Chemosensors, Volume 7, Issue 3 (September 2019) – 19 articles

1-(3-chlorophenyl)piperazine (mCPP) is a wide spread new psychoactive substance produces stimulant and hallucinogenic effects similar to those sought from ecstasy. Hence, in the recent years, mCPP has been introduced by the organized crime through the darknet as a part of the illicit ecstasy market with a variable complex profile of pharmacologically active substances that pose problematic risk patterns among people who take these seized products. Accordingly, the design of selective sensors for the determination of mCPP is a very important demand. In this respect, a supramolecular architecture; [Na(15-crown-5)][BPh₄] from the assembly of 15-crown-5 and sodium tetraphenylboron has been utilized as an ionophore, for the first time in the selective recognition of mCPP in conjunction with potassium tetrakis(p-chlorophenyl)borate and dioctylphthalate through polymeric membrane ion sensors. The ionophore exhibited a strong binding affinity that resulted in a high sensitivity with a slope closed to the ideal Nernstian value; 58.9 ± 0.43 mV/decade, a larger dynamic range from 10⁻⁶ to 10⁻² M, a lower limit of detection down to 5.0 × 10⁻⁷ M and a fast response time of 5 s. Very important also is it was afforded excellent selectivity towards mCPP over psychoactive substances of major concern, providing a potentially useful system for the determination of mCPP in the illicit market. On comparison with the natural β-cyclodextrin as an ionophore, it exhibited more sensitivity and selectivity estimated to be the superior. Full article

Various brain imaging techniques are available, but few are specifically designed to visualize chemical sensory and, in particular, olfactory processing. This review describes the results of quantitative and qualitative studies that have used electroencephalography (EEG) and magneto-encephalography (MEG) to evaluate responses to olfactory stimulation (OS). EEG and MEG are able to detect the components of chemosensory event-related potentials (CSERPs) and the cortical rhythms associated with different types of OS. Olfactory studies are filling the gaps in both the developmental field of the life cycle (from newborns to geriatric age) and the clinical and basic research fields, in a way that can be considered the modern “cognitive neuro-olfactometry”. Full article

In this work, we report a one-step approach for fabricating screened-printed microfluidic paper-based analytical devices (μPADs) using polylactic acid as a new hydrophobic material. A polylactic acid solution was screen printed onto chromatography papers to create hydrophobic patterns for fluidic channels. The optimal polylactic acid concentration for successful device fabrication is 9% w/v. The μPADs were fabricated within 2 min and provided high reproducibility and stability. The utility of polylactic acid screen-printing was demonstrated for the simultaneous detection of nitrite and nitrate using colorimetric detection. Under optimized experimental conditions, the detection limits and the linear ranges, respectively, were 1.2 mg L⁻¹ and 2–10 mg L⁻¹ for nitrite and 3.6 mg L⁻¹ and 10–50 mg L⁻¹ for nitrate. The detection times for both ions were found to be within 12 min. The developed μPAD was applied for the simultaneous determination of these ions in food samples, and no significant differences in the analytical results were observed compared to those of the reference method. The polylactic acid screen-printing approach presented here provides a simple, rapid, and cost-effective alternative fabrication method for fabricating μPADs. Full article

Glucose, fructose and sucrose are sugars with known physiological effects, and their consumption has impact on the human health, also having an important effect on food sensory attributes. The analytical methods routinely used for identification and quantification of sugars in foods, like liquid chromatography and visible spectrophotometry have several disadvantages, like longer analysis times, high consumption of chemicals and the need for pretreatments of samples. To overcome these drawbacks, in this work, a potentiometric electronic tongue built with two identical multi-sensor systems of 20 cross-selectivity polymeric sensors, coupled with multivariate calibration with feature selection (a simulated annealing algorithm) was applied to quantify glucose, fructose and sucrose, and the total content of sugars as well. Standard solutions of ternary mixtures of the three sugars were used for multivariate calibration purposes, according to an orthogonal experimental design (multilevel fractional factorial design) with or without ionic background (KCl solution). The quantitative models’ predictive performance was evaluated by cross-validation with K-folds (internal validation) using selected data for training (selected with the K-means algorithm) and by external validation using test data. Overall, satisfactory predictive quantifications were achieved for all sugars and total sugar content based on subsets comprising 16 or 17 sensors. The test data allowed us to compare models’ predictions values and the respective sugar experimental values, showing slopes varying between 0.95 and 1.03, intercept values statistically equal to zero (p-value ≥ 0.05) and determination coefficients equal to or greater than 0.986. No significant differences were found between the predictive performances for the quantification of sugars using synthetic solutions with or without KCl (1 mol L⁻¹), although the adjustment of the ionic background allowed a better homogenization of the solution’s matrix and probably contributed to an enhanced confidence in the analytical work across all of the calibration working range. Full article

Thin films are being used more and more in gas sensing applications, relying on their high surface area to volume ratio. In this study, ZnO thin film was produced through a thermal aerosol spraying and chemical vapor deposition (spray-CVD) process at 500 °C using zinc acetate as a precursor. The phase identification and the morphologies of the film were investigated by XRD and SEM, respectively. Gas-sensing properties of the ZnO thin film were evaluated toward NO₂, CO, and NO at a moderate temperature range (400–500 °C) in dry and humid air (relative humidity = 2.5, 5, 7.5, and 10% RH). The obtained results show good sensor signal for both NO₂ (ΔR/R₀ = 94%) and CO (92%) and poor sensor signal to NO (52%) at an optimum temperature of 450 °C in dry air. The response and recovery times decrease with the increase of NO₂ concentration. In the presence of humidity (10% of RH), the sensor is more than twice as sensitive to NO₂ (70%) as CO (29%), and accordingly, exhibits good selectivity toward NO₂. As the amount of humidity increases from 2.5 to 10% RH, the selectivity ratio of ZnO thin film to NO₂ against CO increases from 1 to 2.4. It was also observed that the response and the recovery rates decrease with the increase of relative humidity. The significant enhancement of the selectivity of ZnO thin film toward NO₂ in the presence of humidity was attributed to the strong affinity of OH species with NO₂. Full article

This research is devoted to the development and study of novel cross-sensitive sensors based on modified extracting ligands. According to the previous results of liquid extraction studies, the chemical modification of membrane active components would change the analytical characteristics of a sensor comprising them. The sensing elements of the studied sensors consisted of various derivatives of N,N,N′,N′-tetraoctyldiamide of diglycolic acid (TODGA) and di-phenyl-N,N-di-i-sobutylcarbamoylmethylen phoshine oxide (CMPO) used as neutral carriers, CCD (chlorinated cobalt dicarbollide) as a lipophilic additive, different plasticizers, and poly(vinyl chloride) (PVC) as a polymer. TODGA-based sensors demonstrated a stable and reproducible response towards rare earth cations in acidic media (pH = 2). Changing the concentrations and ratio of neutral carriers and the lipophilic additive, it is possible to modify the sensitivity and selectivity of the sensors towards the same target ions. Bonded ligands, such as cobalt dicarbollide covalently attached to TODGA and CMPO, exhibited lower selectivity and sensitivity to rare earth cations. A possibility to vary the cross-sensitivity patterns of the sensors in a wide range might be of great interest for the development of multisensor systems allowing the simultaneous determination of several analytes in multicomponent solutions. Full article

The objective of this study was to examine the sensor response characteristics of three commercial Internet of Things (IoT) compatible metal oxide (MOx) sensors in preparation for the development of field-scale sensor networks for the real-time monitoring of volatile organic compounds (VOCs) in indoor environments located in proximity to brownfield sites. Currently, there is limited examination of such sensor responses to relevant mixtures of target VOCs, such as the common petrochemicals benzene, toluene, ethylbenzene, and xylene (BTEX), as well as chlorinated aliphatic hydrocarbon (CAH) contaminants such as tetrachloroethylene (PCE) and trichloroethylene (TCE) which are frequently associated with deterioration of indoor air quality. To address this, a study of three commercial metal oxide (MOx) sensors (SGP30, BME680, and CCS811) was undertaken to examine the sensor response characteristics of individual components as well as mixtures of each of the target BTEX and CAH chemicals over relevant indoor air concentrations within the operating range of the MOx sensors (0–6000 ppb). Our investigation revealed similar response patterns to those previously reported for the thick film MOx sensor to most individual target VOCs, however, response trends for mixtures were more difficult to discern. In general, the MOx sensors we examined demonstrated similar magnitude responses to the CAHs as BTEX compounds indicating reliable detection of CAHs. Full article

This paper provides a selection of the last two decades publications on the development and application of chemical sensors based on piezoelectric quartz resonators for a wide range of analytical tasks. Most of the attention is devoted to an analysis of gas and liquid media and to industrial processes controls utilizing single quartz crystal microbalance (QCM) sensors, bulk acoustic wave (BAW) sensors, and their arrays in e-nose systems. The unique opportunity to estimate several heavy metals in natural and wastewater samples from the output of a QCM sensor array highly sensitive to changes in metal ion activity in water vapor is shown. The high potential of QCM multisensor systems for fast and cost-effective water contamination assessments “in situ” without sample pretreatment is demonstrated. Full article

Although chemical structural modification of naphthalimides is widely employed for the purpose of sensing explosives, the effects of such modification have been little explored. Herein, we report the design and synthesis of a new naphthalimide-benzothiazole conjugate (1) and its ability to sense various nitrophenols by means of its colorimetric and fluorescent characteristics. Under long-range UV light (365 nm), 1 displayed a color change of its solution from bluish to colorless only upon addition of 2,4,6-trinitrophenol (TNP). Photoluminescence spectroscopy showed quantitative fluorescence quenching by TNP of the emission peaks of 1 at 398 nm and 418 nm due to donor–acceptor electron transfer. The interaction of 1 with TNP was via a cooperative, non-covalent hydrogen-bonding interaction. Receptor 1 exhibited high sensitivity and selectivity towards TNP over various aromatic nitro analytes. The binding constant (K) and Stern–Volmer constant (K_sv) between 1 and TNP were found to be 5.332 × 10⁻⁵ M and 2.271 × 10⁶ M⁻¹, respectively. Furthermore, the limit of detection was calculated and found to be as low as 1.613 × 10⁻¹⁰ M. Full article

The growing concern for sustainability and environmental preservation has increased the demand for reliable, fast response, and low-cost devices to monitor the existence of heavy metals and toxins in water resources. An electronic tongue (e-tongue) is a multisensory array mostly based on electroanalytical methods and multivariate statistical techniques to facilitate information visualization in a qualitative and/or quantitative way. E-tongues are promising analytical devices having simple operation, fast response, low cost, easy integration with other systems (microfluidic, optical, etc) to enable miniaturization and provide a high sensitivity for measurements in complex liquid media, providing an interesting alternative to address many of the existing environmental monitoring challenges, specifically relevant emerging pollutants such as heavy metals and toxins. Full article

A merocyanine dye as a p-toluenesulfonate salt was synthesized. The structure of the dye was characterized using IR, NMR, HR-MS and single crystal X-ray crystallography. The X-ray crystallographic studies revealed the formation of a stacked aggregated structure of the merocyanine dye. The stacking interactions were investigated using the Crystal Explorer program, which estimated the strength of the interactions between different molecular pairs. The merocyanine dye was screened for affinity towards heavy metal ions, which revealed a color change from pink to colorless in the presence of mercuric ions, while other metal ions did not produce a similar change in color. In addition, the fluorescence spectroscopy indicated a change in the fluorescence intensity upon addition of mercuric ions. Both techniques displayed a good limit of detection value towards mercuric ions. In addition, the pixel intensity-based detection technique was also employed for the determination of limit of detection value with the help of a smartphone. The dynamic light scattering (DLS) studies indicated that the optical change occurred in the spectra of the receptor is due to the disaggregation of the receptor induced by mercuric ions. In addition, ¹H-NMR studies were also used for investigating the mechanism of interaction between the receptor and the mercuric ions. The density functional theory (DFT) studies were used to investigate the formation of the complex at the molecular level, while time dependent density functional theory (TD-DFT) studies were used to understand the observed absorption spectra through the calculation of electronic excitation parameters, which indicated an increase in the energy difference between ground and the excited state. Full article

A coumarin-benzothiazole ratiometric probe of ATP was designed and synthesized. The probe is based on incorporation of benzothiazole scaffold as a donor and coumarin nucleus as an acceptor in a single Förster resonance energy transfer/fluorescence resonance energy transfer (FRET) sensing platform. The sensor can detect ATP in aqueous solution with high selectivity over other nucleotide polyphosphate (NPP) anions. Binding of ATP to the sensor results in modulation of FRET efficiency between the donor and the acceptor which afforded a linear relationship between FRET signal and ATP (0.1–10 μM). A limit of detection (LOD) of 94.5 nM was quantified for FRET sensing of ATP by the probe. In addition, Job plot analysis revealed 1:1 binding interaction between the probe and ATP. The FRET probe was successfully utilized in monitoring ATP hydrolysis by apyrase in aqueous solution. Full article

Human fecal contamination is a crucial threat that results in difficulties in access to clean water. Enterococcus faecalis is a bacteria which is utilized as an indicator in polluted water. Nevertheless, existing strategies face several challenges, including low affinity and the need for labelling, which limit their access to large scale applications. Herein, a label-free fingerprint of the surface proteins of waterborne bacteria on a sensor was demonstrated for real-time bacteria detection from aqueous and water samples. The kinetic performance of the sensor was evaluated and shown to have a range of detection that spanned five orders of magnitude, having a low detection limit (3.4 × 10⁴ cfu/mL) and a high correlation coefficient (R² = 0.9957). The sensor also designated a high selectivity while other competitor bacteria were employed. The capability for multiple usage and long shelf-life are superior to other modalities. This is an impressive surface modification method that uses the target itself as a recognition element, ensuring a broad range of variability to replicate others with different structure, size and physical and chemical properties. Full article

This work describes the development of an electrochemical sensor that was used in the determination of ethinyl estradiol (EE) in pharmaceutical formulations, river water, and milk using the square wave voltammetry technique. Studies were carried out using different carbonaceous materials (multiwalled carbon nanotubes, reduced graphene oxide Reduced graphene oxide, graphite) and different metallic phthalocyanines (cobalt, iron and manganese). Based on these studies it was possible to obtain the best system for the construction of the sensor. The device was obtained by the chemical modification of a glassy carbon electrode (GCE) with multiwalled carbon nanotubes (MWCNTs) and cobalt phthalocyanine (CoPc). The materials were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). Under conditions previously optimized for the proposed method, an analytical curve was constructed, presenting linearity in a range of 2.50–90.0 μmol L⁻¹ (R = 0.990), with detection limit of 2.20 μmol L⁻¹ and quantification of 2.50 μmol L⁻¹. The validation of the methodology for the determination of EE using GCE-MWCNTs-CoPc was performed, being accurate, precise, stable and sensitive. The recovery of ethinyl estradiol in the sample of pharmaceutical formulation was 103.93%, in the samples of river water ranged from 92.75% to 96.47%, and in the milk sample was from 88.00% to 96.20%. Thus, the proposed method presented a viable alternative for the determination of ethinyl estradiol in the quality control of pharmaceutical and food formulations as well as in environmental control. Full article

An important component of any chemiresistive gas sensor is the way in which the resistance of the sensing film is interrogated. The geometrical structure of an electrode can enhance the performance of a gas-sensing device and in particular the performance of sensing films with large surface areas, such as carbon nanotubes. In this study, we investigated the influence of geometrical structure on the performance of gas sensors, combining the characteristics of carbon nanotubes with a novel gas sensor electrode structure based on fractal geometry. The fabricated sensors were tested with exposure to nitric oxide, measuring both the sensor resistance and capacitance (RC) of the sensor responses. Experimental results showed that the sensors with fractal electrode structures had a superior performance over sensors with traditional geometrical structures. Moreover, the RC characteristics of these fractal sensors could be further improved by using different test frequencies that could aid in the identification and quantification of a target gas. Full article

This work provides a summary of our results in the area of the experimental development of detection paper for the detection of liquid phase chemical warfare agents (drops, aerosol), the presence of which is demonstrated by the development of characteristic coloring visible to the naked eye. The basis of the detection paper is a cellulose carrier saturated with the dithienobenzotropone monomer (RM1a)–chromogenic chemosensor sensitive to nerve agents of the G type, blister agent lewisite, or choking agent diphosgene. We achieve a higher coloring brilliance and the limit certain interferences by using this chemosensor in the mix of the o-phenylendiamine-pyronine (PY-OPD). We prove that the addition of the Bromocresol Green pH indicator even enables detection of nerve agents of the V type, or, nitrogen mustards, while keeping a high stability of the detection paper and its functions for other chemical warfare agents. We resolve the resistance against the undesirable influence of water by providing a hydrophobic treatment of the carrier surface. Full article

An electronic nose (E-nose), comprising eight metal oxide semiconductor (MOS) gas sensors, was used in situ for real-time classification of black tea according to its quality level. Principal component analysis (PCA) coupled with signal preprocessing techniques (i.e., time set value preprocessing, F1; area under curve preprocessing, F2; and maximum value preprocessing, F3), allowed grouping the samples from seven brands according to the quality level. The E-nose performance was further checked using multivariate supervised statistical methods, namely, the linear and quadratic discriminant analysis, support vector machine together with linear or radial kernels (SVM-linear and SVM-radial, respectively). For this purpose, the experimental dataset was split into two subsets, one used for model training and internal validation using a repeated K-fold cross-validation procedure (containing the samples collected during the first three days of tea production); and the other, for external validation purpose (i.e., test dataset, containing the samples collected during the 4th and 5th production days). The results pointed out that the E-nose-SVM-linear model together with the F3 signal preprocessing method was the most accurate, allowing 100% of correct predictive classifications (external-validation data subset) of the samples according to their quality levels. So, the E-nose-chemometric approach could be foreseen has a practical and feasible classification tool for assessing the black tea quality level, even when applied in-situ, at the harsh industrial environment, requiring a minimum and simple sample preparation. The proposed approach is a cost-effective and fast, green procedure that could be implemented in the near future by the tea industry. Full article

Colorimetric analysis of heavy metal ions can be realized by the aid of Ag nanoparticles to improve the analytical characteristics. The method is based on the localized surface plasmon resonance (LSPR) properties of the Ag nanoparticles (AgNPs). In this work, we applied the AgNPs with the addition of dithizone to further improve the selectivity and sensitivity of Pb²⁺ analysis. Colorimetric sensing of Pb²⁺ ions based on the polyvinyl alcohol (PVA)-stabilized-colloidal AgNPs in the presence of dithizone is reported. A linear decrease in the AgNPs LSPR absorbance at 421 nm was observed along with the increase in the Pb²⁺ concentration in the range of 0.50–10 µg/L. The other ions give a minor change in the LSPR absorbance of colloidal AgNPs. The Pb²⁺ limit of detection, the limit of quantification, and sensitivity were found to be 0.64 ± 0.04 µg/L, 2.1 ± 0.15 µg/L, 0.0282 ± 0.0040 L/µg (n = 5), respectively. The obtained sensitivity is comparable with that of the immunosensing method. The proposed method could offer a good alternative for colorimetric analysis of Pb²⁺ ions by using nanoparticles in the presence of ligands, which can improve selectivity. Full article