three optical sensors for sensing Cu(II), toluene in water samples and ammonia in a gas sample have been fabricated and tested. Preliminary test results obtained in this work illustrate the feasibility of fabricating highly sensitive EW absorption based chemical sensors with the light guiding FFS capillary.     

Fabrication and characterization of low temperature sintering PMN–PZN–PZT step-down multilayer piezoelectric transformer

For the fabrication as step-down multilayer piezoelectric transformer, piezoelectric properties of Pb(Mg_1/3Nb_2/3)O₃–Pb(Zn_1/3Nb_2/3)O₃–Pb(Zr_0.52Ti_0.48)O₃ (PMN–PZN–PZT) ceramics were optimized by ZnO–Li₂CO₃ (ZL) and Pb₃O₄ content. Effects of the additions on the structure, bulk density and electrical properties of ceramics were investigated. The results revealed that the proper additions of ZL with Pb₃O₄ content could modify the electrical properties of the PMN–PZN–PZT ceramics. The composition sintered at 995 °C with 0. 01 wt.% ZL and 0.10 wt.% Pb₃O₄ content showed higher values, which were listed as follows: d₃₃ = 256 pC/N, K_p = 0.60, Q_m = 1910, _r = 1032, tan δ = 0.0070 and r = 2.09 Ω. In addition, the step-down piezoelectric transformers with optimized PMN–PZN–PZT composites were fabricated and the characteristics as the output power and resistance loads were measured. Meanwhile, the step-down piezoelectric transformers sintered at 995 °C showed the favorable characteristics with a higher gain G of 0.204 and a lower temperature rise of 6 °C when the output power was 5 W, and the driving frequency were approximately constant (≈126 kHz) when the output power was from 5 to 13 W. Moreover, the maximum efficiency (90.2%) was obtained at load resistance of 10 Ω.     

Adsorptive voltammetry of Hg(II) ions at a glassy carbon electrode coated with electropolymerized methyl-red film

The glassy carbon electrode coated with electropolymerized methyl-red film, 1.2 × 10⁻⁶ m in thickness, (PMRE) showed high sensitivity towards Hg(II) ions. PMREs were adopted to accumulate and detect Hg(II) ions in a pH 2.56 Britton–Robinson buffer solution. Cyclic voltammogram of the accumulated Hg species on PMREs exhibited an anodic wave at 0.64 V and a cathodic wave at 0.13 V, due to the oxidation of accumulated Hg species on PMREs and the reduction of Hg(II) ions in the solution, respectively. For this heterogeneous adsorption of Hg(II) ions onto PMREs, the maximum surface concentration, adsorption equilibrium, and Gibbs energy change were evaluated to be 5.12 × 10⁻⁶ mol m⁻², 3.7 × 10⁵ l mol⁻¹, and −30.1 kJ mol⁻¹, respectively. The anodic peak current at 0.64 V was linear with the concentration of Hg(II) ions in the range of 1.1 × 10⁻¹⁰ to 1.1 × 10⁻⁷ M with a detection limit of 4.4 × 10⁻¹¹ M. The proposed method was utilized successfully for the detection of Hg(II) ions in the lake water.     

Calorimetric hydrocarbon sensor for automotive exhaust applications

We have developed a calorimetric sensor utilizing a thermoelectric device supported on a planar alumina substrate. By using a highly selective carbon monoxide (CO) oxidation catalyst and a non-selective platinum (Pt) catalyst, the device can be built to detect either CO or hydrocarbons with high selectivity. The CO oxidation catalyst comprises lead-modified platinum and exhibits excellent selectivity over the 200–400 °C temperature range. The thermoelectric device consists of two thick film junctions made of niobium pentoxide (Nb₂O₅)-doped titanium dioxide (TiO₂) and a lithiated nickel (Ni), which are supported on a planar alumina substrate. The thermocouple detects the difference in temperature due to different catalytic reactions over the two junctions and shows a high output signal because of the high Seebeck coefficient of Nb₂O₅-doped TiO₂ (−400 μV/°C). In gas bench tests, the sensor has a linear output of 0–2.75 mV over 0–1000 ppm of propylene and a response time of 2.5 s (at 90% of amplitude) at a gas temperature of 350 °C. An engine dynamometer evaluation shows that the response of the sensor parallels the change in CO and hydrocarbon constituent concentrations when the engine air-to-fuel ratio is varied.     

HCl gas monitoring based on a QCM using morpholine-functional styrene-co-chloromethylstyrene copolymer coatings

Quartz resonators coated with various compositions of poly(styrene-co-chloromethyl styrene) reacted with morpholine as adsorption sites were fabricated for simply but accurately monitoring HCl gas in air. The exposure of all resonators to HCl gas irreversibly decreased the oscillation frequencies, indicating that these devices can be used for one-shot detection of HCl gas. The chemical structure and composition of the copolymer affected the sensitivity. The largest sensitivity was obtained for the copolymer having 40.0 mol% CMSt composition cross-linked with 5.0 mol% DVB. The sensitivity was 0.1 ppm/Hz for 10-min sensor operation, demonstrating a ppm level of HCl detection, although great interference was produced by changes in the humidity.     

Synthesis and luminescence of red MEH-PPV:P3OT polymer

This paper investigates the synthesis processes for poly(3-octylthiophene) (P3OT) and poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV). The proton nuclear magnetic resonance (¹H NMR) and the Fourier transform infrared spectrophotometer (FTIR) were used to identify the chemical structure and functional group of synthesized polymers, respectively. The efficient Förster energy transfer from P3OT to MEH-PPV and the dilution of MEH-PPV with P3OT leaded to an enhanced red emission. When the concentration of P3OT was 30 wt%, the optimal photoluminescence (PL) intensity of MEH-PPV:P3OT was obtained, with wavelength at 580 nm. A PL quenching phenomenon was observed owing to the higher blending concentration of P3OT. The current density was 0.204 A/cm² at 1.3 V for the red polymer light-emitting diode with the structure of Al/MEH-PPV:P3OT/ITO, and the CIE chromaticity coordinates were at x = 0.66 and y = 0.34.     

Molecular imprinting strategy for solvent molecules and its application for QCM-based VOC vapor sensing

Cross-linked polymers made of methyl methacrylate (MMA) as a monomer and divinylbenzene (DVB) as a cross-linking agent were prepared in the presence of toluene or p-xylene as a solvent. The cross-linked polymer prepared in toluene tended to sorb toluene vapor preferably, while the cross-linked polymer prepared in p-xylene sorbed p-xylene vapor preferably. The observed molecular recognition ability can be explained on the bases of an imprinting effect by solvent molecules. Molecularly imprinted polymer (MIP) powders were blended with PMMA, and the blended films were coated on a piezoelectric quartz crystal with a view to preparing QCM-based VOC sensors. The imprint effect was clearly observed, even in these blended films. The response of the sensor towards toluene or p-xylene vapor was reversible; however, the response time was slow due to the existence of the matrix polymer around the MIP particles.     

聚合物光纤布拉格光栅轴向应变传感特性研究

针对固体火箭发动机纤维缠绕壳体状态监测中局部可能出现大应变情况,论证了采用聚合物光纤布拉格光栅(poly-mer optieal fiber Bragg grating,POFBG)传感器对大应变进行检测的可行性,分析了聚合物光纤光栅的工作原理,考虑到聚合物光纤材料特性与石英光纤的差异,建立了引入二次项因素的应变、温度传感模型,并通过MATLAB对聚合物光纤布拉格光栅的应变和温度变化进行了数值仿真.结果表明,反射波长随温度的升高而减小,温度漂移呈现非线性,这与文献报道的实验结果比较吻合.     

Tailorable low modulus, reversibly deformable elastomeric thiol–ene materials for microfluidic applications

The ability to form low-moduli materials with sensitive modulus control over a wide range is advantageous for a variety of applications, including membranes and valves for microfluidic devices. This paper examines the impact of monomer functionality and stoichiometry on the network properties of thiol–vinyl systems from both experimental and theoretical perspectives. Agreement is observed between the model predictions, based on the probability of forming finite polymer network chains, and the measured Young's modulus values for polymer networks ranging in moduli from 1 to 10 MPa. The highest modulus is obtained for polymers containing tetrathiol, and lower-modulus polymers were obtained by copolymerizing monothiol or dithiol monomers. These novel elastomeric systems are also shown to have strain-at-break values of over 1000%. To illustrate one application of these low-modulus materials, the contact liquid photolithographic polymerization (CLiPP) method was used to fabricate thiol–ene valves in a polymeric microdevice. For an applied pressure of 5 psi, the maximum deflection of the valve was varied from 100 to 320 μm simply by tailoring the modulus of the thiol–ene membrane.     

Pyroelectric and dielectric properties of sol–gel derived barium–strontium–titanate (Ba0.64Sr0.36TiO3) thin films

The barium–strontium–titanate (BST, Ba_0.64Sr_0.36TiO₃) thin films have been prepared by the sol–gel method on a platinum-coated silicon substrate. The resulting thin films show very good dielectric and pyroelectric properties. The dielectric constant and dissipation factor for Ba_0.64Sr_0.36TiO₃ thin film at a frequency of 200 Hz were 592 and 0.028, respectively. The dependence of the capacitance as a function of the voltage shows a strongly non-linear character, and two peaks characterizing spontaneous polarization switching can be clearly seen in this curve, indicating that the films have a ferroelectric nature. The capacitance changed from 495 to 1108 pF with the applied voltage in the −5 to +5 V range at a frequency of 100 kHz. The peak pyroelectric coefficient at 30 °C is 1080 μC/m² K. The pyroelectric coefficient at room temperature (25 °C) is 1860 μC/m² K, and the figure-of-merit of this film is 37.4 μC/m³ K. The high pyroelectric coefficients and the greater figures-of-merit of Ba_0.64Sr_0.36TiO₃ thin films make it possible to be used for thermal infrared detection and imaging.     

Novel method for fast determination of ultra trace amounts of timolol maleate by continuous cyclic voltammetry at Au microelectrode in flowing injection systems

A novel method for easy and fast detection of timolol maleate in flow-injection system has been introduced. It was used for analysis of timolol maleate in pure form as well as in its pharmaceutical formulations. The reported method is simple, precise, accurate, time saving and economic as compared to all previously reported methods. The best performance for measurement of timolol maleate was obtained at, pH 2.0, scans rate 300 V s⁻¹, accumulation potential −500 mV and delay time 0.6 s. The advantages of the proposed detection method are, (1) the removal of oxygen from the test solution is not required any more, (2) the detection limit of the method is sub-micromolar, (3) this method is fast enough for determination of the drug compound, in a wide variety of chromatographic techniques. The potential waveform consists of potential steps for cleaning, accumulation and potential ramp that were continuously applied on an Au disk microelectrode (with a radius of 12.5 μm). The detection limit of the method for timolol maleate was 1.58 ng ml⁻¹. The relative standard deviation of the method at 1.0 × 10⁻⁹ M was 2.3% for 20 runs.     

Dynamic strain measurements by fibre Bragg grating sensor

In this work, we describe a fibre Bragg grating (FBG) sensing system for static and dynamic strain measurements. Low cost and simple grating-based demodulation technique has been used to interrogate the strain induced Bragg wavelength shift. Experimental results showing the capability of the proposed system to perform static strain measurements with 1 μ resolution and a linear response are presented. The same system was also used for dynamic strain detection. Here, a fibre grating was bonded to a piezoceramic actuator in different configurations. A laser triangulation-based system has been used as reference measurements up to 10 kHz while dynamic strain measurements by FBG have been carried out up to 50 kHz demonstrating a dynamic resolution of ≈40 n/Hz^1/2, leading to the possibility to perform high frequency detection for on-line structural health monitoring in civil, aeronautic, and aerospace applications.