Temperature sensing using reversible thermochromic polymeric films

Temperature sensing membranes using Nafion^® as the polymeric support matrix have been prepared incorporating common pH indicators and stains as visible indicators. These simple systems depend on the temperature sensitivity of the acid–base equilibria between the indicator and the acidic Nafion^®. The films are able to sense temperature change through a change in film colour resulting from the equilibrium shift between different forms of the indicating dye. The dyes (phenolphthalein, methylene blue, safranin-O and crystal violet) studied covered a temperature range from 4 to 70 °C.     

A fluorescence ratiometric detection scheme for ammonium ions based on the solvent sensitive dye MC 540

Principles of wavelength ratiometric evaluation of fluorescence have been extensively used to cancel out and reference sensor response not associated with the analyte. Main limitations of this technique include wavelength ratiometric properties inherent only to a restricted number of solute specific fluorescent dyes. This study presents a dual-excitation/dual-emission ratiometric detection scheme applied on a two-phase coextraction based fluorosensor. Rather than utilizing spectral shifts associated with various complexation and acid–base equilibria of solute specific indicators, we made use of the fluorescence shift induced by the phase transfer of the solvent sensitive dye merocyanine 540 (MC 540) upon ammonium–nonactin coextraction in a hydrogel–ether emulsion. The two-phase ratiometric fluorosensor was exposed to conditions frequently reported to alter performance of fluorescence based optical sensors. Sensor response was unaffected by O₂ concentrations, and signals caused by variations in excitation light intensity and pH were found more or less completely eliminated by the ratiometric procedure. Selectivity towards NH₄⁺ and possible interferences from K⁺ were more accurately evaluated using the dual-excitation/dual-emission ratio, compared to a single-excitation/single-emission fluorescence scheme. It was not possible to eliminate artifacts associated with fluctuations in temperature, effective MC 540 concentrations and sample ionic strength by the ratiometric reference scheme, most likely due to monomer–dimer complexation of the indicator dye and the formation of larger aggregates at concentrations exceeding the critical salt concentration of MC 540. Principles described for a two-phase ratiometric detection procedure associated with solvent sensitive dyes rather than solute specific fluorescent dyes may provide a powerful tool for direct solute detection. Thus, the limited versatility of wavelength ratiometric fluorescence detection to specially designed compounds with wavelength ratiometric properties directly linked to interactions with the analyte, may be overcome.     

Applications of artificial neural network on signal processing of optical fibre pH sensor based on bromophenol blue doped with sol–gel film

In this paper, the applications of artificial neural network (ANN) in signal processing of optical fibre pH sensor is presented. The pH sensor is developed based on the use of bromophenol blue (BPB) indicator immobilized in a sol–gel thin film as a sensing material. A three layer feed-forward network was used and the network training was performed using the back-propagation (BP) algorithm. Spectra generated from the pH sensor at several selected wavelengths are used as the input data for the ANN. The bromophenol blue indicator, which has a limited dynamic range of 3.00–5.50 pH units, was found to show higher pH dynamic range of 2.00–12.00 and with low calibration error after training with ANN. The enhanced ANN could be used to predict the new measurement spectra from unknown buffer solution with an average error of 0.06 pH units. Changes of ionic strength showed minor effect on the dynamic range of the sensor. The sensor also demonstrated good analytical performance with repeatability and reproducibility characters of the sensor yield relative standard deviation (R.S.D.) of 3.6 and 5.4%, respectively. Meanwhile the R.S.D. value for this photostability test is 2.4% and it demonstrated no hysteresis when the sensor was cycled from pH 2.00–12.00–2.00 (acid–base–acid region) of different pH. Performance tests demonstrated a response time of 15–150 s, depending on the pH and quantity of the immobilized indicator.     

Composites: A novel alternative to construct solid state Ag/AgCl reference electrodes

An Ag/AgCl solid-state reference electrode is developed by means of a graphite–AgCl–Silver dag-epoxy resin composite. The response of the composite reference electrode (CRE) to chloride ions is evaluated; a linear non-nernstian response is observed associated to the following equation E = −15.15 (±1.10) − 44.05 (±0.38) log[Cl⁻]. Comparing the CRE's response potential versus a saturated commercial Ag/AgCl reference in KCl 0.1 M, a mean of 40.7 ± 0.4 mV of the distribution of potential versus time data is observed over a period of 1 h. The performance of the CRE as reference for a glass membrane electrode by means of direct pH measurements and quantitative determination of acids by acid–base titrations is evaluated obtaining statistically stable, precise and exact results compared with those obtained using a combined glass electrode. The typical cylindrical configuration of the CRE is changed to adapt it to a FIA system for the determination of ammonium ion, obtaining a sensitivity 50.30 ± 0.26 mV/log[NH₄⁺] and a linear range 8.5 × 10⁻⁵ to 0.1 M, which are analytical parameters statistically equivalent to those presented by the classical determination system.     

Sol–gel derived polycrystalline Cr1.8Ti0.2O3 thick films for alcohols sensing application

The powder sample of Cr_1.8Ti_0.2O₃ (CTO) was obtained by a sol–gel method. The thick films were developed on identical ceramic tubes of 4 mm length comprising of two Au-electrodes and printing an eight-layer film prepared by mixing CTO with glass powder and -terpinol as an organic vehicle. X-ray powder diffraction (XRD) patterns showed the formation of a single phase. The scanning electron microscope (SEM) images of the ceramic sensor treated at 850 °C revealed that the grain size was larger than 400 nm for the individual isolated grains on the surface, and the agglomerated dense spheroidal platelets had the size of 1–4 μm in diameter. The AC impedance measurement in ambient air showed that the resistance decreased nearly by two orders of magnitude with an increase in temperature in the range of 400–600 °C for both the powder sample and the thick film, and the activation energy E_a derived from the measurement was found to be 0.35 and 0.36 eV for the powder and the film, respectively. The films were exposed to various concentrations of alcohols (0.4–1.2 ppm of methanol and 1.0–5.0 ppm of ethanol), followed by determination of sensor response, sensitivity and reversibility and reproducibility. The origin of the gas response was attributed to the surface reaction of R-OH (R = methyl and ethyl group) with O⁻_(ads) to form adsorbed R-CHO, which was desorbed as a gas at 400 °C after the sensor departing from the gas.     

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.     

An optical biosensor for multi-sample determination of biochemical oxygen demand (BOD)

An optical biosensor for parallel multi-sample determination of biochemical oxygen demand (BOD) in wastewater samples has been developed. The biosensor monitors the dissolved oxygen (DO) concentration in water through an oxygen sensing film immobilized on the bottom of glass sample vials. The oxygen sensing film contains the tris(4,7-diphenyl-1,10-phenanthroline) ruthenium(II) dye (Ru(dpp)) the luminescence intensity of which varies with oxygen concentration. A computer-controlled moving optrode head with four blue light emitting diodes (LEDs) was scanned sequentially under each sample vial. The luminescence signal was collected by an optical cable and transmitted to a photomultiplier tube (PMT) and processed by a microcomputer. The microbial samples (activated sludge and Bacillus subtilis were immobilized in a sol–gel composite material of silica and poly(vinyl alcohol)-grafted-poly(vinylpyridine) on the oxygen sensing film. The performance of the microbial film as a function of cell loading, thickness, temperature and pH and in the presence of heavy metals as well as its stability and service life have been investigated. The BOD value was determined from the rate of oxygen consumption by the microorganisms in the first 20 min. The BOD values obtained from this biosensor correlates well with the results of the conventional 5-day BOD test.     

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.     

Continuous monitoring of gastric carbon dioxide with optical fibres

An optical fibre sensor for the continuous monitoring of gastric carbon dioxide is described, based on the utilisation of a sensing layer, in which the colour of the layer is dependent on the CO₂ concentration. The CO₂-sensitive layer consists basically of a dye/quaternary ammonium ion pair, dissolved in a thin layer of ethylcellulose. The sensor was thoroughly characterised in laboratory and its performances were compared with those of Tonocap, the instrument based on gastric tonometry, which is the present method for detecting partial pressure of gastric carbon dioxide. Its measurement range, 0–150 h Pa, its accuracy, ±2.5 h Pa, and its response time, less than 1 min, were capable of satisfying the physicians’ requirements for clinical application. The clinical tests, carried out on volunteers and on intensive care patients, showed that the developed sensor is definitely superior to the sensor that is at present available on the market: thanks to its short response time, the optical fibre sensor is able to detect rapid changes in pCO₂, currently unknown because of the lack of a tool with which to measure them.     

Perchlorate-selective membrane sensors based on two nickel-hexaazamacrocycle complexes

The perchlorate salts of nickel(II) complexes of 1,3,5,8,10,13-hexaazacyclotetradecane (1) and 1,8-tert-butyl-1,3,5,8,10,13-hexaazacyclotetradecane (2) were used in construction of PVC based membrane electrodes. These sensors show very good selectivity for ClO₄⁻ ions over a wide variety of anions. These electrodes exhibit Nernstian behavior with the slopes of 59.5 and 59.3 mV per decade for (1) and (2), respectively. The working concentration ranges of the sensors are 1.0 × 10⁻¹–9.0 × 10⁻⁷ M (1) and 1.0 × 10⁻¹–5.0 × 10⁻⁷ M (2) with the detection limits of 6.0 × 10⁻⁷ and 2.0 × 10⁻⁷ M, respectively. The response time of the both sensors is very fast, and can be used for 2 (I) and 12 (II) weeks in a pH range of 3.0–11.0. These electrodes were applied to the determination of perchlorate ions in wastewater and cattle urine samples.     

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.     

Development of an optical hydrogen sulphide sensor

A hydrogen sulphide (H₂S)-sensitive optode film has been fabricated by immobilising tetraoctylammonium fluorescein mercury(II) acetate (TOFMA) and tri-n-butyl phosphate in a poly(vinyl chloride) (PVC) matrix. The optode film, coated on an overhead transparency film, was employed as a sensing device for fluorimetric detection of H₂S. The fluorescence intensity monitored at 553 nm (excitation at 503 nm) increased with increasing H₂S concentrations. The optode film showed a good, linear and reversible response to H₂S from 0 to 15 ppm (v/v). It was optically stable and the reproducible response of the film on exposure to 10 ppm (v/v) H₂S was extremely good. There was no sign of degradation after 8 h of continuous use. The response to H₂S levelled off at about 27.5 ppm The response and recovery times of the optical H₂S sensor were fast and less than 2 and 5 s, respectively. An optically-based sensor for H₂S determination was successfully developed. It was anticipated that the system could be used to monitor H₂S with a concentration range of 0–25 ppm (v/v) with satisfactory results. A proposed mechanism for the detection of H₂S by the optode films is described.     

Electrocatalytic oxidation of methanol and other short chain aliphatic alcohols on glassy carbon electrodes modified with conductive films derived from Ni-(N,N′-bis(2,5-dihydroxybenzylidene)-1,2-diaminobenzene)

Complexes of nickel(II) with the ligand N,N′-bis(2,5-dihydroxybenzylidene)-1,2-diaminobenzene (Ni^II-DHS) can be electropolymerized onto glassy carbon surfaces in alkaline solution to give electroactive films strongly adhered on the electrode surface. In alkaline solution, these poly-[Ni^II-DHS]/GC films present the typical voltammetric response of a surface-immobilized redox couple, as can be anticipated for the Ni²⁺/Ni³⁺ transitions into the film. In addition, the films exhibit a potent and persistent electrocatalytic activity towards the oxidation of methanol. The electrocatalytic currents are, at least, 80 times higher than those obtained for the oxidation of methanol at electrodes modified with nickel hydroxide films in alkaline solutions. In addition, the current is proportional to the concentration of methanol from 0.050 to 0.30 μM. The detection limit and the sensitivity were found to be 26 ± 2 nM and 7.4 × 10⁻² ± 6 × 10⁻³ A cm² mol⁻¹ M⁻¹, respectively. Electrodes modified with poly-[Ni^II-DHS]/GC films show a moderate electrocatalytic activity towards the oxidation of other aliphatic short chain alcohols, such as: ethanol, 1-propanol, 2-propanol and n-butanol. In all cases the catalytic currents present linear dependences with the concentration of alcohol in alkaline solution. The analytical properties of these potential alcohol sensors have also been studied.     

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.     

Highly sensitive and fast responding CO sensor using SnO2 nanosheets

A highly sensitive and fast responding CO sensor was fabricated from a sheet-like SnO₂. The SnO sheets were prepared by a room temperature reaction between SnCl₂, hydrazine and NaOH, and they were subsequently oxidized into SnO₂ sheets at high temperature (600 °C). The morphology and size of the SnO₂ sheets could be controlled during the formation of SnO, which influence the sensor response (R_a/R_g) and response time to a great extent. The sensor response of SnO nanosheets to 10 ppm CO was enhanced up to 2.34, and the 90% sensor response time could be reduced to 6 s, which are significantly higher and shorter than those of SnO₂ powders (1.57 and 88 s), respectively. The realization of both a high sensitivity and rapid response were explained in terms of rapid gas diffusion onto the entire sensing surface due to the less-agglomerated and very thin structure of SnO₂ nanosheets and the catalytic effect of Pt.     

Screen printed thick films of NiO and LaFeO3 as gamma radiation sensors

Thick films of nickel oxide (NiO) and perovskite type LaFeO₃ were investigated for γ-radiation dosimetry purposes. Samples were fabricated using the thick film screen printing technique. These films were exposed to a ⁶⁰Co γ-radiation source with a dose rate of 6 Gy/min. The effects of γ-radiation on both the optical and the electrical properties of NiO and LaFeO₃ films were studied. Absorption spectra for the specimens were recorded and the values of the optical band gap for as-printed and γ-irradiated films were calculated. It was found that the optical band gap values decreased with the increase in radiation dose. To study changes in the electrical properties of the materials, two types of specimens having sandwich metal–semiconductor–metal structure were made with layers of NiO and LaFeO₃, respectively. Commercial DuPont 4929 silver paste was used to manufacture electrical contacts. It was observed that radiation induced changes in the electrical properties for both types of thick films, e.g. values of current decreased with an increase in radiation dose. It was found that annealing restored both the electrical and the optical properties of the samples.     

A colorimetric response to hydrogen sulfide

Two simple Cu(II) chromophores [Cu(acac)(dmp)](NO₃) (1) and [Cu(acac)(dpph)](NO₃) (2) (acac = acetylacetone, dmp = 2,9-dimethyl-1,10-phenanthroline and dpph = 4,7-diphenyl-1,10-phenanthroline) have been synthesised and immobilized into a highly permeable polymer matrix and subsequently used in the optical detection of low levels of hydrogen sulfide (10 ppm) over a 2 min period. The system is responsive to a concentration one-tenth that quoted as being immediately dangerous to life and health (IDLH) value (100 ppm) by the National Institute for Occupational Safety and Health (NIOSH). The UV–vis spectral change is a consequence of the hydrogen sulfide gas reducing the Cu(II) to Cu(I) in the polymer matrix. A crystal structure of [Cu(acac)(dpph)](NO₃) (2) was obtained and will also be discussed.     

Optical fiber-based evanescent ammonia sensor

An optical fiber-based evanescent gaseous ammonia sensor is designed and developed. The sensing dye, bromocresol purple (BCP), is immobilized in the substitutional cladding using sol–gel process. The sensing properties of the optical fiber sensor to gaseous ammonia at room temperature are presented. This newly developed ammonia sensor exhibits good reversibility and repeatability. The effect of different carrier gases, argon, nitrogen, and air on sensing properties of the ammonia sensor is investigated. The sensor with air as carrier gas has the best response time and sensitivity. In order to improve the response time of the optical fiber evanescent ammonia sensor, an elevated ambient temperature is applied and thoroughly investigated. A fast response time of 10 s was obtained at 55.5 °C with the carrier gas of air or argon. These experimental results have demonstrated that a fast response optical fiber evanescent gaseous ammonia sensor can be constructed by applying slightly elevated ambient temperature.     

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.     

Searching for optimal sensitivity of single-mode D-type optical fiber sensor in the phase measurement

To improve the sensitivity of a single-mode D-type optical fiber sensor, we selected a D-type optical fiber sensor with 4 mm long and 4 μm core thickness made of a single-mode fiber, a Au-coating on the sensor with a thickness range of 15–32 nm, a light wavelength of 632.8 nm, and an incident angle of 86.5–89.5° for different refractive index (1.33–1.40) sensing. These simulations are based on the surface plasmon resonance (SPR) theory using the phase method which shows that the sensitivity is proportional to the refractive index, Au film thickness and lower incident angle on the sensing interface. The sensitivity is higher than 4000 (degree/RIU), and the resolution is better than 2.5 × 10⁻⁶(RIU) as the minimum phase variation is 0.01°. This device is used to detect the refractive index or gas or liquid concentration in real-time. The proposed sensor is small, simple, inexpensive, and provides an in vivo test.