Poly(acrylamide) derivatives for QCM-based HCl gas sensor applications

Quartz resonators coated with three kinds of poly(acrylamide) derivatives were studied for simply but accurately detecting HCl gas in air. The exposure of the resonator to HCl gas reversibly decreased the oscillation frequencies. The sensitivity, response time, and reversibility were found to depend on the structure of the amide group. Among the polymers used, poly(N,N-dimethylacrylamide) (PDMAA) showed the most relevant data for the HCl sensor. The HCl sensitivity obtained for PDMAA was ca. 250 ppb/Hz. On the other hand, the irreversible response toward NO₂ gas was considerably high, and great interference was also produced by changes in the test gas humidity.     

A new optical sensing reaction for nitric oxide

Based on the reaction between the Cu(II) complex of Eriochrome cyanine R (ECR) and nitric oxide (NO) in phosphate buffer (pH 7.4), a new colorimetric method for the determination of NO concentration has been developed. The linear calibration range for NO was 0–60 μM with a detection limit of 1.24 μM. This reaction was then used as the basis in the development of a fibre optic chemical sensor for NO gas. The copper complex was incorporated into silicone rubber membranes and exposed to NO gas after incubating the films in phosphate buffer (pH 7.4). A linear calibration for NO gas between 0 and 6 ppm was obtained with a detection limit of 0.227 ppm (1 μM 0.031 ppm NO in solution). The sensor response was shown to be reproducible and reversible (2.77%, R.S.D., n=4) upon exposure to aqueous phosphate buffer (pH 7.4). The sensor response was also found to be pH independent between 7 and 10.     

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.     

Development and evaluation of piezoelectric-polymer thin film sensors for low concentration detection of volatile organic compounds related to food safety applications

In this study, the regioregular poly (3-hexyl thiophene) (rr-P3HT) based piezoelectric sensors were developed and evaluated to detect alcoholic volatile organic compounds (VOCs) associated with spoiled and Salmonella typhimurium contaminated packaged beef headspace. The drop coating technique was used to deposit thin films of rr-P3HT on both the sides of quartz crystal microbalance (QCM) electrode. The QCM polymer sensors were found to provide repeatable and reproducible sensor response to alcohol VOCs with a fast recovery (<2 min) at room temperature (25 °C). The principal component analysis on the sensors sensitivities was performed to discriminate the sensed alcohol VOCs, namely: 3-methyl-1-butanol from 1-hexanol. The QCM polymer sensors demonstrated selective response to low concentration of 3-methyl-1-butanol (average estimated lowest detection limit (LDL): 4.35 ppm) and to 1-hexanol (average estimated LDL: 3.20 ppm). The 30 days storage study performed on QCM sensors showed identical sensitivity responses for sensing 3-methyl-1-butanol and 1-hexanol at low concentrations.     

Highly efficient and stable white organic light emitting diode with triply doped structure

A triply doped white organic light emitting diode with red and blue dyes in the light emitting layer and a green dye in another layer is proposed. The device structure was CuPc(12 nm)/NPB(40 nm)/ADN:DCJTB(0.2%):TBPe(1%)(50 nm)/Alq:C545(0.5%)(12 nm)/LiF(4 nm)/Al. Here copper phthalocyanine (CuPc) is a buffer layer, N,N′-di(naphthalene-1-y1)-N,N′-dipheyl-benzidine (NPB) is a hole transporting layer, 9,10-di-(2-naphthyl) anthracene (ADN) is blue emitting layer, tris (8-quinolinolato)aluminium complex (Alq) is an electron transporting layer, 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidy1-9-enyl)-4H- pyran (DCJTB), 2,5,8,11-tetra-butylperylene (TBPe), Coumarin6 and deveriative (C545) are red, blue and green dyes, respectively. This device shows a luminance of 21200 cd/m² at driving current of 400 mA/cm² and 1026 cd/m² at 20 mA/cm². Its efficiency is 6 cd/A and 3.11 Lm/W. It also shows a higher operating stability: the half lifetime is 22,245 h at an initial luminance of 100 cd/m², while the driving voltage increased only 0.3 V.     

Preparation of BST ferroelectric thin film by metal organic decomposition for infrared sensor

Barium strontium titanate (Ba_1−xSr_xTiO₃) ferroelectric thin films have been prepared by metal organic decomposition (MOD) on Pt/Ti/SiO₂/Si and on micromachined wafer with an aim to fabricate dielectric bolometer type infrared (IR) sensor. The XRD pattern and D–V hysteresis curve of the film have been measured in order to investigate the effects of the final annealing temperature and annealing time on the property of the film. The results show that the films annealed at 700 °C or 800 °C all have good perovskite structure, while the film annealed at 800 °C has better ferroelectric loops. Films annealed at 800 °C with different annealing time from 5 to 60 min show a similar perovskite structure, among which films annealed at 30 and 60 min condition have the better ferroelectric loops. Temperature coefficient of dielectric constant (TCD) of the MOD made BST thin film on micromachined substrate is about 1%/K. The uniformity of the BST film on micromachined Si wafer also has been confirmed to be good enough for operation of sensor array. Chopperless operation has been attained and infrared response evaluation of the fabricated sensor also has been carried out with R_v of 0.4 kV/W and D^* of 1.0×10⁸ cm Hz^1/2/W, respectively.     

Ionic liquids used as QCM coating materials for the detection of alcohols

Six imidazolium-based ionic liquids (ILs) were synthesized and employed as sensing materials coated on quartz crystal microbalance for the detection of organic vapors. Acetone, ethanol, dichloromethane, benzene, toluene and hexane were selected as representatives for common environmental pollutants, and good linear responses from 0 to 100% of concentrations were observed. The halogen-anion-containing imidazolium ILs-coated sensors showed fast response, excellent reversibility, and considerable sensitivity and selectivity towards alcohols, and the selective factors were up to 30 times for ethanol versus other VOCs. The existence of water vapor reduced the frequency response of the sensor, but a good linear relationship remained.     

White organic light-emitting devices with non-doped-type structure

A non-doped-type structure was proposed for obtaining organic light-emitting devices with high-efficiency and full-spectrum white light emission. The device structure included indium tin oxide glass substrate/450 Å 4,4′,4″-tris{N-(3-methylphenyl)-N-phenylamin}triphenylamine (m-MTDATA) hole injection layer/100 Å N,N′-bis-(1-naphthyl)-N,N′-diphenyl-1,1′-biph-enyl-4,4′-diamine (NPB) hole transport layer/150 Å 4,4′-bis(2,2′-diphenylvinyl)-1,1′-biphenyl (DPVBi) blue emitting layer/ultrathin [2-methyl-6-[2-(2,3,6,7-tetrahydro-1H, 5H-benzo[ij] quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene] propane-dinitrile (DCM2) yellow-emitting layer/ 80 Å 4,7-diphenyl-1,10-phenanthroline (BPhen) electron transporting layer and hole blocking layer/600 Å tris (8-hydroxyquinoline) aluminium (Alq3) electron-transporting layer /10 Å lithium fluoride (LiF)/aluminum (Al). A white emission (Commission Internationale de l’Eclairage 1931 chromaticity coordinate) (X = 0.3556, Y = 0.3117) at 5 V and (X = 0.282, Y = 0.2658) at 15 V was obtained. Its luminance was 11,497 cd/m² at 15 V, and the maximum efficiency was 4.8 lm/W at 5 V.     

Physiological cost of energy-equivalent noise exposures with a rating level of 85 dB(A):: Hearing threshold shifts associated with energetically negligible continuous and impulse noise

In industry continuous or impulse noise does not occur exclusively; rather it is a combination of both. If low-level continuous noise or impulse noise (below 120 dB) is added to an already existing high-level continuous noise this often numerically causes no essential increase in the rating level. Yet, it cannot be expected that also aural strain of these exposures is always negligible. Therefore, in a cross-over test series, ten male subjects (Ss) were exposed to white noise of 94 dB(A) for 1 h (TS I), energy-equivalent to an 8 h-rating level L_Ard of 85 dB(A). In a second test series (TS II) the same exposure was combined with 900 energetically negligible 5-ms impulses with a noise level of 113 dB(A) which increased the rating level by only 0.4 dB. The noise exposure of TS I and TS II was followed by an idealized resting phase in a soundproof cabin. In a third test series (TS III) the continuous noise of 94 dB(A) / 1 h was followed by 3 h of white noise at 70 dB(A). Such an additional load increases the L_Ard by merely 0.1 dB to 85.1 dB(A). In all three test series, the noise-induced temporary threshold shift (TTS₂) and its restitution were measured. The continuous noise exposure of 94 dB(A) for 1 h was associated with a TTS₂ of around 20 dB which disappeared completely after about 2 h. The additional impulse noise caused a small increase in the TTS₂ and a prolongation of the restitution time. The maximum mean temporary threshold shift for the group increased only slightly (from 22.5 to 25.9 dB, which nevertheless can be statistically proven at a significance level of p 0.99). Yet, more importantly, the restitution time increased from 126 to 175 min, i. e. 3 h, which can be statistically proven at a significance level of p0.95. The TTS₂-values of TS III did not differ significantly from those resulting from TS I. That was expected as the conditions up to that point in time were identical. But due to the additional subsequent exposure, the mean restitution time increased considerably from 126 min up to 240 min (4 h). The mean total physiological cost represented by the integrated restitution temporary threshold shift (IRTTS) increased in TS II by approximately 40% and in TS III even by 140%.

Relevance to industry

The results of the study show that levels of noise which have no influence on the rating level which traditionally is calculated according to the energy-equivalence principle are often of great importance, as they can lead to considerably prolonged restitution times. Therefore, the purely energy-equivalent determination of the rating level of both impulse noise and low sound levels can lead to an underestimation of latent problems so that over time a reversible TTS can evolve into a permanent threshold shift. The results are also of importance for the acoustic design of break rooms for noise-exposed workers. There should be conditions that allow an undisturbed restitution of hearing.     

Equation of state parameters for stable and non-stable transition metal phases from universal binding Energy relations

Remarkable regularities in the behaviour of the binding energy versus distance function (BEDF) of solids were reported years ago by Rose, Ferrante and Smith (RFS). In various phenomena, such as adhesion, chemisorption and bulk cohesion, it was possible to scale the binding energy and the interatomic distance so that data for various systems could be described by the same, “universal”, binding energy relation (UBER). At the 1995 Ringberg Workshop on Unary Data (Calphad 19 (1995) 538) it was recommended that the RFS approach should be considered as an alternative for correlating and predicting cohesive properties, as well as the parameters of the equation of state of solids (EOS). This possibility has been explored by us, using theoretical information on the energy versus volume relations at zero kelvin, that has been obtained in tight-binding linearized-muffin-tin-orbitals (TB-LMTO) calculations. The cohesive energy, equilibrium volume, bulk modulus and its pressure derivative (B_e′) have been obtained for elements of the second row of the periodic table, viz., Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd and Ag, in the bcc, fcc and hcp structures. With this extensive database a critical test of the hypothesis of “universality” has been carried out. Moreover, the applicability of the RFS approach in predicting B_e′ has been examined. The results for stable phases have been compared with experimental data. Finally, the structure dependence of B_e′ has been discussed, which is a key issue in dealing with the EOS of non-stable structures of the elements.     

Layer-by-layer construction of an active multilayer enzyme electrode applicable for direct amperometric determination of cholesterol

A biosensor for direct amperometric determination of cholesterol was constructed by a layer-by-layer nanothin film formation using cholesterol oxidase (COx) and poly(styrenesulfonate) on a monolayer of microperoxidase covalently-immobilized on Au–alkanethiolate electrodes. Cyclic voltammograms (CVs) of microperoxidase covalently-immobilized on mercaptopropionic acid- and aminoethanethiol-monolayer electrodes showed a redox wave with the formal potential of 0.40 V (versus Ag | AgCl | NaCl (sat.)). The formal potential and the apparent heterogeneous electron-transfer rate of immobilized microperoxidase were not specific with the inner Au–alkanethiolate layer. The biosensor shows a linear current response for cholesterol at the applied potential of 0 V in the concentration range of 0.2–3.0 mM with a correlation coefficient of 0.969. The current response of the biosensor for cholesterol was very rapid (response time <20 s) and was highly reproducible; sample standard deviation of the current response at the concentration of 1.5 mM in five individual determinations was 0.09. The magnitude of the amperometric response for cholesterol was 0.13 μA cm⁻² at the concentration of 1.5 mM. The inertness and stability of the biosensor towards the potential electrical interferents, -ascorbic acid, pyruvic acid and uric acid, was tested, and it was found that the biosensor rapidly responses to the addition of cholesterol even in the presence of these interferents.     

Chemical deposition of nanocrystalline nickel oxide from urea containing bath and its use in liquefied petroleum gas sensor

Nanocrystalline nickel oxide (NiO) was deposited onto glass substrates using a chemical deposition method from a bath containing nickel (Ni²⁺) ions and urea at 363 K. The deposition process was based on the reaction between Ni²⁺ and hydroxide ions released from the protolysis of ammonia formed in the decomposition of urea heated at 363 K, which caused to form nickel hydroxide. The structural properties of nickel oxide films were studied by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). The XRD analyses showed that nanocrystalline nature remained after heating at 523 K for 2 h. Surface morphology of the nickel oxide film showed worm-like mesoporous structure with pore size in a nanometer range. The chemically deposited nickel oxide films were effectively used as a liquefied petroleum gas (LPG) sensor and the maximum response of 36.5% was recorded on exposure to 0.3 vol% of LPG at 698 K.     

Characteristics of a label-free piezoelectric immunosensor detecting Pseudomonas aeruginosa

A label-free immunosensor system detecting a psychrophylic bacterium, Pseudomonas aeruginosa was developed as follows. Four types of anti-P. aeruginosa antibody were individually chemisorbed onto one-side gold electrodes of piezoelectric quartz crystals according to a thiolated antibody coupling procedure initiated with a thiol-cleavable heterobifunctional cross-linker, sulfosuccinimidyl-6-[3-(2-pyridyldithio)propionamido]hexanoate. A flow-type biosensor system was operated optimally at 0.2 M sodium potassium phosphate, pH 7.2 with a minimal matrix effect and the selected flow rate for it was 0.155 ml/min. A biosensor response was detected by measuring a steady-state resonant frequency shift after the response time around 8 min. The frequency shifts obtained were quite specific according to the antibody types and P. aeruginosa strains. The biosensor responses to varying concentrations of the P. aeruginosa cells ranging from 1.3×10⁷ to 1.3×10⁸ CFU/ml were determined as 17–176 Hz and a linear calibration curve (r=0.942) was obtained by plotting the responses in a double-logarithmic scale. The selectivity of the biosensor between P. aeruginosa and Xanthomonas spp. which both belong to the aerobic pseudomonads was, however, not so good owing to the property of the antibody used. The sensor chip could be reused at least seven times without an appreciable decrease in sensitivity.     

On-chip Fabry-Pérot interferometric sensors for micro-gas chromatography detection

We fabricated and characterized on-chip Fabry-Pérot (FP) vapor sensors for the development of on-column micro-gas chromatography (μGC) detectors. The FP sensors were made by coating a thin layer of polymer on a silicon wafer. The air-polymer and polymer-silicon interfaces form an FP cavity, whose resonance wavelengths change in response to the vapor absorption/desorption, thus allowing for rapid detection and quantification of vapors. For proof-of-concept, two polymers (PDMS and SU-8) were used independently and placed in an array in a microfluidic channel, and showed different sensitivities for different vapors. A sub-nano-gram detection limit and sub-second response time were achieved, representing orders of magnitude improvement over those previously reported. This on-chip design will enable the unprecedented integration of optical vapor sensors with μGC systems.     

Novel e-nose for the discrimination of volatile organic biomarkers with an array of carbon nanotubes (CNT) conductive polymer nanocomposites (CPC) sensors

We report the original design of a new type of electronic nose (e-nose) consisting of only five sensors made of hierarchically structured conductive polymer nanocomposites (CPC). Each sensor benefits from both the exceptional electrical properties of carbon nanotubes (CNT) used to build the conductive architecture and the spray layer by layer (sLbL) assembly technique, which provides the transducers with a highly specific 3D surface structure. Excellent sensitivity and selectivity were obtained by optimizing the amount of CNT with five different polymer matrices: poly(caprolactone) (PCL), poly(lactic acid) (PLA), poly(carbonate) (PC), poly(methyl methacrylate) (PMMA) and a biobased polyester (BPR). The ability of the resulting e-nose to detect nine organic solvent vapours (isopropanol, tetrahydrofuran, dichloromethane, n-heptane, cyclohexane, methanol, ethanol, water and toluene), as well as biomarkers for lung cancer detection in breath analysis, has been demonstrated. Principal component analysis (PCA) proved to be an excellent pattern recognition tool to separate vapour clusters.     

Fabrication of carbon nanotubes/poly(1,2-diaminobenzene) nanoporous composite via multipulse chronoamperometric electropolymerization process and its electrocatalytic property toward oxidation of NADH

A novel method was proposed for fabrication of a carbon nanotubes/poly(1,2-diaminobenzene) nanoporous composite based electrode. The poly(1,2-diaminobenzene) was deposited onto the surface of a glassy carbon electrode (GCE) modified with multi-wall carbon nanotubes (MWNTs) via multipulse chronoamperometric electropolymerization (MCE) process. Compared with the composite prepared by conventional electropolymerization (CE), the electronic and ionic transport capacity of the MCE-based composite were significantly improved due to its unique nanoporous structure. The surface of the composite-modified GCE was characterized with scanning electron microscopy (SEM) and cyclic voltammetry (CV). The nanoporous MCE-based electrode was applied to determination of NADH at a much low potential of 70 mV, and a linear range from 2.0 μM to 4.0 mM was observed with fast response (within 5 s) and a lower detection limit of 0.5 μM (based on S/N = 3). In comparison, a narrow linear range from 5.0 μM to 2.0 mM, slower response (up to 15 s) and a higher detection limit of 3.0 μM (based on S/N = 3) was obtained with the electrode prepared by CE. The wider linear range, lower detection limit and fast response of the MCE-based electrode implies that the new method proposed can provide more excellent platforms for sensitive electrochemical sensing and biosensing.     

Humidity sensing and electrical properties of a composite material of nano-sized SiO2 and poly(2-acrylamido-2-methylpropane sulfonate)

A composite material of nano-sized SiO₂ and poly(2-acrylamido-2-methylpropane sulfonate) (poly(AMPS)) was used to make a humidity sensor. The infrared (IR) spectra and microstructure of the material were analyzed, and the humidity sensing and electrical properties of the sensor were measured. The sensor well responded to humidity with a relative good linearity, though it depended on the applied frequency. The temperature influence between 15 and 35 °C was −0.71 and −0.15% RH/°C at 30 and 90% RH, respectively. The sensor showed a negligible hysteresis and fast response time upon humidification and desiccation. The stability of the sensor in a highly humid and alcoholic environment increased with increasing the SiO₂ content. The activation energy for conduction reduced with water adsorption. The different impedance plots observed at low and high relative humidity suggested different sensing mechanisms of the SiO₂/poly(AMPS) composite material.     

Kinetic behavior of resistive oxygen sensor using cerium oxide

In order to decrease exhaust gas emissions, oxygen gas sensors with fast response are required. We evaluated two kinds of fast response time (<1 s) for two oxygen sensors with different cerium oxide particle sizes and crystallite sizes, using two methods: the commonly used jump method and the so-called dynamic method. The dynamic method consists of comparing the amplitude of oxygen partial pressure with that of the sensor output, following the changes in oxygen partial pressure produced by periodic modulation of the hydrostatic pressure with the composition of the atmosphere kept constant. The response times obtained with the jump method and dynamic method are defined as t₉₀ and t_b, respectively. Further, we evaluated the relationship between the amplitude magnitude of the oxygen sensor output (A_n) and the frequency of the oxygen partial pressure (f), using the dynamic method. The results obtained were as follows. The value of t_b for the oxygen sensor with a crystallite size and grain size of about 100 nm was 134 ms or less at 1173 K. The value of t₉₀ was 20 and 1 ms when the oxygen partial pressure changed from high to low and from low to high, respectively. From a plot of log A_n versus log f, it was concluded that the kinetics of a sensor using cerium oxide with crystallite and grain sizes from 100 to 300 nm were controlled by diffusion when the oxygen partial pressure was periodically changed in the shape of a sine wave. It was found that the newly developed equipment was able to evaluate two kinds of response times less than 50 ms.     

Organic light-emitting diodes with improved hole–electron balance and tunable light emission with aromatic diamine/bathocuproine multiple hole-trapping-layer

Organic light-emitting diodes (OLEDs) with multiple hole-trapping-layer (HTL) structures, which consist of N,N′-bis-(1-naphthyl)-N, N′-diphenyl-1,1′-biphenyl 4,4′-diamine (NPB), bathocuproine (BCP) and tris(8-hydroxy-quinoline)aluminum (Alq₃) have been fabricated. The emitting zone of the device with the structure of ITO/[NPB/BCP]_n/Alq₃/LiF/Al can be changed by the number n of HTL. The effect of the multiple HTL structure upon the performance of OLEDs with tris(8-hydroxyquinoline) aluminum as the emitting material has been investigated. Compared with the brightness of the conventional green emitting diode without the multiple HTL structure, that of the diode with periodic number of five has been increased from 2512.8 cd/m² to 8661.0 cd/m². Such an improvement in the device performance was attributed to the improved hole–electron balance, which can be further attributed to the introduction of the multiple HTL structure.     

Optimization of single mode fibre sensors to detect organic vapours

The construction of single mode optical fibre (SMF) sensors to handle with volatile organic compounds (VOCs), has been optimized to operate at the third telecommunication window (1550 nm). The main motivation is to take advantage of the photonic devices used in telecommunication systems that makes easier sensors multiplexing. Moreover, the low transmission attenuation at that wavelength offers the possibility of remote sensing. The sensing materials used suffer reversible structural alterations in the presence of VOC, such as colour change, which are detectable with a photonic system. Following the Electrostatic Self Assembly method (ESAm), a nanostructure is constructed onto cleaved ended SMF, which is doped with a sensing material. The fabrication of this type of sensors was focused on multimode fibres (MMF) and in the visible spectral range (VIS) so far. The implementation has been adapted to SMF and to operate around 1550 nm, specifically, by easing the adsorption of the VOCs molecules. It has been observed that the sensing material affects the morphology of the nanostructures as well and so, to the sensors response. The devices implemented show a potential use in the identification of single and complex mixtures of VOCs.