Determination of volatile organic compounds using piezosensors modified with the Langmuir-Blodgett films of calix[4]resorcinarene

A sensor based on a piezoelectric quartz resonator modified with the Langmuir-Blodgett (LB) films of calix[4]resorcinarene is proposed for the detection of volatile organic compounds. Parameters for the formation of ordered LB films based on calix[4]resorcinarene were optimized, and the effects of the pH and metal ion content of the subphase on the behavior of the Langmuir monolayers of calix[4]resorcinarene were studied. The effects of the number of monolayers in a sensor coating, the pH of the subphase from which the monolayers were transferred, and the presence of copper ions in the subphase on the response of the resulting piezoelectric quartz sensors to the vapors of various volatile organic compounds (ethanol, benzene, toluene, ethylbenzene, ethyl acetate, acetone, hexane, and cumene) were studied. It was found that the proposed sensor was characterized by a short response time and reproducible measurements.     

Quartz crystal microbalance determination of vapors of volatile organic compounds on carbon nanotubes under batch conditions

Specific features of the sorption of vapors of monoatomic aliphatic alcohols and aromatic compounds on coatings formed from carbon nanotubes of various genesis studied by the method of piezoelectric micro weighing are considered. The morphology of the coatings is considered in dependence on the conditions of synthesis and aftertreatment of carbon nanotubes. A new method of the processing of signals from an array piezoelectric sensors is proposed; it allows an increase in the selectivity of the determination of volatile organic compounds in an equilibrium gas phase by 2–2.5 times. The advantages of the application of carbon nanotubes as sorption coatings in comparison to the standard polymeric sorbents for piezoelectric micro weighing are demonstrated: the detection limit decreases by 4–15 times and the duration of measurement by 5–55 times.     

Piezoelectric Crystal Membrane Chemical Sensors Based on Fullerene and Macrocyclic Polyethers

Various reusable and sensitive piezoelectric (PZ) quartz crystal membrane sensors with home‐made computer interfaces for signal acquisition and data processing were developed to detect organic/inorganic vapors and organic/inorganic/biologic species in solutions, respectively. Fullerene(C60), fullerene derivatives and artificial macrocyclic polyethers, e.g., crown ethers and cryptands, were synthesized and applied as coating materials on quartz crystals of the PZ crystal sensors. The oscillating frequency of the quartz crystal decreased due to the adsorption of organic or inorganic species onto coating material molecules on the crystal surface. The crown ether‐coated PZ crystal gas detector exhibited high sensitivity with a frequency shift range of 10–340 Hz/(mg/L) for polar organic gases, a short response time (< 2.0 min.), good selectivity, and good reproducibility. The Ag(I)/crptand22 and Ru(III) / crptand22 coated PZ gas detectors were also prepared for nonpolar organic vapors, e.g., alkynes and alkenes. The frequency shifts of the nonpolar PZ sensors were in the order: alkynes > alkenes > alkanes. A Ti(IV)/Cryptand22‐coated PZ crystal sensor was also developed to detect the inorganic air pollutants, e.g., CO and NO₂. A piezoelectric gas sensor for both polar/nonpolar organic vapors based on C60‐cryptand22 was also prepared. The cryptand22‐coated PZ gas sensor was also employed as a GC detector for organic molecules. The cryptand22‐coated piezoelectric GC detectors compared well with the commercial thermal conductivity detector (TCD). The interaction between fullerene C60 and organic molecules was studied with a fullerene coated PZ gas detector. A multi‐channel PZ organic gas detector with PCA(Principal Component Analysis) and BPN (Back Propagation Neural) analysis methods was developed. Various liquid piezoelectric crystal sensors based on long‐chain macrocyclic polyethers, e.g., C₁₀H₂₁‐dibenzo‐16‐crown‐5, C₁₈H₃₇‐benzo‐15‐crown‐5, (C₁₇CO)₂‐cyptand22 and fullerene derivatives, e.g., C60‐NH‐cryptand22 and dibenzo‐16‐crown‐5‐C60, were also developed as HPLC detectors for metal ions, anions, and various organic compounds in solutions. The sensitive and highly selective PZ bio‐sensors based on enzymes, polyvinylaldehyde, polycinnaldehyde‐C60 and C60‐cryptand22 were developed to detect various biologic species, e.g., proteins, glucose, and urea. A quite sensitive EQCM (Electrochemical Quartz Crystal Micro‐balance) detection system was also developed for detection of trace heavy metal ions.     

Chemical Sensors for Electronic Nose Systems

Chemical sensors have been widely used for the analysis of volatile organic compounds. Employing chemical sensors in an array format with pattern recognition provides a higher degree of selectivity and reversibility leading to an extensive range of applications. When such systems are used for odour analysis they are termed electronic noses. Application of electronic noses ranges from the food industry, medical industry to environmental monitoring and process control. Many types of different gas sensors have been employed in the array. These include conducting polymers, metal oxide semiconductors, piezoelectric, optical fluorescence and amperometric gas sensors The transducer principle of these sensors is varied and is discussed in detail within this review. Examples of the current trends in sensor array technology as well as the applications to which the sensor-based noses have been applied are also discussed.     

Sorption specifics of volatile amines on thin films of acid-base indicators

The sorption specifics of various classes of volatile amines on thin films of organic acid-base indicators is studied by piezoelectric quartz micro weighing. The differences in the sorption behavior of amines on indicator films obtained from ethanolic and acetone solutions are revealed. The influence of the indicator acidity on the sorption of amine vapors is studied. An array of piezoelectric sensors based on thin films of acid-base indicators is developed and an algorithm of registering their responds to amines of different structures is proposed for their separate determination in a mixture.     

压电晶体传感器阵列用于混合有机溶剂蒸气中官能团的识别

为模拟生物化学传感体系, 提出了可用于识别有机官能团的传感器阵列, 用作人工气味识别系统。该阵列由八个压电晶体传感器组成, 每个传感器涂以具有广谱响应性能的不同吸附活性材料, 阵列对常见小分子有机溶剂混合蒸气的响应频移数据采用逐步判别分析(SDA)处理, 选出五个供信能力最佳的判别变量, 以此构成的阵列用于小分子有机溶剂混合蒸气中醇羟基、羰基与其它官能团的识别, 并采用主成分分析(PCA)法降维投影, 在二维空间含相同官能团的物质聚为一类; 阵列可用于酒类、软饮料的识别。     

A perfume odour-sensing system using an array of piezoelectric crystal sensors with plasticized PVC coatings

Using PVC polymer as membrane matrix and di-n-octylphenyl phosphate (DOPP) as plasticizer, a piezoelectric crystal sensor (PCS) array with 12 adsorptive materials selected from 68 compounds by cluster analysis has been constructed as a perfume odour-sensing system. The frequency shift data obtained from the sensor array responding to four commercial perfume odours are first autoscaled and then treated by principal component analysis. The experimental results show that the plasticized PVC membrane PCS array provides improved performance of pattern recognition compared with the single adsorptive coating PCS array. The frequency shift response characteristics of these sensors have been investigated experimentally. The proposed sensor array has also been applied to the classification of commercial spirituous liquor, wine and soft drink samples, as well as aliphatic alcohol homologues and isomers.     

A perfume odour-sensing system using an array of piezoelectric crystal sensors with plasticized PVC coatings

Using PVC polymer as membrane matrix and di-n-octylphenyl phosphate (DOPP) as plasticizer, a piezoelectric crystal sensor (PCS) array with 12 adsorptive materials selected from 68 compounds by cluster analysis has been constructed as a perfume odour-sensing system. The frequency shift data obtained from the sensor array responding to four commercial perfume odours are first autoscaled and then treated by principal component analysis. The experimental results show that the plasticized PVC membrane PCS array provides improved performance of pattern recognition compared with the single adsorptive coating PCS array. The frequency shift response characteristics of these sensors have been investigated experimentally. The proposed sensor array has also been applied to the classification of commercial spirituous liquor, wine and soft drink samples, as well as aliphatic alcohol homologues and isomers.     

压电晶体传感器阵列测定装置及数据采集系统

研究了一种利用微机控制测量和采集压电晶体传感器阵列振荡频率的智能型仪器。介绍了其硬件及数据采集软件的功能，结构等。     

Vapor sensing using polymer/carbon black composites in the percolative conduction regime

To investigate the behavior of chemiresistive vapor sensors operating below or around the percolation threshold, chemiresistors have been formed from composites of insulating organic polymers and low mass fractions of conductive carbon black (CB, 1-12% w/w). Such sensors produced extremely large relative differential resistance changes above certain threshold vapor concentrations. At high analyte partial pressures, these sensors exhibited better signal/noise characteristics and were typically less mutually correlated in their vapor response properties than composites formed using higher mass fractions of CB in the same set of polymer sorption layers. The responses of the low-mass-fraction CB sensors were, however, less repeatable, and their nonlinear response as a function of analyte concentration required more complicated calibration schemes to identify and quantify analyte vapors to compensate for drift of a sensor array and to compensate for variability in response between sensor arrays. Because of their much larger response signals, the low-mass-fraction CB sensors might be especially well suited for use with low-precision analog-to-digital signal readout electronics. These sensors serve well as a complement to composites formed from higher mass fractions of CB and have yielded insight into the tradeoffs of signal-to-noise improvements vs complexity of signal processing algorithms necessitated by the use of nonlinearly responding detectors in array-based sensing schemes.     

Procedure for the analysis of sedative drugs with the use of an array of piezoelectric sensors (Exemplified in the determination of the drug Corvalol)

A procedure was developed for the headspace analysis of sedative drugs with the use of a quartz piezoelectric microbalance array. The effects of the nature of film coatings in piezoelectric cell electrodes on the working weight range and the sorption properties of sorbent films were found. An array of six piezoelectric sensors with different response functions in the vapors of the drug Corvalol and its highly volatile constituents was proposed. The procedure is suitable for the quality assessment of other pharmaceuticals based on ethyl alcohol and natural peppermint oil. Original Russian Text ￠ T.A. Kuchmenko, A.V. Kozhukhova, Yu.I. Orobinskii, 2008, published in Zhurnal Analiticheskoi Khimii, 2008, Vol. 63, No. 3, pp. 314–321.     

Development of a chemical vapor sensor using piezoelectric quartz crystals with coated unusual lipids

Piezoelectric quartz crystal sensors were developed using lipids with various properties for highly sensitive detection of chemical vapors. Lipids with varying lengths of alkyl chains were coated onto 10 MHz AT-cut quartz crystal resonators and the response of these modified crystals to chemical vapors were measured. It was shown that hydrophilic compounds, such as ethanol and methanol, could be recognized efficiently by lipids having shorter alkyl chains, whereas lipids with longer alkyl chains showed affinity to more hydrophobic vapors, such as toluene, hexane and cyclohexane. Frequency changes caused by adsorption of alcohols could be enhanced when cholesterol was co-immobilized in the lipid layer. To confirm the assumption that the sensor-response might be affected by the properties of lipids derived from acyl chains, we have examined the effects of two types of newly synthesized unusual lipids on sensor response. When lipids having one triple bond each at different positions on their alkyl chains were coated onto quartz crystals separately, lower responses were observed compared to responses obtained for a sensor with immobilized, saturated phosphatidylcholine. Lipids containing -branched acyl chains, however, showed good affinity for organic vapors, and sensor responses improved 4–5-fold. Moreover, these sensors were shown to have sensitivity of the same order as the humans' sense of smell (10⁻⁵–10⁻⁶ w/w in liquid paraffin) when measured using standard odorants (isovaleric acid, skatole, etc.) for an olfactometry established in Japan.     

Physicochemical characteristics of the reaction of vapors of organic liquids with divinyl-styrene and isoprene polymer films of piezoelectric chemical sorption sensors

The reaction of vapors of organic liquids with films of carbon-chain polymers was studied on piezoelectric quartz resonators. Physicochemical characteristics of sorption processes in the system vapor-film sorbent were determined in the region obeying Henry’s law. It was concluded that divinyl-styrene polymer can be used in piezoelectric chemical sensors for environmental control of trace organic toxicants.     

Chemical vapor discrimination using a compact and low-power array of piezoresistive microcantilevers

A compact and low-power microcantilever-based sensor array has been developed and used to detect various chemical vapor analytes. In contrast to earlier micro-electro-mechanical systems (MEMS) array sensors, this device uses the static deflection of piezoresistive cantilevers due to the swelling of glassy polyolefin coatings during sorption of chemical vapors. To maximize the sensor response to a variety of chemical analytes, the polymers are selected based on their Hildebrand solubility parameters to span a wide range of chemical properties. We utilize a novel microcontact spotting method to reproducibly coat a single side of each cantilever in the array with the polymers. To demonstrate the utility of the sensor array we have reproducibly detected 11 chemical vapors, representing a breadth of chemical properties, in real time and over a wide range of vapor concentrations. We also report the detection of the chemical warfare agents (CWAs) VX and sulfur mustard (HD), representing the first published report of CWA vapor detection by a polymer-based, cantilever sensor array. Comparisons of the theoretical polymer/vapor partition coefficient to the experimental cantilever deflection responses show that, while general trends can be reasonably predicted, a simple linear relationship does not exist.     

Ionic liquid high temperature gas sensors

An ionic liquid piezoelectric gas sensor was demonstrated for detection of polar and nonpolar organic vapors at high temperature with fast linear and reversible response.     

Electrical,electrochemical, and thermometric sensors for the detection of explosives

The main analytical characteristics of electrical, electrochemical, and thermometric sensors in the detection of vapors and traces of explosives and accompanying substances are compared. The limits of detection, sensitivity, sensor setting time (response speed) and, recovery time after exposure to analytes, and the selectivity of sensors are discussed. The efficiency of using nanodimensional structures in the sensing elements of sensors is investigated.     

The character of the response of ZnO and SnO<Subscript>2</Subscript> sensors modified with porphyrins to volatile organic compounds

The influence of the modification of the surface of ZnO and SnO₂ sensors with 5,10,15,20-tetraphenylporphyrin on the parameters of sensor response to high-volatility organic substances was analyzed. The organic substances used were ethanol, acetone, and benzene. The sensor response was characterized by specific sensitivity γ determined as the ratio between a change in the resistance of the sensitive sensor layer and the volume concentration of high-volatility organic compounds introduced into the system. The modification of the sensors with tetraphenylporphyrin caused changes in sensor response, including a change in the sign of the γ parameter, which was of importance for creating “electronic nose” sensor systems.     

Humidity effect on the monolayer-protected gold nanoparticles coated chemiresistor sensor for VOCs analysis

Two gold-thiolate monolayer-protected nanoparticles were synthesized and used as interfacial layers on chemiresistor sensors for the analysis of violate organic compounds (VOCs). Toluene, ethanol, acetone and ethyl acetate were chosen as the target vapors. Both the resistance and capacitance were measured as the function of analyte concentrations. The effect of humidity on the sensor sensitivity to VOCs was investigated. The sensitivity decreases with humidity increasing, depending on the hydrophobicity of the target compounds. Less effect was observed on the higher hydrophobic compounds. While the relative humidity (RH) increased from 0 to 60%, the sensitivity to acetone decreased by 39 and 37%, respectively on the Au-octanethiol (C₈Au) and Au-2-phenylethanethiol (BC₂Au) coated sensors, while the sensitivity to toluene decreased by 12 and 14%, respectively. These results show that the sensors coated with hydrophobic compounds protected-metal nanoparticles can be employed in high humidity for hydrophobic compounds analysis. The resistance responses to VOCs are rapid, reversible, and linear, while the capacitance response is not sensitive and consequently not applicable for VOCs analysis. The response mechanism was also discussed based on the sensor response to water vapor. The capacitance response is not sensitive to the film swelling in dry environment.     

Temperature and humidity compensation in the determination of solvent vapors with a microsensor system

Accounting for changes in temperature and ambient humidity is critical to the development of practical field vapor-monitoring instrumentation employing microfabricated sensor arrays. In this study, responses to six organic vapors were collected from two prototype field instruments over a range of ambient temperatures and relative humidities (RH). Each instrument contains an array of three unthermostated polymer-coated surface acoustic wave (SAW) resonators, a thermally desorbed adsorbent preconcentrator bed, a reversible pump and a small scrubber cartridge. Negligible changes in the vapor sensitivities with atmospheric RH were observed owing, in large part, to the temporal separation of co-adsorbed water from the organic vapor analytes upon thermal desorption of preconcentrated air samples. As a result, calibrations performed at one RH level could be used to determine vapors at any other RH without corrections using standard pattern recognition methods. Negative exponential temperature dependences that agreed reasonably well with those predicted from theory were observed for many of the vapor-sensor combinations. It was possible to select a subset of sensors with structurally diverse polymer coatings whose sensitivities to all six test vapors and selected binary vapor mixtures had similar temperature dependences. Thus, vapor recognition could be rendered independent of temperature and vapor quantification could be corrected for temperature with sufficient accuracy for most applications. The results indicate that active temperature control is not necessary and that temperature and RH compensation is achievable with a relatively simple microsensor system.     

Quartz crystal microbalance sensor array for the detection of volatile organic compounds

A sensor array system consisting of five quartz crystal microbalance (QCM) sensors (four for measuring and one for reference) and an artificial neural network (ANN) method is presented for on-line detection of volatile organic compounds. Three ionic liquids, 1-butyl-3-methylimidazolium chloride (C₄mimCl), 1-butyl-3-methylimidazolium hexafluorophosphate (C₄mimPF₆), 1-dedocyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (C₄mimNTf₂), and silicone oil II, which is widely used as gas chromatographic stationary phase, have been selected as sensitive coatings on the quartz surface allowing the sensor array effective to identify chemical vapors, such as toluene, ethanol, acetone and dichloromethane. The success rate for the qualitative recognition reached 100%. Quantitative analysis has also been investigated, within the concentration range of 0.6-6.1 mg/L for toluene, 0.9-7.5 mg/L for ethanol, 2.8-117 mg/L for dichloromethane, and 0.7-38 mg/L for acetone, with a prediction error lower than 8%.