Lifetime-based optical sensor for high-level pCO2 detection employing fluorescence resonance energy transfer

An optical sensor for the measurement of high levels of carbon dioxide in gas phase has been developed. It is based on fluorescence resonance energy transfer (FRET) between a long-lifetime ruthenium polypyridyl complex and the pH-active disazo dye Sudan III. The donor luminophore and the acceptor dye are both immobilised in a hydrophobic silica sol–gel/ethyl cellulose hybrid matrix material. Tetraoctylammonium hydroxide (TOA-OH) is used as an internal buffering system. Fluorescence lifetime is measured in the frequency domain, using low-cost phase modulation measurement technology. The use of Sudan III as an acceptor dye has enabled the sensor to have a dynamic range up to 100% carbon dioxide. The sensor displays 11.2° phase shift between the limit of detection (LOD) of 0.06 and 100% CO₂ with a resolution of better than 2%. The encapsulation in the silica/polymer hybrid material has provided the sensor with good mechanical and chemical stability. The effect of molecular oxygen, humidity and temperature on the sensor performance was studied in detail.     

Highly sensitive optical humidity probe

A highly sensitive optical humidity probe based on reflectance measurements has been developed using Nafion^®-crystal violet (CV) films. This sensor can be used to calibrate relative humidity (RH) in the range 0-0.25% with a detection limit (blank signal + 3σ_b, where σ_b = the standard deviation (S.D.) of the blank signal) of 0.018% RH (∼4.37 ppm) and exhibited low hysteresis. The sensor films were fully reversible in dry nitrogen and reversal times were shown to be dependent on exposure time and % RH. The response to 1% RH was highly reproducible (S.D. = 1.67%, number of samples (n) = 5). Hydrogen chloride gas did not interfere with the response of the sensor to RH but did reduce sensor reversal times. This sensor displayed sufficient sensitivity that it could be used to detect ppm levels of moisture in process gases such as nitrogen and HCl.     

Humidity sensors using in situ synthesized sodium polystyrenesulfonate/ZnO nanocomposites

Thin film humidity sensors have been prepared using in situ synthesized inorganic/organic nanocomposites of sodium polystyrenesulfonate (NaPSS) and ZnO. Its humidity sensing characteristics and the sensing mechanism have been investigated by measuring the complex impedance spectra of the sensor at different humidities. The logarithm of the impedance of sensor based on composite film changes linearly by four-orders of magnitude over almost whole humidity range (11-97% RH). Furthermore, the sensor exhibits a quick response (absorption: 2 s, desorption: 2 s) and small hysteresis (less than 2% RH). The composite film shows better sensing properties than NaPSS film, such as better linearity, quicker response. Explanation to the improvement is attempted by taking into account of the composition and structure of the nanocomposites.     

Fabrication of an ammonia gas sensor using inkjet-printed polyaniline nanoparticles

This work details the fabrication and performance of a sensor for ammonia gas analysis which has been constructed via the inkjet-printed deposition of polyaniline nanoparticle films. The conducting films were assembled on interdigitated electrode arrays and characterised with respect to their layer thickness and thermal properties. The sensor was further combined with heater foils for operation at a range of temperatures. When operated in a conductimetric mode, the sensor was shown to exhibit temperature-dependent analytical performance to ammonia detection. At room temperature, the sensor responded rapidly to ammonia (t₅₀ = 15 s). Sensor recovery time, response linearity and sensitivity were all significantly improved by operating the sensor at temperatures up to 80 °C. The sensor was found to have a stable logarithmic response to ammonia in the range of interest (1-100 ppm). The sensor was also insensitive to moisture in the range from 35 to 98% relative humidity. The response of the sensor to a range of common potential interferents was also studied.     

Ruthenium(III) Schiff's Base Complex as Novel Chloride Selective Membrane Sensor

A novel chloride PVC‐based membrane sensor based on a ruthenium(III) Schiff's base complex, as an excellent neutral carrier, has been developed. The ruthenium complex, in combination with a ketonic plasticizer and a cationic additive led to ISEs with fundamental characteristics, such as slope sensitivity, short response times and selectivity coefficients, which were sufficient for practical applications. The sensor with composition of 30% PVC, 62% benzyl acetate, 5% ruthenium(III) Schiff's base complex and 3% hexadecyltrimethyl ammonium bromide displays near‐Nernstian behavior in a wide concentration range (1.0×10^?1–3.0×10^?6 M with slope of ?54.5±0.5) with a detection limit of 2.0×10^?6 M (71.0 ng per mL). The response of the electrode is independent on pH in the range of 4.0–10.0 and can it be used for at least ten weeks. The proposed electrode shows a very short response time (<20 s) in whole concentration range. The sensor displays high selectivity toward chloride ions over several organic and inorganic anions. It was successfully applied for the determination of chloride in serum samples. It was also used as an indicator electrode in the potentiometric titration of chloride ions with silver nitrate solution.     

Electrical and humidity characterization of m-NA doped Au/PVA nanocomposites

The Meta-Nitroaniline (m-NA) doped (by varying weight percentage (wt. %)) gold/polyvinyl alcohol (Au/PVA) nanocomposites were synthesized using gold salt and hydrazine hydrate (HH) by in situ process. The composite was coated on ceramic rods having two end electrodes by drop casting method for studying their electrical behavior at different relative humidity (RH) levels, ranging from 4 to 95% RH at room temperature. The optimized wt. % was used to prepare coatings of various thicknesses (20-40 μm) of the films. As the humidity decreases, the resistance increases. The low humidity sensing characteristic can be tailored by varying wt. % of m-NA and thicknesses of the nanocomposite films. The resistive-humidity sensor shows two regions of sensitivity having highest sensitivity for lower RH. The sensor response and recovery time is about 6-10 s and 52 s respectively. The dynamic range of variation of the resistance allows a promising use of the films as a humidity sensor. The material was characterized by X-ray diffraction (XRD) and impedance spectroscopy at 60% RH.     

A simple and high sensitive spectrophotometric method for ultra trace determination of ruthenium with its catalytic effect on the oxidation of pyronin B by periodate

A new simple, selective, high sensitive and rapid method has been developed for spectrophotometric determination of ultra trace amounts of ruthenium based on its catalytic effect on the oxidation of pyronin B by periodate at lambdamax=555 nm. The described method is able to quantify ruthenium in the range of 0.1-100 ng ml-1 (r=0.9973), with a detection limit (S/N=3) of 0.036 ng ml-1. Under optimum conditions, this procedure has been successfully applied to determine the trace levels of ruthenium in the environmental and biological samples. The precision, expressed as relative standard deviation of three measurements, is better than 2.44%.     

Exploring fiber optic approach to sense humid environment over nano-crystalline zinc oxide film

A novel humidity sensor made up of nano-crystalline zinc oxide (ZnO) film, coated onto the U-shaped typical glass substrate as a wave guide, conjugated with an optical fiber and He-Ne un-polarized laser source. The nano-crystalline zinc oxide (ZnO) was synthesized using single molecular precursor method. The resulting material was characterized with Fourier transform infrared spectroscopy (FTIR), X-ray diffractometry (XRD), thermogravimetric-differential thermal analysis (TG-DTA) and scanning electron microscopy (SEM). In the thin film, ZnO particles exhibited the wurtzite phase structure with the particle size in a diameter range of 70-80 nm. The humidity sensing characteristic has been estimated by measuring the optical permeability (OP) as a function of percentage relative humidity (%RH) in the ranging from 5 to 90 inside a closed chamber. The OP decreases linearly with increase in %RH with a respond time of about 30 and recovery time of 35 s. The sensor exhibits the sensitivity of 0.45 in the %RH range 5-50 and 0.30 from 50 to 90.     

Evolution of the adsorbed water layer structure on silicon oxide at room temperature

The molecular configuration of water adsorbed on a hydrophilic silicon oxide surface at room temperature has been determined as a function of relative humidity using attenuated total reflection (ATR)-infrared spectroscopy. A completely hydrogen-bonded icelike network of water grows up to three layers as the relative humidity increases from 0 to 30%. In the relative humidity range of 30-60%, the liquid water structure starts appearing while the icelike structure continues growing to saturation. The total thickness of the adsorbed layer increases only one molecular layer in this humidity range. Above 60% relative humidity, the liquid water configuration grows on top of the icelike layer. This structural evolution indicates that the outermost layer of the adsorbed water molecules undergoes transitions in equilibrium behavior as humidity varies. These transitions determine the shape of the adsorption isotherm curve. The structural transitions of the outermost adsorbed layer are accompanied by interfacial energy changes and explain many phenomena observed only for water adsorption.     

全氟磺酸锂电导率式湿度传感器

以碳纸为电极,Nafion溶液再铸薄膜为感湿材料,并用氯化锂将膜转换成Li+型,制备了固体聚合物电解质湿度传感器.测定了不同相对湿度下,传感器的电导率响应与相对湿度之间关系.结果表明:在相对湿度为10%～97%范围内,传感器的电导率响应对数与相对湿度之间成良好的线性关系,线性度为0.997;传感器响应的时间为40s左右;于200h内稳定性和重复性良好.     

A novel barium polymeric membrane sensor for selective determination of barium and sulphate ions based on the complex ion associate barium(II)-Rose Bengal as neutral ionophore

A simple, long life, rapid response and sensitive barium(II)-PVC membrane sensor that typically follows Nernstian behavior has been developed for the assay of barium(II) ions. The developed sensor has been made by incorporating the complex ion associate of barium(II)-Rose Bengal (Ba-RB) as an ionophore into a plasticized PVC matrix. The sensor is stable and exhibited fast potential response of 20 s and gave a good linear response with a Nernstian slope of 28.5 ± 0.4 mV/decade of activity within the concentration range 5 × 10⁻⁵ to 10⁻¹ M over a wide range of pH 4.5-10.0 for barium(II) ions. The developed sensor showed comparatively good selectivity for barium(II) ions with respect to other alkali, alkaline earth, transition and heavy metal ions. The plasticizer o-nitrophenyloctyl ether controlled significantly the calibration slope and the lifetime of the fabricated sensor. The proposed sensor was used successfully for the analysis of barium(II) ions in wastewater samples and in lithophone pigment with excellent recovery percentages in the range 98.9-99.8 ± 1.6%. The determination of sulphate in fresh and potable water samples with the developed sensor has been also achieved successfully. The described sensor provides a reliable means with good correlation with the data obtained by atomic absorption spectrometry (AAS) and other spectrophotometric methods for the analysis of trace amounts of barium(II) and/or sulphate ions in different matrices.     

温度对Nafion-结晶紫光纤湿度传感器性能的影响

The optical fiber relative humidity sensor based on Nation-crystal violet film was developed.The effect of samplef s temperature in the range from 299.15K to 324.15K on the sensing performance of the sensor was investigated. The mathematical function between temperature and the sensitivity of the sensor was established according to the reactive theory of sensor to the relative humidity, which was validated with the experiment. With the research, the application range of the sensor was extended, which made the sensor keep a good veracity when it was used in situ.     

Chemiluminescent determination of EDTA and related compounds using tris(2,2′-bipyridyl)ruthenium(III) photogenerated on-line

A rapid and sensitive chemiluminescence method using flow-injection has been developed for the determination of EDTA. The method is based on the chemiluminescent reaction of EDTA with tris(2,2'-bipyridyl)ruthenium(III), which is generated on-line through the photooxidation of tris(2,2'-bipyridyl)ruthenium(II) with peroxydisulfate. After optimizing the different experimental parameters, a calibration graph was obtained over the concentration range of 7 x 10(-8) M to 3 x 10(-6) M, with a minimum detectability of 7.2 x 10(-9) M (S/N = 3) observed. The correlation coefficient was 0.9992 (n = 8). The repeatability was 0.88 % (for a level of 4 x 10(-7) M) expressed as the relative standard deviation (n = 10), and the reproducibility (studied on five consecutive days) was 1.5%. The method was successfully applied to the determination of EDTA in ophthalmic collyrium and sauce samples. The method is also useful for determining other aminopolycarboxylic acids, such as NTA, EGTA, DTPA, DCTA and EDDS.     

Luminescence Quenching Behavior of Oxygen Sensing ORMOSIL Films Based on Ruthenium Complex

An organically modified silicate(ORMOSIL) based optical sensor response to gaseous O2 or O2 dissolved in water is presented. The oxygen sensing film mechanism is based on the principle of fluorescence quenching of tris(4,7-diphenyl-l , 10-phenanthroline) ruthenium ( ) ([Ru(dpp)3]2+), which has been entrapped in a porous ORMOSIL film. In order to establish optimum film-processing parameters, comprehensive investigations, including the effects of the polarity and the hydrophobicity of the sensing film on oxygen quenching response and response time, were carried out. The film hydrophobicity increased as a function of dimethyl-dimethoxysilane (DiMe-DMOS) content, which is correlated with enhanced oxygen sensor performance. The sensor developed in the present work exhibits the advantages of fast response time and good reversibility. The detection limits are 0. 5 % and 0. 3 g/mL for O2 in the gaseous and the aqueous phases, respectively.     

Optochemical sensor for determining ozone based on novel soluble indigo dyes immobilised in a highly permeable polymeric film

An optochemical ozone sensor is described that has been manufactured by immobilisation of novel soluble indigo derivatives in permeable transparent polymeric films of polydimethylsiloxane–polycarbonate copolymer. From a number of investigated indigo derivatives, 4,4,7,7-tetraalkoxyindigo 9 has been selected for optimal sensitivity and specificity of ozone detection. A linear calibration for ozone can be obtained in the range between 0.01 and 0.5 ppm. The limit of quantitation is 0.03 ppm, and the accuracy exceeds 8%. It takes about 134 s to measure the relatively low occupational exposure concentration of 0.1 ppm. A reduction of the sensor response time could be achieved through application of double-sided coated sensors instead of single-sided variants. The stability of the sensors and the effect of external parameters like relative humidity (RH), temperature and gas flow on the sensor response have been investigated. The sensor response is affected by varying the gas flow or temperature; however, humidity in the range between 0 and 90% RH does not affect sensor response. The indigo derivative 9 remained stable inside the polymeric film and no chemical reaction, crystallisation or leaching occurred during 10 months of observation. Proper choice of indicator dye and polymeric material and successful application of kinetic evaluation method for the exposure experiments determine the desired features of the sensor.     

Sensitive spectrofluorimetric determination of ruthenium at nanotrace levels using 2-(alpha-pyridyl) thioquinaldinamide [PTQA

A new spectrofluorimetric method for the determination of ruthenium with nonfluorescent 2-(alpha-pyridyl) thioquinaldinamide (PTQA) is described. The oxidative reaction of Ru(III) upon PTQA gives oxidised fluorescent product (lambda(ex(max))=347 nm; lambda(em(max))=486 nm). The sensitivity of the fluorescence reaction between ruthenium and PTQA is greatly increased in the presence of Fe (III). The reaction is carried out in the acidity range 0.01-0.075 M H(2)SO(4). The influence of reaction variables is discussed. The range of linearity is 1-400 microg l(-1) Ru(III). The standard deviation and relative standard deviation of the developed method are +/-1.210 microg l(-1) Ru (III) and 2.4%, respectively (for 11 replicate determinations of 50 microg l(-1) Ru (III)). The effect of interferences from other metal ions, anions and complexing agents was studied; the masking action is discussed. The developed method has been successfully tested over synthetic mixtures of various base metals and platinum group metals, synthetic mixtures corresponding to osmiridium, certified reference materials in spiked conditions and rock samples.     

A BIOFILM USED AS ULTRAVIOLET-DOSIMETER

Abstract— A UV-dosimeter has been developed for routine measurements which mainly weights the various components of the spectrum in relation to their damaging effects on a microorganism. For this purpose a biofilm was constructed, comprising dried spores of Bacillus subtilis (wild-type or DNA repair defective strain), immobilized on transparent polyester plastic sheets. After irradiation, the biofilm was incubated in a growth medium. The proteins, synthesized by the immobilized microorganisms after spore germination and several cell divisions, were stained and determined by photometry, giving a measure of the biological activity. The "biologically effective dose" was determined from a calibration curve. It reflects the dose equivalent to that of the calibration source producing the same effect.
The UV-response of the biofilm is additive and follows the reciprocity law in the range of fluence rates investigated. The response is nearly independent of temperature within the range of -20°C to +70°C as well as of humidity between about 37 and 80% relative humidity. Storage for up to 9 months at <70% relative humidity and room temperature does not significantly influence the viability of the spores.     

Flow injection chemiluminescence determination of paracetamol

A simple chemiluminometric method using flow injection has been developed for the determination of paracetamol (acetaminophen), based on the chemiluminescence produced by the reduction of tris(2,2′-bipyridyl)ruthenium(III). The latter is obtained by oxidation of tris(2,2′-bipyridyl)ruthenium(II) by potassium permanganate in dilute sulphuric acid in the presence of paracetamol. A standard or sample solution was injected into the ruthenium(II) stream (flow rate 1.5 ml min⁻¹) which was then merged with potassium permanganate in dilute sulphuric acid stream (flow rate 0.5 ml min⁻¹). The chemiluminescence intensity is enhanced by the presence of manganese(II) ions. Under the optimum conditions, a linear calibration graph was obtained over the range of 0.3-50.0 μg ml⁻¹ and the detection limit was 0.2 μg ml⁻¹ (s/n = 3). The relative standard deviation of the proposed method calculated from 20 replicate injections of 5.0 μg ml⁻¹ paracetamol was 1.1%. The sample throughput was 90 h⁻¹. The method was successfully applied to the determination of paracetamol in commercial pharmaceutical formulations.     

Determination of carbamazepine by chemiluminescence detection using chemically prepared tris(2,2'-bipyridine)ruthenium(III) as oxidant.

A new chemiluminescence method for the determination of carbamazepine (CBZ) has been developed. The method is based on the chemiluminescence produced in the reaction of tris(2,2'-bipyridine)ruthenium(III) and CBZ in an acidic medium. The chemiluminescence intensity was enhanced by organic solvents in the reaction system. Under the optimum experimental conditions, the calibration curve was linear over the range 4.0 x 10(-3)-8.6 x 10(-7) mol/L for CBZ. The detection limit (S/N = 3) was 2.5 x 10(-7) mol/L and the relative standard deviation of six replicate measurements was 2.6% for 4.0 x 10(-4) mol/L of CBZ. The possible reaction mechanism were also discussed. The chemiluminescence method was successfully applied to assay the CBZ contents in pharmaceutical tablets.     

Fluorescence resonance energy transfer disposable sensor for copper(II)

A disposable sensor has been developed for the measurement of copper(II) concentration in aqueous solution based on a change in the fluorescence of porphyrazine 2,7,12,17-tetra-tert-butyl-5,10,15,20-tetraaza-21H,23H-porphine (TP). The sensor was constructed by spin-coating a polyester support with a PVC solution containing TP, a plasticizer, the chelating agent Zincon and the ion-pairing benzetonium chloride. The measurement principle is based on the radiationless resonance energy transfer (RET) from TP immobilized in membrane, and acting as fluorescence donor, to Zincon acting as an acceptor induced by copper(II). The absorption spectrum of the Zincon-Cu(II) complex presents adequate overlapping with the emission spectrum of TP, producing a useful analytical signal by the RET process.The disposable sensor responds to copper(II) irreversibly over a dynamic range from 0.039 to 14 μmol L⁻¹ (2.5-890 μg L⁻¹) with a sensor-to-sensor reproducibility (relative standard deviation RSD) of 1.9%, as log aCu2+, at the medium level of the range and a response time of 10 min. The performance of the optical disposable sensor was tested for the analysis of copper in different types of natural waters (river, well, spring and swimming pool), validating results against a reference procedure.