Chemosensors, Volume 10, Issue 2 (February 2022) – 52 articles

The Mn₂BPMP complex has an intrinsic peroxidase-like activity in the pH range of 5 to 8, especially a maximum activity at pH 7, while most peroxidase mimics operate at an acidic pH (mainly pH 4). Its peroxidase-like activity is high among small-molecule-based peroxidase mimics with a high reproducibility. In addition, we recently revealed that adenosine mono/diphosphate (AMP and ADP) significantly boosted the peroxidase-like activity of Mn₂BPMP. These advantages imply that Mn₂BPMP is suitable for biosensing as a substitute for horseradish peroxidase (HRP). Herein, we established a colorimetric one-pot assay system using the enzyme cascade reaction between analyte oxidase and ADP-boosted Mn₂BPMP. The simple addition of ADP to the Mn₂BPMP-based assay system caused a greater increase in absorbance for the same concentration of H₂O₂, which resulted in a higher sensitivity. It was applied to one-pot detection of glucose and cholesterol at 25 °C and pH 7.0 for a few minutes. Full article

Array-based optical sensing is an efficient technique for the determination and discrimination of small organic molecules. This study is aimed at the development of a simple and rapid strategy for obtaining an optical response from a wide range of low-molecular-weight organic compounds. We have suggested a colorimetric and fluorimetric sensing platform based on the combination of two response mechanisms using carbocyanine dyes: aggregation and oxidation. In the first one, the analyte forms ternary aggregates with an oppositely charged surfactant wherein the dye is solubilized in the hydrophobic domains of the surfactant accompanied with fluorescent enhancement. The second mechanism is based on the effect of the analyte on the catalytic reaction rate of dye oxidation with H₂O₂ in the presence of a metal ion (Cu²⁺, Pd²⁺), which entails fluorescence waning and color change. The reaction mixture in a 96-well plate is photographed in visible light (colorimetry) and the near-IR region under red light excitation (fluorimetry). In this proof-of-concept study, we demonstrated the feasibility of discrimination of nine medicinal compounds using principal component analysis: four cephalosporins (ceftriaxone, cefazolin, ceftazidime, cefotaxime), three phenothiazines (promethazine, promazine, chlorpromazine), and two penicillins (benzylpenicillin, ampicillin) in an aqueous solution and in the presence of turkey meat extract. The suggested platform allows simple and rapid recognition of analytes of various nature without using spectral equipment, except for a photo camera. Full article

The dichromatism of Bromophenol blue (BPB) was investigated by varying its concentration in the absence and presence of surfactant. A model of the indicator behavior was carried out, justifying the experimental shapes of the sigmoidal profiles of the hue (H) coordinate. The model applied to the solution was compared with the performance of colorimetric sensor arrays (CSAs) with increasing BPB concentrations. The H shape and the prediction errors of the CSAs were very similar to those predicted. The experimental results enable the changing of the slope of the calibration profiles, at will, by varying only the BPB concentration. Full article

Radiological detection where Cherenkov residual background can be prominent requires scintillators with increased emission wavelength. Cherenkov residual background precludes the use of UV-emitting sensors such as plastic scintillators. However, the literature is scarce in red-emitting plastic scintillators and only one commercial scintillator is currently available (BC-430, from Saint-Gobain Crystals and Detectors). In addition, X-ray imaging or time-of-flight positron emission tomography (ToF-PET) applications are also demanding on this type (color) of scintillators, but such applications also require that the material displays a fast response, which is not particularly the case for BC-430. We present herein our latest developments in the preparation and characterization of fast and red plastic scintillators for this application. Here, ‘fast’ means nanosecond range decay time and ‘red’ is an emission wavelength shifted towards more than 550 nm. At first, the strategy to the preparation of such material is explained by decomposing the scintillator to fundamental elements. Each stage is then optimized in terms of decay time response, then the elemental bricks are arranged to give plastic scintillator formulations that are compatible with the abovementioned characteristics. The results are compared with the red-emissive BC-430 commercial plastic, and the ultra-fast, violet-emitting BC-422Q 1% plastic. In particular, the first-time use of trans-4-dimethylamino-4′-nitrostilbene in the scintillation field as a red wavelength shifter allowed preparing plastic scintillators with the following properties: ${\mathsf{\lambda }}_{\mathrm{em}}^{\max }$ 554 nm, photoluminescence decay time 4.2 ns, and light output ≈ 6100 ph/MeV. This means a scintillator almost as bright as BC-430 but at least three times faster. This new sensor might provide useful properties for nuclear instrumentation. Full article

The technological developments of recent times have allowed the use of innovative approaches to support the diagnosis of various diseases. Many of such clinical conditions are often associated with metabolic unbalance, in turn producing an alteration of the gut microbiota even during asymptomatic stages. As such, studies regarding the microbiota composition in biological fluids obtained by humans are continuously growing, and the methodologies for their investigation are rapidly changing, making it less invasive and more affordable. To this extent, Electronic Nose and Electronic Tongue tools are gaining importance in the relevant field, making them a useful alternative—or support—to traditional analytical methods. In light of this, the present manuscript seeks to investigate the development and use of such tools in the gut microbiota assessment according to the current literature. Significant gaps are still present, particularly concerning the Electronic Tongue systems, however the current evidence highlights the strong potential such tools own to enter the daily clinical practice, with significant advancement concerning the patients’ acceptability and cost saving for healthcare providers. Full article

The acquisition of nutrient data on a precise scale has played a vital role in nutrient management processes for soils. However, the lack of rapid precise and multi-index detection techniques for soil macronutrient contents hinders both rational fertilization and cost reduction. In this paper, a rapid detection method and device were devised, combining capillary electrophoresis (CE) and capacitively coupled contactless conductivity detection (C4D), and presented to detect macronutrient contents of soil. The device consisted of a capillary channel, C4D detector, high-voltage system, etc. It separated macronutrient ions using capillary electrophoresis and then measured the ion concentration based on the C4D principle. Lime concretion black soil samples from a complete field were collected and detected. NO₃⁻, NH₄⁺, H₂PO₄⁻ and K⁺ in sample solutions could be detected in 5 min with relative standard deviations (RSDs) from 1.0 to 7.51%. The injection voltage was set to 10 kV for 5 s, and the separation voltage was set to 14 kV. This demonstrated the excellent performance of the C4D device on the detection of soil macronutrients, which could help to guide fertilization operations more effectively. Full article

In this study, a novel cobalt polyphthalocyanine/carboxylic acid functionalized multiwalled carbon nanotube nanocomposite (CoPPc/MWCNTs-COOH) to detect lactic acid was successfully fabricated. The nanocomposite was systematically characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, ultraviolet–visible absorption spectroscopy, and X-ray photoelectron spectroscopy. The nanocomposite provided excellent conductivity for effective charge transfer and avoided the agglomeration of MWCNTs-COOH. The electrochemical surface area, diffusion coefficient and electron transfer resistance of the CoPPc/MWCNTs-COOH glassy carbon electrode (CoPPc/MWCNTs-COOH/GCE) were calculated as A = 0.49 cm², D = 9.22 × 10⁻⁵ cm²/s, and R_ct = 200 Ω, respectively. The lactic acid sensing performance of the CoPPc/MWCNTs-COOH was evaluated using cyclic voltammetry in 0.1 M PBS (pH 4). The results demonstrated that the novel electrode exhibited excellent electrochemical performance toward lactic acid reduction over a wide concentration range (10 to 240 μM), with a low detection limit (2 μM (S/N = 3)), and a reasonable selectivity against various interferents (ascorbic acid, uric acid, dopamine, sodium chloride, glucose, and hydrogen peroxide). Additionally, the electrode was also successfully applied to quantify lactic acid in rice wine samples, showing great promise for rapid monitoring applications. Full article

A large amount of power equipment works in closed or semi-closed environments for a long time. Carbon monoxide (CO) is the most prevalent discharge gas following a fault in the components. Based on the density functional theory of first principles, the adsorption behavior of CO gas molecules on intrinsic, Ag-doped and Au-doped hafnium disulfide (HfS₂) monolayers was systematically studied at the atomic scale. Firstly, the intrinsic HfS₂ monolayer, Ag-doped HfS₂ (Ag-HfS₂) monolayer and Au-doped HfS₂ (Au-HfS₂) monolayer, with different doping sites, were created. The structural stability, dopant charge transfer, substrate conductivity and energy band structure of different doping sites of the Ag-HfS₂ and Au-HfS₂ monolayer structures were calculated. The most stable doping structure was selected with which to obtain the best performance on the subsequent gas adsorption test. Then, the CO adsorption models of intrinsic HfS₂, Ag-HfS₂ and Au-HfS₂ were constructed and geometrically optimized. The results show that the adsorption energy of the Ag-HfS₂ monolayer for CO gas is −0.815 eV, which has good detection sensitivity and adsorption performance. The adsorption energy of CO on the Au-HfS₂ monolayer is 2.142 eV, the adsorption cannot react spontaneously, and the detection sensitivity is low. The research content of this paper provides a theoretical basis for the design and research of gas sensing materials based on HfS₂, promoting the development and application of HfS₂ in gas sensing and other fields. Full article

The present work deals with the development of a Love-wave biosensor for the diagnosis of the modification of cell viscosity. The relevant device performance such as insertion loss, attenuation, phase velocity, and sensitivity needs to be analysed as a function of the device structure and also regarding the effect of the liquid loading. In this study, we used an analytical model based on the equation of motions for a Love wave propagating in a three-layer structure. We show that the effect of the viscous coupling leads to insertion losses and a phase shift that impact the acoustic ratio. A comparison between experimental and theoretical results showed a good agreement between the behaviours as it was observed for the phase shift vs. the insertion loss with a limited difference in values (3.11/3.09—experimental/simulation for the sensitivity to the viscosity for different insertion losses) due to the assumptions made on the model used. Full article

A NIR cyanine@imidazole derivative Cy1 was synthesized and evaluated as a metal ion sensor in solution. Cy1 was shown to be very sensitive to all metal ions tested, presenting a blue shift in the absorption from 668 nm to 633 nm, followed by a change in colour from pale green to blue with Zn²⁺, Cd²⁺, Co²⁺, Ni²⁺ and Hg²⁺ ions. Despite the blue shift in the absorption, a decrease at 633 nm (with a colour change from pale green to colourless), as well as a quenching in the emission intensity at 785 nm were observed for Cu²⁺ ions. The results show the formation of sandwich complexes of two ligands per metal ion with the highest association constant observed for Cu²⁺ (Log K_ass.abs = 14.76 ± 0.09; Log K_ass.emis. = 14.79 ± 0.06). The minimal detectable amounts were found to be 31 nM and 37 nM, with a naked eye detection of 2.9 ppm and 2.1 ppm for Hg²⁺ and Cu²⁺ ions, respectively. These results prompted us to explore the applicability of Cy1 by its combination with nanomaterials. Thus, Cy1@ doped MNs and Cy1@ doped PMMA nanoparticles were synthesized. Both nanosystems were shown to be very sensitive to Cu²⁺ ions in water, allowing a naked-eye detection of at least 1 ppm for Cy1@ doped MNs and 7 ppm for Cy1@ doped PMMA. This colourimetric response is an easy and inexpensive way to assess the presence of metals in aqueous media with no need for further instrumentation. Full article

This work deals with the development of water-soluble optical sensors based on ruthenium(II) tris(diimine) complexes that exhibit high molar absorptivity and are emissive in aqueous media. Palladium-catalyzed arylation of polyamines with 3-bromo-1,10-phenanthroline (Brphen) and [Ru(bpy)₂(Brphen)](PF₆)₂ (bpy = 2,2’-bipyridine) was explored to prepare Ru²⁺ complexes with 1,10-phenanthrolines (phen) substituted by linear polyamines (PAs) at position 3 of the heterocycle ([Ru(bpy)₂(phen–PA)](PF₆)₂). The most convenient synthetic pathway leading to the target molecular probes includes the preparation of phen–PA ligands, followed by ruthenium complexation using cis-Ru(bpy)₂Cl₂. Complexes bearing a polyamine chain directly linked to phenanthroline core are emissive in aqueous media and their quantum yields are comparable to that of parent [Ru(bpy)₃](PF₆)₂. Their structure can be easily adapted for detection of various analytes by modification of amine groups. As an example, we prepared the emissive complex Ru(N₂P₂phen) which is suitable for the dual channel (spectrophotometry and luminescence (ON–OFF probe)) selective detection of Cu²⁺ ions at the physiological pH levels with limits of detection (LOD) by spectrophotometry and fluorescence spectroscopy equal to 9 and 6 μM, respectively, that is lower than the action level in drinking water for copper as prescribed by the US Environmental Protection Agency. Full article

A two-dimensional (2D) Dy₂O₃-Pd-PDA/rGO heterojunction nanocomposite has been synthesised and tested for hydrogen (H₂) gas sensing under various functioning conditions, including different H₂ concentrations (50 ppm up to 6000 ppm), relative humidity (up to 25 %RH) and working temperature (up to 200 °C). The material characterisation of Dy₂O₃-Pd-PDA/rGO nanocomposite performed using various techniques confirms uniform distribution of Pd NPs and 2D Dy₂O₃ nanostructures on multi-layered porous structure of PDA/rGO nanosheets (NSs) while forming a nanocomposite. Moreover, fundamental hydrogen sensing mechanisms, including the effect of UV illumination and relative humidity (%RH), are investigated. It is observed that the sensing performance is improved as the operating temperature increases from room temperature (RT = 30 °C) to the optimum temperature of 150 °C. The humidity effect investigation revealed a drastic enhancement in sensing parameters as the %RH increased up to 20%. The highest response was found to be 145.2% towards 5000 ppm H₂ at 150 °C and 20 %RH under UV illumination (365 nm). This work offers a highly sensitive and selective hydrogen sensor based on a novel 2D nanocomposite using an environmentally friendly and energy-saving synthesis approach, enabling us to detect hydrogen molecules experimentally down to 50 ppm. Full article

In this work, an optical fiber sensor based on the localized surface plasmon resonance (LSPR) phenomenon has been designed for the detection of two different chemical species (mercury and hydrogen peroxide) by using Layer-by-Layer Embedding (LbL-E) as a nanofabrication technique. In the first step, silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs) have been synthesized by using a chemical protocol as a function of the strict control of three main parameters, which were polyelectrolyte concentration, a loading agent, and a reducing agent. In the second step, their incorporation into nanometric thin films have been demonstrated as a function of the number of bilayers, which shows two well-located absorption peaks associated to their LSPR in the visible region at 420 nm (AgNPs) and 530 nm (AuNPs). Finally, both plasmonic peaks provide a stable real-time reference measurement, which can be extracted from the spectral response of the optical fiber sensor, which shows a specific sensing mechanism as a function of the analyte of study. Full article

This study aimed to remove carbamazepine from aqueous solutions, using functional silica phenylamine (SiBN), which is characterized and showed excellent chemical and thermal stability. Adsorbents based on silica were developed due to their unusually large surface area, homogenous pore structure, and well-modified surface properties, as silica sparked tremendous interest. It was determined to develop a novel silica adsorbent including phenylamine and amide (SiBCON). The adsorbents obtained were analyzed by various spectroscopy devices, including SEM, FT-IR and TGA analysis. The maximum removal rates for carbamazepine were 98.37% and 98.22% for SiBN and SiBCON, respectively, when optimized at room temperature, pH 9.0, initial concentration of 10 mg·L⁻¹ and contact time of 15 min. Theoretical tools are widely used in the prediction of the power of interactions between chemical systems. The computed data showed that new amine modified silica is quite effective in terms of the removal of carbamazepine from aqueous solution. Calculation binding energies and DFT data showed that there is a powerful interaction between amine-modified silica and carbamazepine. Full article

The use of graphene and other carbon nanoparticles is now of interest for developing chemical (gas and compounds detectors) and physical sensors. In this work, a graphene nanoplatelet (GNP)-PDMS sensor is proposed. More specifically, its strain-sensing capabilities under consecutive cycles as well as the crack propagation mechanisms are widely analyzed. First, an analysis of the electrical properties shows that the increase of the GNP content leads, as expected, to an increase of the electrical conductivity, ranging from values around 10⁻³ to 1 S/m for 5 and 11 wt.% samples. The analysis of crack propagation monitoring capabilities shows an exceptional sensitivity of the proposed flexible sensors, with a highly exponential behavior of the electrical resistance due to the prevalent breakage of the electrical pathways as crack propagation occurs. Furthermore, the analysis of the electrical response under cyclic load proves a very high robustness, with a similar response when comparing different cycles and an electrical sensitivity that increases when decreasing the GNP content (from 15–25 to 25–50 at 7 and 11 wt.% GNP content, respectively), a fact that is explained by the prevalence of tunneling mechanisms at low contents. Finally, a proof-of-concept of human motion monitoring by the detection of neck, wrist and facial movements is successfully achieved, indicating the high applicability of the proposed sensors. Full article

The application of ion-selective electrodes (ISEs) in the detection and determination of environmental pollutants has become a very important mission in the last few years. Two selective and sensitive membrane electrodes were fabricated in the laboratory and intended to evaluate the electrochemical response of bromazepam (BRZ) using phosphotungstic acid (PTA) and sodium tetraphenylborate (TPB) as ion pairing agents. The linearity range of the fabricated electrodes was between 1 × 10⁻⁶ M to 1 × 10⁻³ M. Nernstian slopes of 54 mV/decade and 57 mV/decade were obtained for the BRZ-PTA and BRZ-TPB membrane electrodes, respectively. The performance of the fabricated membranes was optimum in the pH range of 3–6. Optimum electrochemical response was attained through the careful adjustment of all assay settings. The cited method was successfully applied for the selective determination of BRZ in either its pure form or real wastewater samples obtained from a pharmaceutical industrial plant. The main core of novelty in the suggested method lies in the application of the membranes for the sensitive, selective, and economic determination of BRZ in real wastewater effluents without the tedious sample pretreatment procedures. This can make the suggested method considered an eco-friendly method, as it minimizes the use of organic solvents and chemicals used in the pretreatment process. Full article

Novel water-swollen photo-crosslinked membranes were obtained by copolymerization of the N-vinylpyrrolidone, butyl acrylate and ethyl methacrylate monomers functionalized with naphthalimide groups, as pH sensitive fluorescence probes. For that purpose, two monomers with pending naphthalimide groups anchored to ethyl methacrylate through alkyl chains with different length, were previously synthesized. The membranes were characterized using different techniques. The pH dependence of absorbance and the corresponding quenching of fluorescence were investigated and related to the structure of naphthalimide substituents linked to the membrane. The new solid sensors exhibited sensitive fluorescence changes at pH < 3, and lower time response was determined for membranes where the sensing group was linked through longer alkyl chain to the polymer matrix. The membranes were solid, thermally stable and easily handled to be applied as sensor materials, and showed a reversible behavior, which is an important feature for further fabrication of an economical on-site tool for the acidity detection in aqueous environments. Full article

On-site determination of trace copper ions in natural waters is of great significance to environmental monitoring, and how to develop accurate and specific point-of-care test methods is one critical issue. In the study, a paper-based analytical device (PAD) being modified with a new truncated DNAzyme (CLICK-T, which was derived from a reported DNAzyme-CLICK-17) was developed for Cu ions detection. The detection mechanism was based on Cu(II)-catalyzed azide-alkyne cycloaddition (Cu(II)AAC) reaction. It can directly conduct on-site analysis of Cu(II) ions based on fluorescent signals detected using a mobile phone. In the assay, the CLICK-T was firstly modified on the PADs. Then, water samples containing Cu ions mixed with 3-azido-7-hydroxycoumarin and 3-butyn-1-ol were instantly dripped on PADs and incubated for 20 min. Finally, the PADs were excited at 365 nm and emitted fluorescence which could be analyzed on site using smart phones. The Cu(II) concentration could be quantified through RGB analysis with the aid of iPhone APP software. The limit of detection is 0.1 µM by the naked eye due to the fact that CLICK-T exhibited a good catalytic effect on Cu(II)AAC. The Cu(II) concentration could also be directly detected without using reductant, such as ascorbic acid, which is prone to be oxidized in air. This simplifies the PDA detection process improves its efficiency. The PAD is convenient for the on-site analysis of Cu ions in natural waters. Full article

Peptide-based materials provide a versatile platform for sensing and ion sequestration since peptides are endowed with stimuli-responsive properties. The mechanism of molecular sensing is often based on peptide structural changes (or switching), caused by the binding of the target molecule. One scope of sensing applications is the selection of a specific analyte, which may be achieved by adjusting the structure of the peptide binding site. Therefore, exact knowledge of peptide properties and 3D-structure in the ‘switched’ state is desirable for tuning the detection and for further molecular construction. Hence, here we demonstrate the performance of Electron Paramagnetic Resonance (EPR) spectroscopy in the identification of metal ion binding by the antimicrobial peptide trichogin GA IV. Na(I), Ca(II), and Cu(II) ions were probed as analytes to evaluate the impact of coordination number, ionic radii, and charge. Conclusions drawn by EPR are in line with literature data, where other spectroscopic techniques were exploited to study peptide-ion interactions for trichogin GA IV, and the structural switch from an extended helix to a hairpin structure, wrapped around the metal ion upon binding of divalent cations was proposed. Full article

In this work, sensing behaviors and mechanisms of two crosslinked copolymers with dimethylamine and dimethylamide functional groups were compared and investigated for their ability to detect hydrogen chloride (HCl) gas. The crosslinked copolymer films were photopolymerized on quartz crystal electrodes using a micro-contact printing technique. The gas sensing behaviors were analyzed by measuring resonant frequency (Δf) of quartz crystal microbalance (QCM). The HCl binding capacity of photopolymerized films, with a mass between 4.6 and 5.9 μg, was optimized. Under optimized film mass conditions, the poly(2-dimethylaminoethyl methacrylate-co-ethylene glycol dimethacrylate) (DMAEMA-co-EGDMA), poly(DMAEMA-co-EGDMA), film, C2-DMA, showed a 13.9-fold higher binding capacity than the poly(N,N-dimethylacrylamide-co-ethylene glycol dimethacrylate, poly(DMAA-co-EGDMA), film, C0-DMA, during HCl gas adsorption. HCl gas was effectively adsorbed on the C2-DMA film because of the formation of tertiary amine salts through protonation and strong ionic bonding. Furthermore, the C2-DMA film exhibited excellent sensitivity, of 2.51 (ng/μg) (1/ppm), and selectivity coefficient (k* = 12.6 for formaldehyde and 13.5 for hydrogen fluoride) compared to the C0-DMA film. According to the experimental results, and due to its high functionality and stability, the C2-DMA film-coated QC electrode could be used as an HCl gas sensor, with low-cost and simple preparation, in future endeavors. Full article

These structurally isomeric rhodamine 6G-based amino derivatives are designed to detect Sn²⁺ ions. The receptors exhibit rapid fluorescent “turn-on” responses towards Sn²⁺. The absorption (530 nm) and fluorescent intensity (551 nm) of the receptors increase when increasing the concentration of Sn²⁺. The hydrazine derivative exhibits more rapid sensitivity towards Sn²⁺ than the ethylene diamine derivative, indicating that the presence of an alkyl chain in the diamine decreases the sensitivity of the receptors towards Sn²⁺. The presence of carbonyl groups and terminal amino groups strongly influences the sensitivity of the chemosensors toward Sn²⁺ by a spirolactam ring-opening mechanism. The receptors exhibit 1:1 complexation with Sn²⁺ as evidenced by Job plot, and the corresponding limit of detection was found to be 1.62 × 10⁻⁷ M. The fluorescence images of the receptors and their complexes reveal their potential applications for imaging of Sn²⁺ in real/online samples. Full article

Miniature and low-power gas sensing elements are urgently needed for a portable electronic nose, especially for outdoor pollution monitoring. Hereby we prepared chemiresistive sensors based on wide-area graphene (grown by chemical vapor deposition) placed on Si/Si₃N₄ substrates with interdigitated electrodes and built-in microheaters. Graphene of each sensor was individually functionalized with ultrathin oxide coating (CuO-MnO₂, In₂O₃ or Sc₂O₃) by pulsed laser deposition. Over the course of 72 h, the heated sensors were exposed to randomly generated concentration cycles of 30 ppb NO₂, 30 ppb O₃, 60 ppb NO₂, 60 ppb O₃ and 30 ppb NO₂ + 30 ppb O₃ in synthetic air (21% O₂, 50% relative humidity). While O₃ completely dominated the response of sensors with CuO-MnO₂ coating, the other sensors had comparable sensitivity to NO₂ as well. Various response features (amplitude, response rate, and recovery rate) were considered as machine learning inputs. Using just the response amplitudes of two complementary sensors allowed us to distinguish these five gas environments with an accuracy of ~ 85%. Misclassification was mostly due to an overlap in the case of the 30 ppb O_3, and 30 ppb O₃ + 30 ppb NO₂ responses, and was largely caused by the temporal drift of these responses. The addition of recovery rates to machine learning input variables enabled us to very clearly distinguish different gases and increase the overall accuracy to ~94%. Full article

Electrochemical sensors integrating hybrid nanostructured platforms are a promising alternative to conventional detection techniques for addressing highly relevant challenges of heavy metal determination in the environment. Hybrid nanocomposites based on graphene derivatives and inorganic nanoparticles (NPs) are ideal candidates as active materials for detecting heavy metals, as they merge the relevant physico-chemical properties of both the components, finally leading to a rapid and sensitive current response. In this work, a hybrid nanocomposite formed of reduced graphene oxide (RGO) sheets, surface functionalized by π-π interactions with 1-pyrene carboxylic acid (PCA), and decorated in situ by Au NPs, was synthesized by using a colloidal route. The hybrid nanocomposite was characterized by cyclic voltammetry and electrochemical impedance spectroscopy with respect to the corresponding single components, both bare and deposited as a layer-by-layer junction onto the electrode. The results demonstrated the high electrochemical activity of the hybrid nanocomposite with respect to the single components, highlighting the crucial role of the nanostructured surface morphology of the electrode and the PCA coupling agent at the NPs-RGO interphase in enhancing the nanocomposite electroactivity. Finally, the Au NP-decorated PCA-RGO sheets were tested by anodic stripping voltammetry of As(III) ion—a particularly relevant analyte among heavy metal ions—in order to assess the sensing ability of the nanocomposite material with respect to its single components. The nanocomposite has been found to present a sensitivity higher than that characterizing the bare components, with LODs complying with the directives established by the U.S. EPA and in line with those reported for state-of-the-art electrochemical sensors based on other Au-graphene nanocomposites. Full article

Lanthanide-doped metal-organic frameworks (Y/Yb/Er-MOF) were synthesized by a low-cost solvothermal method. The obtained Y/Yb/Er-MOF shows the cooperative upconversion luminescence of Yb³⁺ and upconversion luminescence of Er³⁺ (Yb³⁺-sensitized) irradiated by a continuous wave 980 nm laser. In order to explore the potential application of Y/Yb/Er-MOF in relative humidity (RH) sensors, the RH responsiveness of Y/Yb/Er-MOF was investigated by measuring the intensity changes of upconversion luminescence. The Y/Yb/Er-MOF possesses two luminescence centers, in which Yb³⁺ forms emission at 500 nm through the cooperative luminescence effect, and Er³⁺ achieves 660 nm emission through excited state absorption and successive energy transfer from Yb³⁺. Hence, the ratio meter luminescence sensor for RH is constructed based on Y/Yb/Er-MOF. The results show that the response of Y/Yb/Er-MOF to RH presents a linear relationship in the range of 11–95%. The cycle stability of Y/Yb/Er-MOF responses to RH was investigated with the intensity changes of upconversion luminescence, and the recovery ratio was more than 93% each time. Therefore, the Y/Yb/Er-MOF is a humidity-sensitive material with great potential for applications such as humidity sensors. Full article

Recent advances in 3D printing technologies and materials have enabled rapid development of innovative sensors for applications in different aspects of human life. Various 3D printing technologies have been adopted to fabricate biosensors or some of their components thanks to the advantages of these methodologies over the traditional ones, such as end-user customization and rapid prototyping. In this review, the works published in the last two years on 3D-printed biosensors are considered and grouped on the basis of the 3D printing technologies applied in different fields of application, highlighting the main analytical parameters. In the first part, 3D methods are discussed, after which the principal achievements and promising aspects obtained with the 3D-printed sensors are reported. An overview of the recent developments on this current topic is provided, as established by the considered works in this multidisciplinary field. Finally, future challenges on the improvement and innovation of the 3D printing technologies utilized for biosensors production are discussed. Full article

Acid-base and redox reactions are important mechanisms that affect the optical properties of fluorescent probes. Fluorescent carbon nanoparticles (CNPs) that possess tailored surface functionality enable a prompt response to regional stimuli, offering a useful platform for detection, sensing, and imaging. In this study, mPA CNPs were developed through one-pot hydrothermal reaction as a novel fluorescent probe (quantum yield = 10%) for pH and hypochlorite sensing. m-Phenylenediamine was chosen as the major component of CNPs for pH and hypochlorite responsiveness. Meanwhile, ascorbic acid with many oxygen-containing groups was introduced to generate favorable functionalities for improved water solubility and enhanced sensing response. Thus, the mPA CNPs could serve as a pH probe and a turn-off sensor toward hypochlorite at neutral pH through fluorescence change. The as-prepared mPA CNPs exhibited a linear fluorescence response over the pH ranges from pH 5.5 to 8.5 (R² = 0.989), and over the concentration range of 0.125–1.25 μM for hypochlorite (R² = 0.985). The detection limit (LOD) of hypochlorite was calculated to be 0.029 μM at neutral pH. The mPA CNPs were further applied to the cell imaging. The positively charged surface and nanoscale dimension of the mPA CNPs lead to their efficient intracellular delivery. The mPA CNPs were also successfully used for cell imaging and sensitive detection of hypochlorite as well as pH changes in biological systems. Given these desirable performances, the as-synthesized fluorescent mPA CNPs shows great potential as an optical probe for real-time pH and hypochlorite monitoring in living cells. Full article

This paper proposes a novel strategy for low humidity detection, an optical waveguide (OWG) sensor that is locally coated with polyvinylpyrrolidone (PVP) film. The humidity sensor was fabricated using a spin coating on a K+-exchanged glass optical waveguide with PVP film. Its sensing properties were investigated by injecting a humid air range of 10.6~32%RH (relative humidity) at room temperature. The surface morphology of the PVP film was characterized by an atomic force microscope (AFM). The possible humidity sensing mechanism of the proposed sensor was discussed by using absorption spectra. This study showed that the PVP-coated OWG sensor possessed high sensitivity, stability, and rapid response/recovery. Therefore, these observed results demonstrate that the low-cost OWG humidity sensor could be applied in real-time low concentration water vapor monitoring. Full article

Antibodies produced in response to adaptive immunity provide a receptor with multiple sites for binding to a distinct epitope of an antigen. Determining antibody levels to specific antigens has important clinical applications in assessing immune status or deficiency, monitoring infectious or autoimmune diseases, and diagnosing allergies. Leveraging that a specific antibody will bind to a distinct small peptide epitope without requiring the entire antigen to be present, we demonstrate in this work a proof-of-concept assay to detect the presence of an antibody by using peptide epitopes linked to an amphiphile to generate a vesicle-based sensing system. By affording multiple copies of the epitope site on the vesicle, we revealed that the vesicles visibly aggregate in response to an antibody specific for that epitope due to multivalent binding provided by the antibody. We also uncovered the role of peptide surface density in providing accessible epitopes on the vesicles for antibody binding. In summary, using a peptide derived from the coat protein of human influenza virus directly linked to a diacetylene-containing amphiphile afforded peptide-laden vesicles that proved capable of detecting the presence of antibodies specific for human influenza hemagglutinin. Full article

One of the major difficulties in the development of evanescent wave optical fiber sensors (EWOFS) lies in the complexity of the manufacturing of the chemosensitive element, particularly when using plastic optical fibers (POFs). While these fibers are appealing waveguides thanks to their low cost, ease of connectorization and robustness, the need for removing the cladding material complicates the EWOFS fabrication. In this paper we discuss how 3D printing filaments can serve as an alternative to commercially available POF for the development of EWOFS. In the process of replacing the traditional POF, we compared the performance of two EWOFS for monitoring airborne formaldehyde. These sensitive elements were manufactured either from 1.75 mm diameter 3D printing filaments, or from a commercially available POF. After the optimization of their respective fabrication protocols, the analytical performance of the two formaldehyde EWOFS was compared in terms of sensitivity and reproducibility. In this regard, the easy-to-manufacture 3D printing filament-based waveguides provided 5-fold lower detection limits with respect to the commercial POF-based sensors. Although no statistically significant differences were found in terms of reproducibility, the simplification of the sensor manufacturing process together with the increased analytical performance for chemical sensing spur the use of 3D printing filaments for the development of new POF-based EWOFS. Full article

In this work, a system consisting of two resistive sensors working in tandem to detect and quantify the acetic acid released during the degradation of cellulose acetate-based ancient cinematographic and photographic films is presented. Acetic acid must be constantly monitored to prevent reaching concentrations at which autocatalytic degradation processes begin. The sensors are constituted by a thin layer of metal oxide (tungsten oxide and tin oxide) deposited over an interdigitated electrode capable of being heated, chosen to maximize the array response towards acetic acid vapors. The signals obtained from the sensor array are mathematically processed to reduce the background signal due to interferent gases produced during degradation of ancient cinematographic films. The sensor array reported a LOD of 30 ppb for acetic acid, with a linearity range up to 30 ppm. Finally, the sensor array was tested with different cinematographic and photographic film samples made of cellulose acetate, whose degradation state and acetic acid production was validated using the conventional technique (A-D strips). The presented array is suitable for remote monitoring large number of films in collections since, compared to the official technique, it has a lower detection limit (30 ppb vs. 500 ppb) and is much quicker in providing accurate acetic acid concentration in the film boxes (15 min vs. 24 h). Full article