Development of a flow injection analytical system for short chain amide determination based on a tubular bioreactor and an ammonium sensor.

Pseudomonas aeruginosa (P. aeruginosa) possesses intracellular amidase activity, which catalyses the hydrolysis of short aliphatic amides producing NH4+, and has already been used along with an ammonium ion selective electrode for amide quantification. However, the incorporation of a biological membrane turned to be a challenging process and either the final arrangement was prone to amidase losses or the recovery of the sensor coating after the interaction took too long. In this article a flow injection system with an ammonium acoustic wave sensor is proposed, and after testing several different arrangements for the biological element, the ultimate choice consisted of the immobilization of a P. aeruginosa cell-free extract in the inner wall of a tubular glass reactor, which resulted in a reliable analytical system. Response times less than one minute and complete recovery in less than two minutes assured conveniently fast analysis. The analytical system, as long as the column was properly stored in HEPES buffer containing 2 mM ß-mercaptoethanol and 1 mM benzamidine and refrigerated when not in use, could be used at least for 20 working days, along a period of one month, maintaining the initial sensitivity.

Cheeses Made from Raw and Pasteurized Cow's Milk Analysed by an Electronic Nose and an Electronic Tongue.

Cheese prepared from whole milk, raw and pasteurized, were analysed by an electronic nose based on piezoelectric quartz crystals and an electronic tongue based on potentiometric sensors, immediately after their preparation and along ripening (after 7 and 21 days). Whey was also analysed by the potentiometric electronic tongue. Results obtained by the electronic nose and tongue were found to be complementary, with the electronic nose being more sensitive to differences in the milk and the electronic tongue being more sensitive to milk pasteurization. Electronic tongue was able to distinguish cheeses made from raw and pasteurized milk, both analysing the whey or the curd, with correct classification rate of 96% and 84%, respectively. Besides, the electronic nose was more sensitive than the electronic tongue to the ripening process, with large differences between samples after 7 and 21 days, while the electronic tongue was only sensitive to the initial maturation stages, with large difference between freshly prepared cheese and with seven days of maturation.

N-Confused Porphyrin Immobilized on Solid Supports: Synthesis and Metal Ions Sensing Efficacy.

In this work, the N-confused porphyrin 5,10,15,20-tetraphenyl-2-aza-21-carbaporphyrin (NCTPP) was immobilized on neutral or cationic supports based on silica and on Merrifield resin. The new materials were characterized by appropriate techniques (UV-Vis spectroscopy, SEM, and zeta potential analysis). Piezoelectric quartz crystal gold electrodes were coated with the different hybrids and their ability to interact with heavy metals was evaluated. The preliminary results obtained showed that the new materials can be explored for metal cations detection and the modification of the material surface is a key factor in tuning the metal selectivity.

Potentiometric chemical sensors from lignin-poly(propylene oxide) copolymers doped by carbon nanotubes.

Hardwood and softwood lignins obtained from industrial sulphite and kraft and laboratory oxygen-organosolv pulping processes were employed in co-polymerization with tolylene 2,4-diisocyanate terminated poly(propylene glycol). The obtained lignin-based polyurethanes were doped with 0.72 w/w% of multiwall carbon nanotubes (MWCNTs) with the aim of increasing their electrical conductivity to the levels suitable for sensor applications. Effects of the polymer doping with MWCNTs were assessed using electrical impedance (EIS) and UV-Resonance Raman (UV-RR) spectroscopy. Potentiometric sensors were prepared by drop casting of liquid polymer on the surface of carbon glass or platinum electrodes. Lignin-based sensors displayed a very low or no sensitivity to all alkali, alkali-earth and transition metal cations ions except Cr(VI) at pH 2. Response to Cr(VI) values of 39, 50 and 53 mV pX(-1) for the sensors based on kraft, organosolv and lignosulphonate lignins, respectively, were observed. Redox sensitivity values close to the theoretical values of 20 and 21 mV pX(-1) for organosolv and lignosulphonate based sensors respectively were detected in the Cr(III)/Cr(VI) solutions while a very low response was observed in the solutions containing Fe(CN)(6)(3-/4-). Conducting composite lignin-based polyurethanes doped with MWCNTs were suggested as being promising materials for Cr(VI)-sensitive potentiometric sensors.

Polyoxometalate Functionalized Sensors: A Review.

Polyoxometalates (POMs) are a class of metal oxide complexes with a large structural diversity. Effective control of the final chemical and physical properties of POMs could be provided by fine-tuning chemical modifications, such as the inclusion of other metals or non-metal ions. In addition, the nature and type of the counterion can also impact POM properties, like solubility. Besides, POMs may combine with carbon materials as graphene oxide, reduced graphene oxide or carbon nanotubes to enhance electronic conductivity, with noble metal nanoparticles to increase catalytic and functional sites, be introduced into metal-organic frameworks to increase surface area and expose more active sites, and embedded into conducting polymers. The possibility to design POMs to match properties adequate for specific sensing applications turns them into highly desirable chemicals for sensor sensitive layers. This review intends to provide an overview of POM structures used in sensors (electrochemical, optical, and piezoelectric), highlighting their main functional features. Furthermore, this review aims to summarize the reported applications of POMs in sensors for detecting and determining analytes in different matrices, many of them with biochemical and clinical relevance, along with analytical figures of merit and main virtues and problems of such devices. Special emphasis is given to the stability of POMs sensitive layers, detection limits, selectivity, the pH working range and throughput.

A new formaldehyde optical sensor: Detecting milk adulteration.

A sensor consisting of an optical fibre with the exposed tip coated with the polyoxometalate salt [(C4H9)4N]4H[PMo10V2O40], specially designed to be insoluble in water, which UV-Vis spectrum changed in contact with formaldehyde, is presented. The sensor limit of detection for formaldehyde was 0.2 mg L-1, and the limit of quantification was 0.6 mg L-1, which were close to the conventional spectrophotometric method values of 0.2 mg L-1 and 0.5 mg L-1, respectively, and lower than the tolerable limit for ingested food. The sensor was tested for formaldehyde quantification in milk, as its deliberate addition is a matter of concern. The results obtained analysing formaldehyde in milk samples by the optical sensor and by the conventional method were not statistically different (α = 0.05).

Molecularly Imprinted Polymer Thin-Film Electrochemical Sensors.

Preparation of potentiometric and amperometric sensors with thin-film membranes based on molecularly imprinted polymers (MIP) is described. Spherical MIP microparticles with diameter below 1 µm are suitable for incorporation into the sensing membrane by the deposition of a conducting polymer on the electrode surface. This is achieved through electropolymerization from the suspension of MIP particles in monomer solution. Procedures of the synthesis of MIP particles, preparation of sensing membranes, and analytical application of potentiometric and amperometric sensors with MIP-modified membranes are described.

Preserve Your Books through the Smell.

The identification of paper composition, pH, early signs of paper degradation, and emitting volatile organic compounds (VOCs) are mandatory for effective preventive conservation of paper/books. Sampling restrictions in the analysis of cultural heritage materials limit the choice of appropriate analytical methods. Solvent-free analytical techniques with nondestructive sampling are needed. Addressing this challenge, an electronic nose based on six-coated piezoelectric quartz crystals was assembled and used to analyze VOCs emitted from books. Careful selection of sensor coatings and cluster analysis allowed us to achieve a clear distinction between cotton/linen rag and wood pulp paper, and among the letter group, the discrimination between papers manufactured from alkaline and acidic stocks. This six-element sensor array was therefore able to replace destructive tests as the ones ordinarily used for paper pH measurements. The same electronic nose was able to separate aged pale-yellow paper, a visible initial sign of paper degradation, from well-preserved still white papers, even when made from the same raw material. One of the used sensors detected furfural, often seen as a marker of cellulose degradation, at lower levels than the detection limit found in the literature with gas chromatography-mass spectrometry, a much more complex bulky and expensive instrument.

Aluminium migration into beverages: are dented cans safe?

Aluminium (Al) migration from cans to beer and tea was studied along time. Analyses of Al in the canned drinks were performed till the sell-by date, and, in seven months, aluminium migration was found to increase 0.14 mg L(-1) in beer, and 0.6 mg L(-1) in tea. This study included dented cans from which aluminium migration into tea was found to be particularly severe. Al concentration in dented canned tea increased 9.6 mg L(-1) in seven months.

Analysing sulphate and chloride in mineral drinking water by flow injection analysis with a single acoustic wave sensor.

Sulphate is a very hydrophilic anion, and, therefore, difficult to be selectively determined in aqueous solution with a coated sensor. Zinc(II) 2,3,9,10,16,17,23,24-Octatosylaminophthalocyanine was used for the first time as a sensitive coating. Selectivity to sulphate regarding chloride was not enough to ignore its contribution in mineral waters, and, therefore, an analytical protocol was carefully designed to allow the determination of both anions with this sensor. Results displayed on the label of eight commercial bottles of mineral waters are within the confidence interval of the values obtained with the FIA-sensor system, both for chloride and sulphate. However, results for chloride obtained by titrimetry are, in half of the cases, statistically different from the ones obtained by the sensor, and in 7 out of 8 of them more precise. There is an evidence of a systematic error in the chloride titrimetric analysis, consistent with a small overtaking of the equivalence point. Precision of the results obtained by the titrimetric analysis of sulphate were in 6 out of 8 of the analysis less precise than with the sensor, probably due to losses of the barium sulphate precipitate, which is consistent with the occurrence of lower values.

Determination of 5-hydroxymethylfurfural in honey, using headspace-solid-phase microextraction coupled with a polyoxometalate-coated piezoelectric quartz crystal.

High concentrations of 5-hydroxymethylfurfural (HMF) in honey provide an indication of overheating under inappropriate storage conditions or aging. Conventional methods for determining HMF are cumbersome and require expensive equipment or hazardous reagents. Hence the aim of this study was to propose a new analytical tool for HMF determination in honey, using a low cost acoustic wave sensor. Volatile organic compounds (VOCs) of honey samples were extracted, using the solid phase microextraction (SPME) technique, and HMF was quantified, using a piezoelectric quartz crystal with gold electrodes coated with a layer of decamolybdodivanado phosphoric acid, sensitive to HMF. The reliability of the proposed method was confirmed after comparing the results of HMF quantification with those obtained by the conventional spectrophotometric White method, and no statistical differences were found (α=0.05).

[28]Hexaphyrin derivatives for anion recognition in organic and aqueous media.

Hexaphyrin-based anion chemosensors are reported for the first time. The meso-hexakis(ethylenediamine)-substituted [28]hexaphyrins 2 and 3 revealed strong affinity for F(-), AcO(-) and H2PO4(-). Adsorption constants in aqueous media were determined on a gold piezoelectric crystal coated with 2 and 3. (1)H NMR titrations and molecular dynamics simulations showed the main interactions between hosts and guests.

Assessment of copper toxicity using an acoustic wave sensor.

A piezoelectric quartz crystal microbalance has been shown to be useful to monitor real time bacterial growth. Monitoring bacterial growth can give an insight into the ecosystem, as it is highly affected by the presence of toxic elements or nutrients. The frequency of an uncoated piezoelectric quartz crystal was monitored while in contact with bacteria, isolated from water sampled from a Portuguese lagoon, growing in two different media: a saline nutrient broth (NM) and the natural water. The sensor was used to evaluate the effect of copper on bacterial growth. Copper concentrations up to 18.8 microg l(-1) showed an increase in bacterial growth in NM, and a decrease beyond 25.0 microg l(-1). Copper added to the natural water had negative effects on bacterial growth beyond 18.8 microg l(-1). Copper concentrations in the natural water from the lagoon were determined using a similar quartz crystal to detect the mass deposited by anodic stripping voltammetry, and was found to be 3.38 +/- 0.09 microg l(-1).

Thin-film electrochemical sensor for diphenylamine detection using molecularly imprinted polymers.

This work reports on the development of a new voltammetric sensor for diphenylamine based on the use of a miniaturized gold electrode modified with a molecularly imprinted polymer recognition element. Molecularly imprinted particles were synthesized ex situ and further entrapped into a poly(3,4-ethylenedioxythiophene) polymer membrane, which was electropolymerized on the surface of the gold electrode. The thickness of the polymer layer was optimized in order to get an adequate diffusion of the target analyte and in turn to achieve an adequate charge transfer at the electrode surface. The resulting modified electrodes showed a selective response to diphenylamine and a high sensitivity compared with the bare gold electrode and the electrode modified with poly(3,4-ethylenedioxythiophene) and non-imprinted polymer particles. The sensor showed a linear range from 4.95 to 115 µM diphenylamine, a limit of detection of 3.9 µM and a good selectivity in the presence of other structurally related molecules. This sensor was successfully applied to the quantification of diphenylamine in spiked apple juice samples.

New porphyrin derivatives for phosphate anion sensing in both organic and aqueous media.

New porphyrin-based anion receptors have been prepared from meso-tetrakis(pentafluorophenyl)porphyrin () and diamine derivatives. These receptors (compounds ) interact preferentially with phosphate anions both in organic solutions and in basic aqueous media when coated on gold piezoelectric quartz crystals. A single crystal X-ray structure of the bis-HF complex of a imine derivative of was obtained; it serves to highlight the main interactions between the anion and cation receptors in the solid state.

Following butter flavour deterioration with an acoustic wave sensor.

Off-flavours develop naturally in butter and the process is accelerated by heat. An acoustic wave sensor was used to detect the aroma compounds evolved from heated butter and the results have shown that registered marked changes were coincident to odour changes detected by sensory analysis. The flavour compounds have also been analysed by GC/MS for identification. The response of the sensor was fully characterized in terms of the sensitivity to each of the identified compounds, and sensitivities of the system SPME/sensor were compared with the sensitivities of the system SPME/GC/MS. It was found that the sensor analytical system was more sensitive to methylketones than to fatty acids. The SPME/GC/MS system also showed the highest sensitivity to 2-heptanone, followed by 2-nonanone, but third place was occupied by undecanone and butanoic acid, to which the sensor showed moderate sensitivity. 2-heptanone was found to be an appropriate model compound to follow odour changes till the 500 h, and the lower sensitivity of the sensor to butanoic acid showed to be a positive characteristic, as saturation was prevented, and other more subtle changes in the flavour could be perceived.

An insight into the adsorption and electrochemical processes occurring during the analysis of copper and lead in wines, using an electrochemical quartz crystal nanobalance.

Copper and lead in wine were quantified by anodic stripping voltammetry (ASV), performed onto the gold electrode of a piezoelectric quartz crystal. Both current or mass changes could be used as analytical signals, without a statistical difference in the results (α=0.05). However, the plot of mass vs. potential provided an in depth understanding of the electrochemical processes and allowed studying adsorption phenomena. Copper interaction with fructose is an example of a process which was not possible to ignore by observing the mass change on the gold electrode of the piezoelectric quartz crystal.

Development of an electronic nose to identify and quantify volatile hazardous compounds.

A new electronic nose was developed to identify the chemical compound released when a 2.5-L flask was broken inside a 3 m x 3 m x 2.5 m store-room. Flasks of 10 different hazardous compounds were initially present in the room: ammonia, propanone, hexane, acetic acid, toluene, methanol, tetrachloromethane, chloroform, ethanol and dichloromethane. Besides identification, quantification of the compound present in the air was also performed by the electronic nose, in order to evaluate the risk level for room cleaning. An array of six sensors based on coated piezoelectric quartz crystals was used. Although none of the individual sensors was specific for a single compound, an artificial neural network made it possible to identify and quantify the released vapour, among a series of 10 compounds, with six sensors. The neural network could be simplified, and the number of neurons reduced, provided it was used just for the identification task. Quantification could be performed later using the individual calibration of the sensor most sensitive to the identified compound.

The quality of our drinking water: aluminium determination with an acoustic wave sensor.

A new methodology based on an inexpensive aluminium acoustic wave sensor is presented. Although the aluminium sensor has already been reported, and the composition of the selective membrane is known, the low detection limits required for the analysis of drinking water, demanded the inclusion of a preconcentration stage, as well as an optimization of the sensor. The necessary coating amount was established, as well as the best preconcentration protocol, in terms of oxidation of organic matter and aluminium elution from the Chelex-100. The methodology developed with the acoustic wave sensor allowed aluminium quantitation above 0.07 mg L(-1). Several water samples from Portugal were analysed using the acoustic wave sensor, as well as by UV-vis spectrophotometry. Results obtained with both methodologies were not statistically different (alpha=0.05), both in terms of accuracy and precision. This new methodology proved to be adequate for aluminium quantitation in drinking water and showed to be faster and less reagent consuming than the UV spectrophotometric methodology.

Detecting spoiled fruit in the house of the future.

An electronic nose based on acoustic wave sensors has been developed to detect spoilt fruit. Different varieties of fruits, edible and rotten, were analysed. Starting from six sensors, the minimum number of sensors capable of discriminating between spoiled and unspoiled fruit was found. The discrimination capability of the sensor array was studied separately for each fruit variety, as well as for the whole set. Mathematical models were built to classify the fruits within a fruit variety, in an objective and clear way. The models were able to distinguish between edible and rotten fruits with 100% success for New Hall oranges, Golden apples, Kiwis and William pears, and with 97.2% of success for the Starking apples. Without forming fruit variety subsets, discrimination between edible and rotten fruit was achieved with 95% success.