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Chemosensors, Volume 10, Issue 4 (April 2022) – 29 articles

Cover Story (view full-size image): The development of porphyrin-based multifunctional materials destined both to capture carbon dioxide and to monitor toxic metal ions from waters represents an actual task of sustainable research. A carboxyl-substituted A3B porphyrin was obtained and fully characterized, and a novel porphyrin-k-carrageenan composite material able to capture CO2 in ambient conditions was realized. A good performance of 6.97 mmol CO2/1 g adsorbent was confirmed. An extension of this porphyrin-k-carrageenan material’s functionality toward Mn2+ detection from polluted waters and medical samples, relying on its synergistic partnership with gold nanoparticles (AuNPs), was achieved. The plasmonic porphyrin-k-carrageenan-AuNPs material detected Mn2+ in the range of concentration from 4.56 × 10−5 M to 9.39 × 10−5 M (5–11 mg/L). View this paper
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11 pages, 3095 KiB  
Article
Real-Time Fluorescence Imaging of His-Tag-Driven Conjugation of mCherry Proteins to Silver Nanowires
by Martyna Jankowska, Karolina Sulowska, Kamil Wiwatowski, Joanna Niedziółka-Jönsson and Sebastian Mackowski
Chemosensors 2022, 10(4), 149; https://doi.org/10.3390/chemosensors10040149 - 18 Apr 2022
Cited by 1 | Viewed by 2859
Abstract
In this work, we aimed to apply fluorescence microscopy to image protein conjugation to Ni-NTA modified silver nanowires in real time via the His-tag attachment. First, a set of experiments was designed and performed for the mixtures of proteins and silver nanowires in [...] Read more.
In this work, we aimed to apply fluorescence microscopy to image protein conjugation to Ni-NTA modified silver nanowires in real time via the His-tag attachment. First, a set of experiments was designed and performed for the mixtures of proteins and silver nanowires in order to demonstrate plasmon enhancement of mCherry protein fluorescence as well as the ability to image fluorescence of single molecules. The results indicated strong enhancement of single-protein fluorescence emission upon coupling with silver nanowires. This conclusion was supported by a decrease in the fluorescence decay time of mCherry proteins. Real-time imaging was carried out for a structure created by dropping protein solution onto a glass substrate with functionalized silver nanowires. We observed specific attachment of mCherry proteins to the nanowires, with the recognition time being much longer than in the case of streptavidin–biotin conjugation. This result indicated that it is possible to design a universal and efficient real-time sensing platform with plasmonically active functionalized silver nanowires. Full article
(This article belongs to the Special Issue Nanomaterials-Based Sensors)
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Figure 1

Figure 1
<p>(<b>A</b>) Crystal structure of mCherry protein (Shu X., Remington S. J., RCSB PDB, 2006); (<b>B</b>) absorption (blue line) and emission (red line) spectra of mCherry protein and extinction spectrum of AgNWs (black line) measured in solution.</p>
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<p>Fluorescence intensity maps of mCherry mixed with AgNWs (on the <b>left</b>) and cross-section along the silver nanowire and on glass (on the <b>right</b>). (<b>A</b>,<b>B</b>) sample with mCherry solution 0.5 µg/mL with AgNW, (<b>C</b>,<b>D</b>) sample with solution of single mCherry with AgNW.</p>
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<p>Histogram of fluorescence intensities of single mCherry proteins on AgNWs (red) and in the background on glass (black).</p>
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<p>Fluorescence intensity maps of mCherry conjugate with AgNWs (on the <b>left</b> (<b>A</b>)) and cross-section along the silver nanowire and on glass (on the <b>right</b> (<b>B</b>)).</p>
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<p>Fluorescence intensity decay measured for mCherry on glass (black line) and conjugated to AgNWs (red line).</p>
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<p>Fluorescence intensity maps of mCherry solution (<b>A</b>) before deposition and (<b>B</b>) at the time of deposition. (<b>C</b>–<b>F</b>) Protein conjugation process over time.</p>
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<p>(<b>A</b>). Fluorescence intensity in time measured along the AgNWs (blue) and for background signal level on glass (black), (<b>B</b>). Time profiles of fluorescence intensity of mCherry along a single AgNW.</p>
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<p>(<b>A</b>). Fluorescence intensity in time measured along the AgNWs (blue) and for background signal level on glass (black), (<b>B</b>). Time profiles of fluorescence intensity of mCherry along a single AgNW.</p>
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15 pages, 3243 KiB  
Article
Composite Electrodes Based on Carbon Materials Decorated with Hg Nanoparticles for the Simultaneous Detection of Cd(II), Pb(II) and Cu(II)
by Laia L. Fernández, Julio Bastos-Arrieta, Cristina Palet and Mireia Baeza
Chemosensors 2022, 10(4), 148; https://doi.org/10.3390/chemosensors10040148 - 15 Apr 2022
Cited by 10 | Viewed by 2956
Abstract
Monitoring water quality has become a goal to prevent issues related to human health and environmental conditions. In this sense, the concentration of metal ions in water sources is screened, as these are considered persistent contaminants. In this work, we describe the implementation [...] Read more.
Monitoring water quality has become a goal to prevent issues related to human health and environmental conditions. In this sense, the concentration of metal ions in water sources is screened, as these are considered persistent contaminants. In this work, we describe the implementation of customized graphite electrodes decorated with two types of Hg nanoparticles (Hg-NPs), optimized toward the electrochemical detection of Cd, Pb and Cu. Here, we combine Hg, a well-known property to form alloys with other metals, with the nanoscale features of Hg-NPs, resulting in improved electrochemical sensors towards these analytes with a substantial reduction in the used Hg amount. Hg-NPs were synthesized using poly(diallyldimethylammonium) chloride (PDDA) in a combined role as a reducing and stabilizing agent, and then appropriately characterized by means of Transmission Electron Microscopy (TEM) and Zeta Potential. The surface of composite electrodes with optimized graphite content was modified by the drop-casting of the prepared Hg-NPs. The obtained nanocomposite electrodes were morphologically characterized by Scanning Electron Microscopy (SEM), and electrochemically by Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS). The results show that the Hg-NP-modified electrodes present better responses towards Cd(II), Pb(II) and Cu(II) detection in comparison with the bare graphite electrode. Analytical performance of sensors was evaluated by square-wave anodic stripping voltammetry (SWASV), obtaining a linear range of 0.005–0.5 mg·L−1 for Cd2+, of 0.028–0.37 mg·L−1 for Pb2+ and of 0.057–1.1 mg·L−1 for Cu2+. Real samples were analyzed using SWASV, showing good agreement with the recovery values of inductively coupled plasma–mass spectrometry (ICP-MS) measurements. Full article
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Graphical abstract

Graphical abstract
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<p>TEM images for (<b>A</b>) Hg-NPs<sup>Route A</sup> and (<b>B</b>) Hg-NPs<sup>Route B</sup>. Inset histograms related.</p>
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<p>Retrodispersive (<b>A</b>), secondary electron SEM image (<b>B</b>) and EDX graphs (<b>C</b>) for 20% graphite. Retrodispersive (<b>D</b>), secondary electron SEM image (<b>E</b>) and EDX graphs (<b>F</b>) for Hg-NPs<sup>Route A</sup> @graphite electrode. Retrodispersive (<b>G</b>), secondary electron SEM image (<b>H</b>) and EDX graphs (<b>I</b>) for Hg-NPs<sup>Route B</sup> @graphite electrode. Retrodispersive (<b>J</b>), secondary electron SEM image (<b>K</b>) and EDX graphs (<b>L</b>) for Hg-NPs<sup>Route B</sup>/PDDA @graphite electrode. Both retrodispersive and secondary electron SEM images have the same scale: 1 µm.</p>
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<p>Electrochemical electrode characterization. (<b>A</b>) Superposition of the cyclic voltammograms obtained for each type of electrode: bare (20% graphite), Hg-NPs<sup>Route A</sup>, Hg-NPs<sup>Route B</sup>, Hg-NPs<sup>Route B</sup>/PDDA. Scan rate: 10 mV·s<sup>−1</sup>. (<b>B</b>) Electrochemical impedance spectroscopy obtained for each type of electrode: bare (20% graphite), Hg-NPs<sup>Route A</sup>, Hg-NPs<sup>Route B</sup>, Hg-NPs<sup>Route B</sup>/PDDA.</p>
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<p>Calibration curves of Cd<sup>2+</sup> (<b>A</b>), Pb<sup>2+</sup> (<b>B</b>) and Cu<sup>2+</sup> (<b>C</b>) using the four different electrodes under study ■ 20% graphite; ▲ Hg-NPs<sup>Route A</sup>; ▼Hg-NPs<sup>Route B</sup>; ● Hg-NPs<sup>Route B</sup>/PDDA. The experimental error was estimated as the standard deviation (<span class="html-italic">n</span> = 3).</p>
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<p>Summary of the currents obtained for the maximum concentrations of interference evaluated in the presence or not of the analyte: (<b>A</b>) 0.11 mg·L<sup>−1</sup> Cd<sup>2+</sup>-125 mg·L<sup>−1</sup> O<sub>2</sub>; (<b>B</b>) 0.11 mg·L<sup>−1</sup> Cd<sup>2+</sup>-0.87 mg·L<sup>−1</sup> Fe(II); (<b>C</b>) 0.11 mg·L<sup>−1</sup> Cd<sup>2+</sup>-0.86 mg·L<sup>−1</sup> Fe(III); (<b>D</b>) 0.09 mg·L<sup>−1</sup> Pb<sup>2+</sup>-125 mg·L<sup>−1</sup> O<sub>2</sub>; (<b>E</b>) 0.09 mg·L<sup>−1</sup> Pb<sup>2+</sup>-0.87 mg·L<sup>−1</sup> Fe(II); (<b>F</b>) 0.09 mg·L<sup>−1</sup> Pb<sup>2+</sup>-0.86 mg·L<sup>−1</sup> Fe(III); (<b>G</b>) 0.08 mg·L<sup>−1</sup> Cu<sup>2+</sup>-125 mg·L<sup>−1</sup> O<sub>2</sub>; (<b>H</b>) 0.08 mg·L<sup>−1</sup> Cu<sup>2+</sup>-0.87 mg·L<sup>−1</sup> Fe(II); (<b>I</b>) 0.08 mg·L<sup>−1</sup> Cu<sup>2+</sup>-0.86 mg·L<sup>−1</sup> Fe(III).</p>
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<p>SWASV results obtained for tap water sample spiked with Hg-NPs<sup>Route A</sup>-modified electrodes obtaining the peaks of Cd<sup>2+</sup> (−0.68 V), Pb<sup>2+</sup> (−0.5 V) and Cu<sup>2+</sup> (−0.25 V) for each addition. In the inset are the addition standard curves for each metal.</p>
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22 pages, 7715 KiB  
Article
UV-Activated NO2 Gas Sensing by Nanocrystalline ZnO: Mechanistic Insights from Mass Spectrometry Investigations
by Artem Chizhov, Pavel Kutukov, Alexander Gulin, Artyom Astafiev and Marina Rumyantseva
Chemosensors 2022, 10(4), 147; https://doi.org/10.3390/chemosensors10040147 - 15 Apr 2022
Cited by 12 | Viewed by 2825
Abstract
In this work, the photostimulated processes of O2 and NO2 molecules with the surface of ZnO under UV radiation were studied by in situ mass spectrometry in the temperature range of 30–100 C. Nanocrystalline needle-like ZnO was synthesized by decomposition [...] Read more.
In this work, the photostimulated processes of O2 and NO2 molecules with the surface of ZnO under UV radiation were studied by in situ mass spectrometry in the temperature range of 30–100 C. Nanocrystalline needle-like ZnO was synthesized by decomposition of basic zinc carbonate at 300 C, and the surface concentration of oxygen vacancies in it were controlled by reductive post-annealing in an inert gas at 170 C. The synthesized materials were characterized by XRD, SEM, low-temperature nitrogen adsorption (BET), XPS, Raman spectroscopy, and PL spectroscopy. Irradiation of samples with UV light causes the photoabsorption of both O2 and NO2. The photoadsorption properties of ZnO are compared with its defective structure and gas-sensitive properties to NO2. A model of the sensor response of ZnO to NO2 under UV photoactivation is proposed. Full article
(This article belongs to the Special Issue Gas Sensors: Simulation, Modeling, and Characterization)
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Figure 1

Figure 1
<p>(<b>a</b>) Al<sub>2</sub>O<sub>3</sub> measuring plate equipped with two platinum electrodes for measuring the resistance of the sensor layer (image from an optical microscope); (<b>b</b>) SEM image of a measuring plate with an applied ZnO layer; (<b>c</b>) current–voltage characteristic of ZnO sensor measured at 100 <math display="inline"><semantics> <msup> <mrow/> <mo>∘</mo> </msup> </semantics></math>C in the dark; (<b>d</b>) evaluation of the thickness of the applied ZnO layer (SEM image).</p>
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<p>Block representation of the setup for sensor measurements.</p>
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<p>The design of the cell used for photostimulated MS experiments. The inset shows the emission spectrum of the LEDs used for irradiation.</p>
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<p>XRD patterns of ZnO-300 (<b>a</b>) and ZnO-V<sub>O</sub> (<b>b</b>) powder samples; (<b>c</b>) bar diffractogram of wurtzite ZnO (ICDD # 98-002-9272).</p>
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<p>SEM images of synthesized nanocrystalline ZnO powder at different magnifications: (<b>a</b>)—micrometer-sized aggregates; (<b>b</b>–<b>d</b>)—needle-shaped ZnO nanoparticles in aggregates.</p>
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<p>XP-spectra of ZnO-300 (<b>a</b>) and ZnO-V<sub>O</sub> (<b>b</b>) samples in the O1s region.</p>
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<p>(<b>a</b>) Normalized PL spectra of ZnO-300 (1) and ZnO-V<sub>O</sub> (2) samples at RT (excitation wavelength 360 nm); (<b>b</b>) Raman spectra of ZnO-300 (1) and ZnO-V<sub>O</sub> (2) samples at RT (excitation wavelength 785 nm).</p>
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<p>Mass spectrum of the carrier gas leaving the cell with loaded ZnO tablets under stationary dark conditions (black line) and after 9 min of turning on UV radiation (red line).</p>
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<p>Comparative baseline-corrected graphics showing photoadsorption of oxygen from carrier gas on ZnO-300 (1) and ZnO-V<sub>O</sub> (2) tablets under UV light illumination (370 nm) in the temperature range of 30–150 <math display="inline"><semantics> <msup> <mrow/> <mo>∘</mo> </msup> </semantics></math>C, determined from the ion current by <span class="html-italic">m</span>/<span class="html-italic">z</span> = 32.</p>
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<p>Changes in the ionic current during heating and UV illumination of ZnO tablets obtained from MS: (<b>a</b>) NO<sub>2</sub> (<span class="html-italic">m</span>/<span class="html-italic">z</span> = 30) in an atmosphere of He/100 ppm NO<sub>2</sub> (black line) and He/20% O<sub>2</sub>/100 ppm NO<sub>2</sub> (red line) for ZnO-300 sample; (<b>b</b>) NO<sub>2</sub> (<span class="html-italic">m</span>/<span class="html-italic">z</span> = 30) in an atmosphere of He/100 ppm NO<sub>2</sub> (black line) and He/20% O<sub>2</sub>/100 ppm NO<sub>2</sub> (red line) for ZnO-V<sub>O</sub> sample; (<b>c</b>) O<sub>2</sub> (<span class="html-italic">m</span>/<span class="html-italic">z</span> = 32) in the He/100 ppm NO<sub>2</sub> atmosphere for ZnO-300 sample; (<b>d</b>) oxygen (<span class="html-italic">m</span>/<span class="html-italic">z</span> = 32) in the He/100 ppm NO<sub>2</sub> atmosphere for ZnO-V<sub>O</sub> sample; (<b>e</b>,<b>f</b>) temperature profile of the experiment.</p>
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<p>Gas-sensing measurements for ZnO-300 and ZnO-V<sub>O</sub> samples for NO<sub>2</sub> in dark and under UV activation at 30 <math display="inline"><semantics> <msup> <mrow/> <mo>∘</mo> </msup> </semantics></math>C (<b>a</b>), 50 <math display="inline"><semantics> <msup> <mrow/> <mo>∘</mo> </msup> </semantics></math>C (<b>b</b>), and 100 <math display="inline"><semantics> <msup> <mrow/> <mo>∘</mo> </msup> </semantics></math>C (<b>c</b>).</p>
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<p>The concentration dependence of the sensor signal to NO<sub>2</sub> for ZnO-300 (rounds) and ZnO-V<sub>O</sub> (squares) sensors, measured under UV irradiation at temperatures of 30 <math display="inline"><semantics> <msup> <mrow/> <mo>∘</mo> </msup> </semantics></math>C, 50 <math display="inline"><semantics> <msup> <mrow/> <mo>∘</mo> </msup> </semantics></math>C, and 100 <math display="inline"><semantics> <msup> <mrow/> <mo>∘</mo> </msup> </semantics></math>C (solid lines) and under dark conditions at 100 <math display="inline"><semantics> <msup> <mrow/> <mo>∘</mo> </msup> </semantics></math>C (dashed line).</p>
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<p>NO<sub>2</sub> photoadsorption experiments on ZnO samples with different treatment history: (<b>a</b>) as-prepared ZnO was post-annealed in (He + 20% O<sub>2</sub>) atmosphere at 170 <math display="inline"><semantics> <msup> <mrow/> <mo>∘</mo> </msup> </semantics></math>C for 12 h (arrows show “turn-on”- and “turn-off”-induced photoadsorption peaks); (<b>b</b>) ZnO sample after annealing of the previous sample in He atmosphere at 170 <math display="inline"><semantics> <msup> <mrow/> <mo>∘</mo> </msup> </semantics></math>C for 12 h; (<b>c</b>) ZnO sample after exposing of the previous sample in (He + 20% O<sub>2</sub>) atmosphere at RT for 12 h.</p>
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<p>Temperature dependence of the rate of NO<sub>2</sub> photoadsorption under UV irradiation (370 nm) from an oxygen-rich atmosphere (He + 20% O<sub>2</sub> + 100 ppm NO<sub>2</sub>) on the ZnO surface on the Arrhenius plot.</p>
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<p>(<b>a</b>) Diagram shows the photoadsorption rate of NO<sub>2</sub> from an oxygen-rich atmosphere on ZnO-300 and ZnO-V<sub>O</sub> samples at different temperatures (data extracted from graphs in <a href="#chemosensors-10-00147-f009" class="html-fig">Figure 9</a>); (<b>b</b>) diagram shows sensor response of ZnO-300 and ZnO-V<sub>O</sub> samples to 3.8 ppm NO<sub>2</sub> at different temperatures (data extracted from graphs in <a href="#chemosensors-10-00147-f012" class="html-fig">Figure 12</a>).</p>
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10 pages, 1411 KiB  
Article
Potentiometric Determination of Moxifloxacin by Solid-Contact ISEs in Wastewater Effluents
by Sherif A. Abdel-Gawad, Hany H. Arab and Ahmed A. Albassam
Chemosensors 2022, 10(4), 146; https://doi.org/10.3390/chemosensors10040146 - 14 Apr 2022
Cited by 9 | Viewed by 2636
Abstract
In recent years, the use of ion-selective membranes in the sensing and assessment of environmental contaminants has become a critical goal. Using sodium tetraphenylborate (TPB) and phosphotungstic acid (PTA) as ion-pairing agents, two sensitive and selective sensors were manufactured to evaluate the electrochemical [...] Read more.
In recent years, the use of ion-selective membranes in the sensing and assessment of environmental contaminants has become a critical goal. Using sodium tetraphenylborate (TPB) and phosphotungstic acid (PTA) as ion-pairing agents, two sensitive and selective sensors were manufactured to evaluate the electrochemical response of moxifloxacin hydrochloride (MOX). The optimal electrochemical behavior was attained by fine-tuning all assay parameters. The manufactured membranes’ performance was optimal in a pH range from 1.0 to 5.0 with a linearity between 1 × 10−6 M and 1 × 10−2 M. The MOX–TPB and MOX–PTA membrane electrodes have Nernstian slopes of 59.2 ± 0.60 mV/decade and 58.4 ± 0.50 mV/decade, respectively. The proposed method was used to determine MOX in its pure form as well as real pharmaceutical wastewater effluents. The fabricated electrodes were effectively applied for the sensitive and selective determination of MOX in actual wastewater effluents without the need for any pre-treatment processes. Full article
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Figure 1
<p>Chemical structure of moxifloxacin hydrochloride.</p>
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<p>Diagram for the liquid contact ISE (<b>A</b>) and solid contact ISE (<b>B</b>).</p>
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<p>Profile of the potential (in mV) versus −log concentration (in M) for MOX sensors at pH 3.</p>
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<p>pH effect on the potential response of MOX membrane sensors.</p>
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<p>Stability of the MOX membrane sensors.</p>
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18 pages, 7809 KiB  
Article
Electrochemical Oxidation of Sodium Metabisulfite for Sensing Zinc Oxide Nanoparticles Deposited on Graphite Electrode
by Kailai Wang and Edward P. C. Lai
Chemosensors 2022, 10(4), 145; https://doi.org/10.3390/chemosensors10040145 - 13 Apr 2022
Cited by 2 | Viewed by 4008
Abstract
A novel concept was successfully evaluated for the electrochemical quantitative analysis of zinc oxide nanoparticles originally in aqueous suspension. An aliquot of the suspension was first placed on the working area of a graphite screen-printed electrode and the water was evaporated to form [...] Read more.
A novel concept was successfully evaluated for the electrochemical quantitative analysis of zinc oxide nanoparticles originally in aqueous suspension. An aliquot of the suspension was first placed on the working area of a graphite screen-printed electrode and the water was evaporated to form a dry deposit of ZnO nanoparticles. Deposition of ZnO nanoparticles on the electrode was confirmed by energy-dispersive X-ray spectroscopy. A probe solution containing KCl and sodium metabisulfite was added on top of the deposit for electrochemical analysis by cyclic voltammetry. The anodic peak current (Ipa) for metabisulfite, measured at +1.2 V vs. Ag/AgCl, afforded a lower detection limit of 3 µg and exhibited a linear dependence on the mass of deposited ZnO nanoparticles up to 15 μg. Further, the current increased nonlinearly until it reached a saturation level beyond 60 μg of ZnO nanoparticles. The diffusion coefficient of metabisulfite anions through the electrical double layer was determined to be 4.16 × 10−5 cm2/s. Apparently the surface reactivity of ZnO originated from the oxide anion rather than the superoxide anion or the hydroxyl radical. Enhancement of the metabisulfite oxidation peak current can be developed into a sensitive method for the quantitation of ZnO nanoparticles. Full article
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Figure 1
<p>Cyclic voltammetric measurement results of metabisulfite and ascorbic acid (0.003 M in 1.0 M KCl) oxidation peak currents vs. concentration of ZnO nanoparticles dispersed in sample solution.</p>
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<p>Cyclic voltammograms of sodium metabisulfite (0.003 M in 1.0 M KCl) on graphite electrode with ZnO nanoparticles in suspension (0.21 mg/mL) versus ZnO nanoparticles deposited on graphite electrode (150 µL of 0.21 mg/mL). E<sub>initial</sub> = 0.0 V, E<sub>final</sub> = 1.4 V, scan rate = 0.10 V/s, scan direction = positive.</p>
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<p>Energy dispersive X-ray spectroscopy of (<b>a</b>) blank screen-printed electrode, and (<b>b</b>) screen-printed electrode with a deposit of ZnO nanoparticles.</p>
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<p>Energy dispersive X-ray spectroscopy of (<b>a</b>) blank screen-printed electrode, and (<b>b</b>) screen-printed electrode with a deposit of ZnO nanoparticles.</p>
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<p>Energy dispersive X-ray analysis results of Zn element % by weight vs. mass of ZnO nanoparticles deposited on graphite electrode.</p>
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<p>Cyclic voltammetric measurement results of sodium metabisulfite (0.003 M and 0.010 M in 1.0 M KCl) oxidation peak currents with (<b>a</b>) 0 to 15 μg and (<b>b</b>) 0 to 140 μg of ZnO nanoparticles deposited on graphite electrode.</p>
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<p>(<b>a</b>) Cyclic voltammograms of 0.003 M sodium metabisulfite on graphite electrodes deposited with different masses of ZnO nanoparticles. (<b>b</b>) Metabisulfite oxidation peak potential vs. mass of ZnO nanoparticles deposited.</p>
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<p>(<b>a</b>) Cyclic voltammograms of sodium metabisulfite at different concentrations on graphite electrodes deposited with 60 µg of ZnO nanoparticles. (<b>b</b>) Metasulfite oxidation peak potential vs. metabisulfite concentration tested.</p>
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<p>(<b>a</b>) Linear dependence of metasulfite oxidation peak current (I<sub>pa</sub>) on square root of potential scan rate (<span class="html-italic">ν</span>); (<b>b</b>) dependence of ln(I<sub>pa</sub>) on ln(<span class="html-italic">ν</span>). Mass of ZnO nanoparticles deposited on SPE = 129 μg; metabisulfite concentration in 1.0 M KCl for CV analysis = 0.003 M; potential scan rate = 0.006 to 0.15 V/s.</p>
Full article ">Figure 8 Cont.
<p>(<b>a</b>) Linear dependence of metasulfite oxidation peak current (I<sub>pa</sub>) on square root of potential scan rate (<span class="html-italic">ν</span>); (<b>b</b>) dependence of ln(I<sub>pa</sub>) on ln(<span class="html-italic">ν</span>). Mass of ZnO nanoparticles deposited on SPE = 129 μg; metabisulfite concentration in 1.0 M KCl for CV analysis = 0.003 M; potential scan rate = 0.006 to 0.15 V/s.</p>
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<p>(<b>a</b>) Chronoamperograms obtained at graphite screen-printed electrode (0.3 cm diameter, deposited with 120 μg of ZnO nanoparticles) at 1.0 M KCl for different concentrations of sodium metabisulfite (from 0.00 to 12.1 mM). Applied potential = 1.40 V vs. Ag/AgCl reference electrode. (<b>b</b>) Plot of Cottrell equation slopes against sodium metabisulfite concentrations.</p>
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10 pages, 2040 KiB  
Article
Estimation of Grain Size in Randomly Packed Granular Material Using Laser-Induced Breakdown Spectroscopy
by Songting Li, Yaju Li, Xiaolong Li, Liangwen Chen, Dongbin Qian, Shaofeng Zhang and Xinwen Ma
Chemosensors 2022, 10(4), 144; https://doi.org/10.3390/chemosensors10040144 - 13 Apr 2022
Cited by 5 | Viewed by 2461
Abstract
Grain size is one of the most important physical parameters for randomly packed granular (RPG) materials. Its estimation, especially in situ, plays a key role in many natural and industrial processes. Here, the application of laser-induced breakdown spectroscopy (LIBS) was investigated experimentally to [...] Read more.
Grain size is one of the most important physical parameters for randomly packed granular (RPG) materials. Its estimation, especially in situ, plays a key role in many natural and industrial processes. Here, the application of laser-induced breakdown spectroscopy (LIBS) was investigated experimentally to estimate the grain size in RPG materials. The experiment was performed by taking sieved copper microspheres with discrete median diameters ranging from 53 to 357 μm as examples and by measuring the plasma emissions induced by 1064 nm laser pulses with a duration of 7 ns in an air environment. It was found that the plasma emission measurements were successful in estimating the grain median diameter via monitoring the variations in plasma temperature (electron density) at the range of median diameter below (above) a critical value. In addition, it was demonstrated that, when plasma temperature serves as an indicator of grain size, the intensity ratio between two spectral lines from different upper energy levels of the same emitting species can be used as an alternative indicator with higher sensitivity. The results show the potential of using LIBS for in situ estimation of grain size in RPG materials for the first time. Full article
(This article belongs to the Special Issue Application of Laser-Induced Breakdown Spectroscopy)
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Figure 1
<p>(<b>a</b>) Spectra recorded in the wavelength range of 508–524 nm for the nine RPG samples. (<b>b</b>) Intensities of Cu I lines at 510.6, 515.3, and 521.8 nm as a function of the grain median diameter. Error bars represent the standard deviation of 6 independent measurements.</p>
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<p>(<b>a</b>) Typical Stark broadening profile of Cu I line at 510.6 nm; red line is the Lorentzian fitting. (<b>b</b>) Electron density as a function of the grain median diameter; error bars represent the standard deviation of 6 independent measurements; red line is the exponential fitting, <span class="html-italic">R</span><sup>2</sup> = 0.97.</p>
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<p>Plasma temperature as a function of the grain median diameter. Error bars represent the standard deviation of 6 independent measurements. Red line is the linear fitting, <span class="html-italic">R</span><sup>2</sup> = 0.95.</p>
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<p>Intensity ratio of Cu I 521.8 nm to Cu I 510.6 nm and plasma temperature as a function of the grain median diameter. Error bars represent the standard deviation of 6 independent measurements and red lines are the linear fittings.</p>
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15 pages, 3228 KiB  
Article
Application of Multiharmonic QCM-D for Detection of Plasmin at Hydrophobic Surfaces Modified by β-Casein
by Sandro Spagnolo, Eric S. Muckley, Ilia N. Ivanov and Tibor Hianik
Chemosensors 2022, 10(4), 143; https://doi.org/10.3390/chemosensors10040143 - 11 Apr 2022
Cited by 7 | Viewed by 3094
Abstract
Plasmin protease plays an important role in many processes in living systems, including milk. Monitoring plasmin activity is important for control of the nutritional quality of milk and other dairy products. We designed a biosensor to detect the proteolytic activity of plasmin, using [...] Read more.
Plasmin protease plays an important role in many processes in living systems, including milk. Monitoring plasmin activity is important for control of the nutritional quality of milk and other dairy products. We designed a biosensor to detect the proteolytic activity of plasmin, using multiharmonic quartz crystal microbalance with dissipation (QCM-D). The β-casein immobilized on the hydrophobic surface of 1-dodecanethiol on the AT-cut quartz crystal was used to monitor plasmin activity. We demonstrated detection of plasmin in a concentration range of 0.1–20 nM, with the limit of detection about 0.13 ± 0.01 nM. The analysis of viscoelastic properties of the β-casein layer showed rapid changes of shear elasticity modulus, μ, and coefficient of viscosity, η, at plasmin sub-nanomolar concentrations, followed by modest changes at nanomolar concentrations, indicating multilayer architecture β-casein. A comparative analysis of viscoelastic properties of β-casein layers following plasmin and trypsin cleavage showed that the higher effect of trypsin was due to larger potential cleavage sites of β-casein. Full article
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<p>Plot of the kinetics of (<b>a</b>) resonant frequency and (<b>b</b>) overtone number-normalized frequency changes of the QCM crystal after incubation with different solutions: (1) rinsing of the 1-dodecanethiol-coated crystal with TRIS buffer; (2) incubation with 0.1 mg/mL of β-casein; (3) rinsing with TRIS buffer to remove weakly bound β-casein; (4) addition of plasmin in a concentration of 10 nM and incubation for 30 min; (5) rinsing with TRIS buffer.</p>
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<p>Plot of the dissipation changes, ΔD, of the QCM crystal vs. time after incubation with different solutions at fundamental resonance frequency until 9th overtone: (1) initial rinsing of the 1-dodecanethiol-coated crystal with TRIS buffer; (2) incubation with 0.1 mg/mL β-casein; (3) rinsing with TRIS buffer to remove weakly bound β-casein; (4) incubation with plasmin at concentration of 10 nM for 30 min; (5) final rinsing with TRIS buffer.</p>
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<p>The kinetics of the changes of the 3rd harmonic frequency (<b>a</b>) and dissipation (<b>b</b>) at different concentrations of plasmin (see the legend) after the stabilization of the newly formed β-casein adlayer.</p>
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<p>(<b>a</b>) The plot of the normalized frequency changes at different plasmin concentrations, fitted with inverse Michaelis–Menten equation. (<b>b</b>) Lineweaver-Burk plot obtained from the data of <a href="#chemosensors-10-00143-f004" class="html-fig">Figure 4</a>a and linear fit using Origin Pro 8. The red lines are the fitted curves.</p>
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<p>Variation of (<b>a</b>) thickness and shear modulus and (<b>b</b>) viscosity coefficient vs. concentration of the plasmin.</p>
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<p>The plot of (<b>a</b>) shear modulus and (<b>b</b>) viscosity coefficient vs. concentration of trypsin and plasmin analyzed by Voinova–Voigt model.</p>
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<p>The scheme of cleavage sites for trypsin and plasmin at β-casein formed at hydrophobic surface and the scheme of β-casein layer after cleavage by proteases.</p>
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13 pages, 2476 KiB  
Article
Dual-Signal-Encoded Barcodes with Low Background Signal for High-Sensitivity Analysis of Multiple Tumor Markers
by Bo Zhang, Wan-Sheng Tang and Shou-Nian Ding
Chemosensors 2022, 10(4), 142; https://doi.org/10.3390/chemosensors10040142 - 9 Apr 2022
Cited by 2 | Viewed by 2524
Abstract
The suspension array technology (SAT) is promising for high-sensitivity multiplexed analysis of tumor markers. Barcodes as the core elements of SAT, can generate encoding fluorescence signals (EFS) and detection fluorescence signals (DFS) in the corresponding flow cytometer channel. However, the bleed-through effect of [...] Read more.
The suspension array technology (SAT) is promising for high-sensitivity multiplexed analysis of tumor markers. Barcodes as the core elements of SAT, can generate encoding fluorescence signals (EFS) and detection fluorescence signals (DFS) in the corresponding flow cytometer channel. However, the bleed-through effect of EFS in the DFS channel and the reagent-driven non-specific binding (NSB) lead to background interference for ultrasensitive assay of multiple targets. Here, we report an ingenious method to eliminate background interference between barcode and reporter using low-background dual-signal-encoded barcodes (DSBs) based on microbeads (MBs) and quantum dots (QDs). The low-background DSBs were prepared via combination strategy of two signals containing scatter signals and fluorescence signals. Three types of MBs were distinguished by the scattering channel of flow cytometer (FSC vs. SSC) to obtain the scattered signals. Green quantum dots (GQDs) or red quantum dots (RQDs) were coupled to the surface of MBs by sandwich immune structure to obtain the distinguishable fluorescent signals. Furthermore, the amount of conjugated capture antibody on the MB’s surface was optimized by comparing the change of detection sensitivity with the addition of capture antibody. The combination measurements of specificity and NSB in SAT platform were performed by incubating the capture antibody-conjugated MBs (cAb-MBs) with individual QD-conjugated detection antibody (QDs-dAb). Finally, an SAT platform based on DSBs was successfully established for highly sensitive multiplexed analysis of six tumor markers in one test, which suggests the promising tool for highly sensitive multiplexed bioassay applications. Full article
(This article belongs to the Special Issue Application of Luminescent Materials for Sensing)
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<p>DSBs distinguishability validation. (<b>a</b>) The scatter signal barcodes of SiO<sub>2</sub>-L, PS-L, and PS-S can be distinguished by the scatter plot of SSC versus FSC. Histograms of three groups of fluorescent signal barcodes. (<b>b</b>) GQD-SCCA-PS-L and RQD-AFP-PS-L, (<b>c</b>) GQD-NSE-PS-S and RQD-CA724-PS-S, and (<b>d</b>) GQD-CEA-SiO<sub>2</sub>-L and RQD-CA125-SiO<sub>2</sub>-L.</p>
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<p>Optimization of added amounts of cAb-CEA. Histograms of GQD-CEA-SiO<sub>2</sub>-L barcodes with (<b>a</b>–<b>f</b>) 25, 250, 500, 1000, 2500, and 5000 ng of cAb-CEA, respectively. (<b>g</b>) Optimal amount of antigen of cAb-CEA (500 ng). (<b>h</b>) Laser-scanning confocal images of GQD -CEA-SiO<sub>2</sub>-L with different amounts of cAb-CEA.</p>
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<p>Optimization of added amounts of cAb-CA125. Histograms of RQD-CA125-SiO<sub>2</sub>-L barcodes with (<b>a</b>–<b>f</b>) 36, 360, 720, 1440, 3600, and 7200 ng of cAb-CA125, respectively. (<b>g</b>) Optimal amount of antigen of cAb-CA125 (1440 ng). (<b>h</b>) Laser-scanning confocal images of GQD-CA125-SiO<sub>2</sub>-L with different amounts of cAb-CA125.</p>
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<p>Combinatorial experiments of 6-plex specific and non-specific binding. (<b>a</b>,<b>b</b>) cAb-MB (column) and Ag (row) incubation and then addition of QDs-dAb. Diagonal and off-diagonal represent specific and non-specific antigen binding, respectively. Histograms of the count for (cAb, Ag) are on the right.</p>
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<p>(<b>a</b>) Schematic illustration for the sandwich immunoassay of tumor markers. (<b>b</b>) Standard curves of CEA, SCCA, NSE, CA125, AFP, and CA724 in 6-plexed tumor markers assay.</p>
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<p>Schematic illustration of the flow cytometric readout microbeads and the dual-signal-encoded strategy.</p>
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<p>Construction of DSBs. (<b>a</b>) GQDs or (<b>b</b>) RQDs were coupled to the surface of MBs by sandwich immune structure. Laser-scanning confocal images of corresponding DSBs are on the right.</p>
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16 pages, 3203 KiB  
Article
Microfluidic-Enabled Multi-Cell-Densities-Patterning and Culture Device for Characterization of Yeast Strains’ Growth Rates under Mating Pheromone
by Jing Zhang, Wenting Shen, Zhiyuan Cai, Kaiyue Chen, Qi Ouyang, Ping Wei, Wei Yang and Chunxiong Luo
Chemosensors 2022, 10(4), 141; https://doi.org/10.3390/chemosensors10040141 - 8 Apr 2022
Cited by 2 | Viewed by 2684
Abstract
Yeast studies usually focus on exploring diversity in terms of a specific trait (such as growth rate, antibiotic resistance, or fertility) among extensive strains. Microfluidic chips improve these biological studies in a manner of high throughput and high efficiency. For a population study [...] Read more.
Yeast studies usually focus on exploring diversity in terms of a specific trait (such as growth rate, antibiotic resistance, or fertility) among extensive strains. Microfluidic chips improve these biological studies in a manner of high throughput and high efficiency. For a population study of yeast, it is of great significance to set a proper initial cell density for every strain under specific circumstances. Herein, we introduced a novel design of chip, which enables users to load cells in a gradient order (six alternatives) of initial cell density within one channel. We discussed several guidelines to choose the appropriate chamber to ensure successful data recording. With this chip, we successfully studied the growth rate of yeast strains under a mating response, which is crucial for yeasts to control growth behaviors for prosperous mating. We investigated the growth rate of eight different yeast strains under three different mating pheromone levels (0.3 μM, 1 μM, and 10 μM). Strains with, even, a six-fold in growth rate can be recorded, with the available data produced simultaneously. This work has provided an efficient and time-saving microfluidic platform, which enables loading cells in a pattern of multi-cell densities for a yeast population experiment, especially for a high-throughput study. Besides, a quantitatively analyzed growth rate of different yeast strains shall reveal inspiring perspectives for studies concerning yeast population behavior with a stimulated mating pheromone. Full article
(This article belongs to the Special Issue Microfluidic Devices for Biological Quantitative Analysis)
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<p>Schematic of the experimental system setup and microfluidic chip design. (<b>a</b>) The experimental platform consists of a newly designed microfluidic chip, syringe pumps, microscope, and computer. During the experiment, four culture solutions with different concentrations of α-factor (0 μM, 0.3 μM, 1 μM, 10 μM) were injected into four identical observation regions of the chip. (<b>b</b>) Overview of the chip. Different colored dotted boxes present different functional parts of the chip. Current design allows 6 different strains growing under same environment. (<b>c</b>) Schematic diagram of 1 set of observation chambers, which includes 6 observation chambers, fence, main channel, and by-pass channel. During preparation, the loaded cells were flowing with the medium from the right side (as the arrow on the right shows). For each strain, there are six chambers for researchers to choose for an appropriate initial cell density. Circled number 1–6 marks a gradient distribution of initial cell density. During experiment, the culture medium would be injected by the syringe pump from the left side as the 7 arrows on the left shows. The various heights of each region were denoted by different colors in the diagram. (<b>d</b>) The microfluidic chip with 2 different inks load into, placed with a ruler. (<b>e</b>) Inside channels and observation chambers of this microfluidic chip observed by a 4× objective.</p>
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<p>Results of simulations finished by COMSOL accompanied with microscope images. (<b>a</b>) We list several information about the simulation process here. (<b>b</b>) Simulation results on velocity field when loading cells. We can clearly tell that the No. 6 chamber has the biggest velocity, while the No. 1 chamber has the smallest velocity. (<b>c</b>) Simulation results under circumstance of culturing cells with by-pass channel. (<b>d</b>) Simulation results under circumstance of culturing cells without by-pass channel. The white arrows represent the direction of medium. The top of (<b>b</b>–<b>d</b>) is the overview of the chip while the bottom of (<b>b</b>–<b>d</b>) is the enlarged view of every chamber. The legend of (<b>b</b>–<b>d</b>) shows the correspondence of color and velocity. Circled number at lower right of every image correspond to each observation chambers.</p>
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<p>Schematic diagram of yeast mating response pathway and trains we used in this work. (<b>a</b>) Mating response pathway of budding yeast. For <span class="html-italic">MATa</span> yeast, binding of α-factor to Ste2 protein, a seven-transmembrane G-protein-coupled receptor, causes the release of Gβγ heterodimer form the G-protein heterotrimer which concluded Gpa1, Ste18, and Ste4 (Gpa1: Gα subunit; Ste4: Gβ subunit; Ste18: Gγ subunit). Gβγ then binds with the scaffold protein Ste5. With recruitment of activated Cdc42 to cell membrane, the activated Cdc42 activates Ste20, and then a sequential phosphorylation happens from Ste11, Ste7, and, finally, to Fus3. Activated Fus3p then activates Ste12, while the activated proteins regulate the downstream proteins of mating pathway. (<b>b</b>) We chose genes from 3 different categories: (1) Growth related; (2) Mating signal related; and (3) New construction for this work. We then chose relating single-gene knock-out strains from yeast deletion library for genes belonging to (1) and (2). Strain of <span class="html-italic">ste4</span>-Δ/<span class="html-italic">loc1</span>-Δ is new strain constructed by LiAc transformation method for this work.</p>
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<p>Verification process on function of loading yeasts with pattern of gradient density distribution. (<b>a</b>) An ideal trial of loading yeasts from many attempts. Circled number at lower right of every image corresponds to each observation chamber. Number of yeasts increased from chamber No. 1 to chamber No. 6, which corresponds to the increasing distance for these chambers to loading well. (<b>b</b>) An ideal example for selecting chambers for successfully recording available data. In this situation, yeasts will not grow out of the chamber at the end of the experiment. (<b>c</b>) One of the situations that will not be selected where initial cell density is too high, so that yeasts grow out of the chamber when the experiment ends. (<b>d</b>) Another situation that will not be picked, where yeasts stay at the edge of the chamber after being loaded. Yeasts will grow directly into the main channel during the experiment. The left half of (<b>b</b>–<b>d</b>) is the schematic diagram, and the other half is from loading trials.</p>
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<p>Growth rate analyzation on the wild type strain, in terms of population number and area. For a specific strain, we recorded time-series images under four α-factor concentrations: 0 μM, 0.3 μM, 1 μM, and 10 μM. (<b>a</b>) Microscopic images from 2 conditions (0 μM and 1 μM); the 4 images in each row of (<b>a</b>) were four time points (0 h, 1.5 h, 3 h, and 6 h). Values of the population’s size (area and number) are marked under every image in (<b>a</b>), where a value outside the brackets is an area of yellow-circled populations, while the one inside the brackets is a number. (<b>b</b>) Fitting the results of the populations exhibited in (<b>a</b>) in terms of area and number. (<b>c</b>) GRa and GRn from all four conditions for the wild type strain. Each column in (<b>c</b>) is obtained by calculating the average and standard deviation of fitting results from at least three parallel observation points from the same strain. (<b>d</b>) DRPUa and DRPUn are calculated by using formula (1).</p>
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<p>Growth rate analyzation on <span class="html-italic">swe1</span>-Δ and <span class="html-italic">loc1</span>-Δ strains, in terms of population area (GRa) and number (GRn). Analyzation pipeline is the same as what was described for the wild type strain. (<b>a</b>) Microfluidic images of the two strains from four time points (0 h, 1.5 h, 3 h, 6 h), under 0 μM and 1 μM. Values outside the brackets are population area, and values inside the brackets are population number. (<b>b</b>) Fitting results corresponding to a certain strain under a certain condition in (<b>a</b>). (<b>c</b>,<b>d</b>) Summary of GRa and GRn under four conditions for <span class="html-italic">swe1</span>-Δ. (<b>e</b>,<b>f</b>) Summary of GRa and GRn under four conditions of <span class="html-italic">loc1</span>-Δ strain. Each column in (<b>c</b>–<b>f</b>) is obtained by calculating the average and standard deviation of the fitting results from at least three parallel observation points from the same strain.</p>
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<p>Growth rate analyzation on <span class="html-italic">ste4</span>-Δ and <span class="html-italic">ste4</span>-Δ/<span class="html-italic">loc1</span>-Δ of strains, in terms of population area (GRa) and number (GRn). The analyzation pipeline is the same as what was described for the wild type strain. (<b>a</b>) Microfluidic images of the two strains from four time points (0 h, 1.5 h, 3 h, 6 h) under 0 μM and 1 μM. The values outside brackets are population area, and the values inside brackets are population number. (<b>b</b>) Fitting results corresponding to certain strain under certain condition in (<b>a</b>). (<b>c</b>,<b>d</b>) Summary of GRa and GRn under four conditions for the <span class="html-italic">ste4</span>-Δ strain. (<b>e</b>,<b>f</b>) Summary of GRa and GRn under four conditions for the <span class="html-italic">ste4</span>-Δ/<span class="html-italic">loc1</span>-Δ strain. Each column in (<b>c</b>–<b>f</b>) is obtained by calculating the average and standard deviation of fitting results, from at least three parallel observation points for the same strain.</p>
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<p>The growth difference ΔGRa ratio and ΔGRn ratio of all strains, as compared with the wild type strains under four α-factor concentrations. The x axis represents ΔGRa ratio and y axis is ΔGRn ratio. Each point represented a specific strain and is obtained by calculating the average data calculated from at least three parallel observation points from the same strain. The color blocks in each figure represent the area where strains have a faster (yellow area) or smaller (blue area) growth rate than the wild type strains. The hollow circle inside each figure represents (0, 0), where the strain has the same growth rate as the wild type strains in terms of both area and number. The line of y = x represents the set of points where the ΔGRa ratio is equal to the ΔGRn ratio.</p>
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13 pages, 3994 KiB  
Article
Cholesteric Liquid Crystal Photonic Hydrogel Films Immobilized with Urease Used for the Detection of Hg2+
by Jie Liu, Wenjun Tai, Deliang Wang, Jie Su and Li Yu
Chemosensors 2022, 10(4), 140; https://doi.org/10.3390/chemosensors10040140 - 8 Apr 2022
Cited by 10 | Viewed by 3523
Abstract
Mercury ion is one of the most widespread heavy metal contaminants which can accumulate in the body through multiple channels, posing a detrimental impact on human health. We demonstrate a simple and low-cost method for the detection of Hg2+ assisted by a [...] Read more.
Mercury ion is one of the most widespread heavy metal contaminants which can accumulate in the body through multiple channels, posing a detrimental impact on human health. We demonstrate a simple and low-cost method for the detection of Hg2+ assisted by a cholesteric liquid crystal photonic hydrogel (polyacrylic acid (PAA)) film with immobilized urease (CLC-PAAurease film). In the absence of Hg2+, a significant change in color and an obvious red shift in the reflected light wavelength of the prepared film were observed, since urease can hydrolyze urea to produce NH3, resulting in an increasing pH value of the microenvironment of CLC-PAAurease film. Hg2+ can inhibit the activity of urease so that the color change of the film is not obvious, corresponding to a relatively small variation of the reflected light wavelength. Therefore, Hg2+ can be quantitatively detected by measuring the displacement of the reflected light wavelength of the film. The detection limit of Hg2+ is about 10 nM. This approach has a good application prospect in the monitoring of heavy metal ions in environmental water resources. Full article
(This article belongs to the Special Issue Feature Papers on Luminescent Sensing)
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<p>Schematic diagram of CLC-PAA urease PC films for the detection of Hg<sup>2+</sup>.</p>
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<p>Comparison diagram of PAA gel film in water: (<b>a</b>) before and (<b>b</b>) after the swelling.</p>
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<p>Swelling ratio (φ) of PAA gel film (<b>a</b>) at different amounts of TPGDA (ζ) and (<b>b</b>) at different pH. φ is defined as (m<sub>2</sub> − m<sub>1</sub>)/m<sub>1</sub>, where m<sub>2</sub> and m<sub>1</sub> are the mass of gel film in water and dry state, respectively.</p>
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<p>SEM images of (<b>a</b>) fractured surface and (<b>b</b>) the upper surface of prepared CLC PC films. (<b>c</b>) UV–vis spectra and the optical photographs of Ex-CLC, CLC PC and CLC-PAA PC film.</p>
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<p>SEM images of fractured surface of (<b>a</b>) CLC film and (<b>b</b>) CLC-PAA photonic crystal hydrogel film when the films were cut perpendicularly to the surface of films. scale bar: 1 μm.</p>
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<p>Tensile stress–strain curves of CLC, PAA and CLC-PAA films.</p>
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<p>(<b>a</b>) UV-visible reflection spectra of CLC-PAA PC films at different pH; (<b>b</b>) The wavelengths of the reflection light and the optical images of CLC-PAA PC films under different pH.</p>
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<p>FTIR spectra of (<b>a</b>) CLC PC films, (<b>b</b>) CLC-PAA PC films, and (<b>c</b>) CLC-PAA<sub>urease</sub> PC films, respectively.</p>
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<p>UV-visible reflection spectra of CLC-PAA<sub>urease</sub> photonic crystal hydrogel films after dropping urea solution (200 µL) with different concentrations for 10 min.</p>
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<p>(<b>a</b>) The UV-visible reflection spectra of CLC-PAA PC films at different concentrations of urease (The films were treated with 10 mM urea for 10 min.); (<b>b</b>) The wavelength values of the reflection light; (<b>c</b>) The optical images of CLC-PAA PC films at different concentrations of urease. scale bar: 1 mm.</p>
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<p>(<b>a</b>) The UV-visible reflection spectra of CLC-PAA<sub>urease</sub> PC films at different concentrations of Hg<sup>2+</sup> (The films were treated with 10 mM urea for 10 min.); (<b>b</b>) The wavelength values of the reflection light of CLC-PAA<sub>urease</sub> PC films at different concentrations of Hg<sup>2+</sup>; (<b>c</b>) The optical images of CLC-PAA <sub>urease</sub> PC films at different concentrations of Hg<sup>2+</sup>. scale bar: 1 mm.</p>
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<p>(<b>a</b>) UV-visible reflection spectra of CLC-PAA<sub>urease</sub> PC films with various metal ions (The films were treated with urea (10 mM) for 10 min); (<b>b</b>) The wavelength values of the reflected light of CLC-PAA<sub>urease</sub> PC films with various metal ions.</p>
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10 pages, 1110 KiB  
Article
Simple and Fast Two-Step Fully Automated Methodology for the Online Speciation of Inorganic Antimony Coupled to ICP-MS
by Lindomar A. Portugal, Edwin Palacio, Víctor Cerdà, Joao H. Santos-Neto, Laura Ferrer and Sergio L. C. Ferreira
Chemosensors 2022, 10(4), 139; https://doi.org/10.3390/chemosensors10040139 - 8 Apr 2022
Cited by 4 | Viewed by 2489
Abstract
A very simple, fast and non-chromatographic methodology for inorganic antimony speciation based on Multisyringe Flow Injection Analysis (MSFIA) employing online hydride generation (HG) ICP-MS was developed. The fully automated analysis is performed in two steps: firstly, Sb(III) is quantified by ICP-MS after chemical [...] Read more.
A very simple, fast and non-chromatographic methodology for inorganic antimony speciation based on Multisyringe Flow Injection Analysis (MSFIA) employing online hydride generation (HG) ICP-MS was developed. The fully automated analysis is performed in two steps: firstly, Sb(III) is quantified by ICP-MS after chemical vapor generation; then, total antimony is determined in the presence of potassium iodide as a pre-reducer of Sb(V) to Sb(III). The Sb(V) concentration is quantified by the difference between the total antimony and Sb(III) concentrations, reaching an analysis frequency of 30 h−1. The optimization was performed using a Box Behnken design. The MSFIA-HG-ICP-MS system allows the antimony speciation analysis with a detection limit of 0.016 µg L−1 for Sb(III), working in a linear range of 0.053 to 5.0 µg L−1. This method was applied for the determination of Sb(III) and Sb(V) in water samples from Maiorca Island, Spain, and the concentrations found varied from 0.10 to 0.14 µg L−1 for Sb(III) and from 0.12 to 0.28 µg L−1 for Sb(V). The results were validated by addition/recovery tests, obtaining recoveries between 90 and 111% in both cases. Furthermore, a good precision was achieved, 1.4% RSD, and sample and reagent consumption were reduced to a few mL, with the consequent decrease in waste generation. Thus, the proposed method is a good tool for the speciation of inorganic antimony at ultra-trace levels in waters, allowing its risk assessment. Full article
(This article belongs to the Section Analytical Methods, Instrumentation and Miniaturization)
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<p>MSFIA-HG-ICP-MS method for automated online inorganic antimony speciation. GLS: gas-liquid separator; MCx: methacrylate connector; RCx: reaction coil; R1: carrier; R2: KI solution; R3: NaBH<sub>4</sub> solution; R4: HCl solution; Vx: solenoid valves.</p>
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<p>Optimization of nebulizer gas flow rate. <sup>121</sup>Sb 5 µg L<sup>−1</sup> standard solution and blank of reagent signals were analyzed for each flow rate.</p>
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<p>Time to sweeps per reading optimization. <sup>121</sup>Sb 5 µg L<sup>−1</sup> standard solution was read using different integration times, working with a 0.7 L min<sup>−1</sup> Ar flow rate.</p>
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9 pages, 1745 KiB  
Article
Highly Sensitive Detection of Carbaryl Pesticides Using Potentiometric Biosensor with Nanocomposite Ag/r-Graphene Oxide/Chitosan Immobilized Acetylcholinesterase Enzyme
by Mashuni Mashuni, Halimahtussaddiyah Ritonga, M. Jahiding, Bonni Rubak and Fitri Handayani Hamid
Chemosensors 2022, 10(4), 138; https://doi.org/10.3390/chemosensors10040138 - 7 Apr 2022
Cited by 10 | Viewed by 3403
Abstract
Novel, sensitive, selective, efficient and portable electrochemical biosensors are needed to detect residual contaminants of the pesticide 1-naphthyl methylcarbamate (carbaryl) in the environment, food, and essential biological fluids. In this work, a study of nanocomposite-based Ag reduced graphene oxide (rGO) and chitosan (CS) [...] Read more.
Novel, sensitive, selective, efficient and portable electrochemical biosensors are needed to detect residual contaminants of the pesticide 1-naphthyl methylcarbamate (carbaryl) in the environment, food, and essential biological fluids. In this work, a study of nanocomposite-based Ag reduced graphene oxide (rGO) and chitosan (CS) that optimise surface conditions for immobilisation of acetylcholinesterase (AChE) enzyme to improve the performance of catalytic biosensors is examined. The Ag/rGO/CS nanocomposite membrane was used to determine carbaryl pesticide using a potentiometer transducer. The AChE enzyme-based biosensor exhibits a good affinity for acetylthiocholine chloride (ATCl). It can catalyse the hydrolysis of ATCl with a potential value of 197.06 mV, which is then oxidised to produce a detectable and rapid response. Under optimal conditions, the biosensor detected carbaryl pesticide at concentrations in the linear range of 1.0 × 10−8 to 1.0 μg mL−1 with a limit of detection (LoD) of 1.0 × 10−9 μg mL−1. The developed biosensor exhibits a wide working concentration range, detection at low concentrations, high sensitivity, acceptable stability, reproducibility and simple fabrication, thus providing a promising tool for pesticide residue analysis. Full article
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<p>(<b>A</b>,<b>B</b>) SEM images, (<b>C</b>) EDX analysis; (<b>D</b>) elemental mapping of the Ag/rGO/CS nanocomposite.</p>
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<p>XRD patterns of the Ag/rGO/CS nanocomposite.</p>
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<p>(<b>a</b>) Graph of the relationship of –Log [Carbaryl] with the E (mV vs. Ag/AgCl) and (<b>b</b>) the %I of carbaryl pesticide.</p>
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16 pages, 3361 KiB  
Article
Design, Elaboration, and Characterization of an Immunosensor for the Detection of a Fungal Toxin in Foodstuff Analyses
by Zeineb Ben Abdallah, Halim Sghaier, Ibtissem Gammoudi, Fabien Moroté, Sébastien Cassagnère, Lena Romo, Laure Béven, Christine Grauby-Heywang and Touria Cohen-Bouhacina
Chemosensors 2022, 10(4), 137; https://doi.org/10.3390/chemosensors10040137 - 6 Apr 2022
Cited by 6 | Viewed by 3016
Abstract
This work describes the complete elaboration of an immunosensor for the detection of the fungal B1 aflatoxin (AFB1). In a first step, a system made of three screen-printed electrodes (SPEs) was manufactured using gold, silver/silver chloride, and carbon pastes. Raman spectroscopy showed that [...] Read more.
This work describes the complete elaboration of an immunosensor for the detection of the fungal B1 aflatoxin (AFB1). In a first step, a system made of three screen-printed electrodes (SPEs) was manufactured using gold, silver/silver chloride, and carbon pastes. Raman spectroscopy showed that the thermal treatment applied to the electrodes enabled a strong decrease in the amount of undesirable organic molecules for each paste. Atomic Force Microscopy was also used to reveal the morphology of the electrode surfaces. In a second step, an autonomous and cheap electronic system was designed for the control of the sensor and electrochemical measurements, showing current variations significantly higher than those observed with a commercial system. In a last step, the gold working electrode of this system was functionalized by a simple self-assembly method, optimized in a previous work, with a molecular architecture including an antibody recognizing specifically AFB1. The complete device was finally realized by combining the SPEs and the electronic platform. The resulting setup was able to detect AFB1 toxin in a buffer with an LOD of about 50 fg/mL. It was then applied to the detection of AFB1 in rice milk, a more realistic medium comparable with those met in an agrifood context. The electrochemical detection of AFB1 was possible in a range of concentration between 0.5 pg/mL and 2.5 pg/mL, with the sensor behaving linearly in this range. Full article
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<p>Geometries of (<b>a</b>) the working electrode (gold) and (<b>b</b>) the reference (Ag/AgCl) and counter (carbon) ones for the electrochemical homemade sensor. (<b>c</b>) Scheme and dimensions of the microelectrochemical chip and image of the manufactured microsensor.</p>
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<p>Raman spectra of pastes used for electrodes before and after fritting: (<b>a</b>) gold paste; (<b>b</b>) Ag/AgCl one; (<b>c</b>) carbon one. Corresponding 3D height AFM images (30 µm × 30 µm) and zoomed images (5 µm × 5 µm) of the gold, Ag/AgCl, and carbon electrodes after fritting (height scale of 1 µm indicated in (<b>c</b>)).</p>
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<p>Overall principle of the homemade electrochemical platform composition.</p>
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<p>CV and CA processes developed with LabVIEW.</p>
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<p>Schematic organization of components of the conditioning card.</p>
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<p>Test of our electronic system using a calibrated resistance of 10 kΩ. (<b>a</b>) Triangular <span class="html-italic">E(t)</span> applied potential and resulting <span class="html-italic">I(t)</span> current using the dummy cell; (<b>b</b>) Linear <span class="html-italic">I = f(E)</span> relationship in agreement with the Ohm’s law and the value of the resistance.</p>
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<p>(<b>a</b>) CV diagrams of homemade and commercial microsensors; (<b>b</b>) 3 consecutive CV curves recorded during the stabilization of the sensor response; measurements were made in the [−0.4 V; +0.6 V] range at a scan rate of 100 mV/s and using a solution of 10 mM of Fe<sup>3+</sup>/Fe<sup>2+</sup> redox couple in TBS.</p>
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<p>(<b>a</b>,<b>b</b>) Typical CV diagrams (using the Fe<sup>3+</sup>/Fe<sup>2+</sup> redox couple) as a function of the scan rate for (<b>a</b>) the homemade sensor and (<b>b</b>) the commercial one; (<b>c</b>) oxidation current; and (<b>d</b>) Δ<span class="html-italic">Ep</span> value versus the square root of the scan rate for both sensors.</p>
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<p>(<b>a</b>) Best functionalization protocol of the working electrode; (<b>b</b>) CV diagrams at each functionalization step (using the Fe<sup>3+</sup>/Fe<sup>2+</sup> redox couple and a scan rate of 100 mV/s); (<b>c</b>) CV diagrams, with the same redox couple, obtained at increasing AFB1 concentrations within a concentration range between 50 fg/mL and 5 ng/mL (scan rate of 100 mV/s); (<b>d</b>) Linear response of the sensor in terms of <span class="html-italic">I<sub>pa</sub></span> values in this range of concentrations [<a href="#B51-chemosensors-10-00137" class="html-bibr">51</a>].</p>
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56 pages, 40584 KiB  
Review
Plasmonic Nanomaterials for Colorimetric Biosensing: A Review
by Adriano Acunzo, Emanuela Scardapane, Maria De Luca, Daniele Marra, Raffaele Velotta and Antonio Minopoli
Chemosensors 2022, 10(4), 136; https://doi.org/10.3390/chemosensors10040136 - 5 Apr 2022
Cited by 18 | Viewed by 5596
Abstract
In the last few decades, plasmonic colorimetric biosensors raised increasing interest in bioanalytics thanks to their cost-effectiveness, responsiveness, and simplicity as compared to conventional laboratory techniques. Potential high-throughput screening and easy-to-use assay procedures make them also suitable for realizing point of care devices. [...] Read more.
In the last few decades, plasmonic colorimetric biosensors raised increasing interest in bioanalytics thanks to their cost-effectiveness, responsiveness, and simplicity as compared to conventional laboratory techniques. Potential high-throughput screening and easy-to-use assay procedures make them also suitable for realizing point of care devices. Nevertheless, several challenges such as fabrication complexity, laborious biofunctionalization, and poor sensitivity compromise their technological transfer from research laboratories to industry and, hence, still hamper their adoption on large-scale. However, newly-developing plasmonic colorimetric biosensors boast impressive sensing performance in terms of sensitivity, dynamic range, limit of detection, reliability, and specificity thereby continuously encouraging further researches. In this review, recently reported plasmonic colorimetric biosensors are discussed with a focus on the following categories: (i) on-platform-based (localized surface plasmon resonance, coupled plasmon resonance and surface lattice resonance); (ii) colloid aggregation-based (label-based and label free); (iii) colloid non-aggregation-based (nanozyme, etching-based and growth-based). Full article
(This article belongs to the Special Issue Progress of Nanomaterials for Colorimetric Sensing)
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<p>(<b>a</b>) Schematic illustration of the LSP excitation. (<b>b</b>) Extinction efficiency as a function of NP diameter. (<b>c</b>) Sketch of the visual colour change of a nanostructured substrate as a consequence of the LSPR redshift. Adapted from Refs. [<a href="#B12-chemosensors-10-00136" class="html-bibr">12</a>,<a href="#B40-chemosensors-10-00136" class="html-bibr">40</a>] Copyright (2021) The Authors. Advanced Materials Interfaces published by Wiley-VCH GmbH and (2018) The Authors, published by IOP Publishing Ltd. These articles are distributed under a Creative Commons Attribution (CC-BY) license.</p>
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<p>(<b>a</b>) Schematic of membrane-integrated device used for the detection of NS1 dengue antigen in human whole blood; calibration curve. Adapted from Ref. [<a href="#B48-chemosensors-10-00136" class="html-bibr">48</a>] Copyright (2019), with permission from Elsevier B.V. (<b>b</b>) Perspective and cross-sectional views of the device architecture (scale bar: 40 nm); LSPR wavelength shifts and drain-source current of the MoS<sub>2</sub> channel (when V<sub>drain-source</sub> = 1.0 V) as functions of the bulk RI; calibration curves for CitH3. Adapted from Ref. [<a href="#B49-chemosensors-10-00136" class="html-bibr">49</a>] Copyright (2019), with permission from Wiley-VCH. (<b>c</b>) SEM image of the Au nanocup array onto PDMS; scheme used for Anti-Human IgG detection; simulated relationship between reflectance minima and RI; experimental reflectance response after Human IgG functionalization and Anti-Human IgG detection. Adapted from Ref. [<a href="#B50-chemosensors-10-00136" class="html-bibr">50</a>] Copyright (2017), Springer Nature. This article is distributed under a Creative Commons Attribution (CC-BY) license.</p>
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<p>(<b>a</b>) Working scheme of the 3D Au stripe arrays for the detection of micro-RNA let-7a in saline buffer; typical LSPR shift of device response, dose-response curve, nanostructure’s SEM images (inset scale bar: 500 nm) after enzyme precipitation when target micro-RNAs are absent or present. Reused from Ref. [<a href="#B54-chemosensors-10-00136" class="html-bibr">54</a>] Copyright (2018), Elsevier B.V. This article is distributed under a Creative Commons Attribution (CC-BY-NC-ND) license. (<b>b</b>) 3D model and 45°-tilted SEM image of an array of epoxy nanopillars with Au nanodisks atop; normalized absorbance spectra measured in different environments; calibration curve for the target DNA sequence from Giardia lamblia; control experiments. Adapted from Ref. [<a href="#B55-chemosensors-10-00136" class="html-bibr">55</a>] Copyright (2020), American Chemical Society. This article is distributed under a Creative Commons Attribution (CC-BY) license. (<b>c</b>) Schematic of the bowtie-like nanoantenna array with metal-insulator-metal structure; electric field intensity enhancements at 1064 nm for arrays with different geometries; simulated calibration curve for superstrate RI in the case of an optimized platform. Adapted from Ref. [<a href="#B57-chemosensors-10-00136" class="html-bibr">57</a>] Copyright (2019), with permission from Springer Nature.</p>
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<p>(<b>a</b>) Schematic representation of the plasmon hybridization model. (<b>b</b>) Sketch of the near-field coupling among two neighbouring nanoparticles in a two-dimensional hexagonal lattice. (<b>c</b>) Schematic illustration of the electric field enhancement in the case of LSPR mode and c-LSPR mode for a homodimer configuration. Adapted from Ref. [<a href="#B12-chemosensors-10-00136" class="html-bibr">12</a>]. Copyright (2021) The Authors. Advanced Materials Interfaces published by Wiley-VCH GmbH. This article is distributed under a Creative Commons Attribution (CC-BY) license.</p>
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<p>(<b>a</b>) SEM images associated extinction spectra (when the superstrate RI is 1.33) and x-polarized field enhancement profiles (at 797 nm) of two Au nanobar arrays with different morphologies. Adapted from Ref. [<a href="#B68-chemosensors-10-00136" class="html-bibr">68</a>] Copyright (2021), with permission from American Physical Society. (<b>b</b>) Schematic of the array of Au crossed-bowtie nanoantennas and Au nanocross walls; bulk RI calibration curves for arrays with different values W of the Au walls width (the inset shows the bulk RI sensing scheme); typical reflectance spectra before (solid line) and after (dotted line) the addition of a 2 nm thick layer with RI of 1.53 over the nanostructure (the inset shows the localized RI sensing scheme). Adapted from Ref. [<a href="#B69-chemosensors-10-00136" class="html-bibr">69</a>] Copyright (2021), Royal Society of Chemistry. This article is distributed under a Creative Commons Attribution (CC-BY) license. (<b>c</b>) Absorption spectra of the Au finger-like hexagonal array before and after immobilization of different probes and targets; associated c-LSPR peak wavelengths and intensities. Tilted SEM image of the substrate. Adapted from Ref. [<a href="#B73-chemosensors-10-00136" class="html-bibr">73</a>] Copyright (2017), with permission from Elsevier B.V.</p>
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<p>(<b>a</b>) Conceptual illustration for the label-free DNA hybridization detection by the hexagonal core–shell-structured Au nanocone array, together with a simulation of the electric field enhancement around a nanocone (once irradiated by white light); calibration curve for target DNA; peak wavelength shifts due to hybridization of noncomplementary DNA (Mis.), 1-base mismatch DNA (1-Mis.), and fully complementary DNA (Comp.). Adapted from Ref. [<a href="#B33-chemosensors-10-00136" class="html-bibr">33</a>] Copyright (2019), with permission from American Chemical Society. (<b>b</b>) Schematic of the hexagonal Au–Ag alloy nanodisk array and its working scheme; LSPR position of the green band peak as a function of the bulk RI; green band peak shifts (black line) and red/green ratio reduction (blue line) induced at different concentrations of streptavidin, with the inset showing smartphone images of bare sample (<b>top</b>), thiol-PEG-biotin modified sample (<b>middle</b>), and 10<sup>–6</sup> M streptavidin incubated sample (<b>bottom</b>). Adapted from Ref. [<a href="#B77-chemosensors-10-00136" class="html-bibr">77</a>] Copyright (2018), with permission from American Chemical Society. (<b>c</b>) SEM image of a Au nanoring array; simulated reflectance spectra for a 500 nm periodic nanoring array at reducing nanoring gap distance (the dashed green lines underline the occurrence of bonding and antibonding c-LSPs modes while reducing the gap); experimental reflectance spectra for a 600 nm periodic nanoring array as a function of the nanoring gap distance. Adapted from Ref. [<a href="#B79-chemosensors-10-00136" class="html-bibr">79</a>] Copyright (2017), with permission from American Chemical Society.</p>
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<p>(<b>a</b>) Schematic representation of far-field coupling among two nanoparticles in a two-dimensional rectangular lattice. Adapted from Ref. [<a href="#B12-chemosensors-10-00136" class="html-bibr">12</a>]. Copyright (2021) The Authors. Advanced Materials Interfaces published by Wiley-VCH GmbH. This article is distributed under a Creative Commons Attribution (CC-BY) license. (<b>b</b>) Simulated transmission spectrum of a periodic linear chain of AuNPs whose lattice constant is comparable to the wavelength of the incident perturbation. Adapted from Ref. [<a href="#B29-chemosensors-10-00136" class="html-bibr">29</a>] Copyright (2018), with permission from American Chemical Society.</p>
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<p>(<b>a</b>) Schematics of SLRs excitation in direct geometry over the Au nanodot lattices, together with their SEM images; single-particle array RI calibration curves for medium-related (red line) and substrate-related (blue line) modes in direct geometry; double-particle array RI calibration curves for medium-related (red lines) and substrate-related (blue lines) modes in ATR geometry (solid lines refers to measurements at the total internal reflection (TIR) angle while dotted lines to measurements before TIR). Adapted from Ref. [<a href="#B86-chemosensors-10-00136" class="html-bibr">86</a>] Copyright (2017), with permission from Elsevier B.V. (<b>b</b>) Schematics of the hexagonal array of hydrogel-coated AuNPs on glass substrate in the case of a (quasi-)symmetric environment; absorbance spectra for arrays with increasing lattice constants in the case of a (quasi-)symmetric environment; experimental peak wavelengths (filled and empty black circles) and <span class="html-italic">Q</span>-factors (filled and empty red circles) as a function of Δ<span class="html-italic">λ</span> = <span class="html-italic">λ</span><sub>diffraction</sub> − <span class="html-italic">λ</span><sub>LSPR</sub> in the case of a (quasi-)symmetric environment (grey area corresponds to the region where SLRs do not occur, i.e., there are only LSPRs). Adapted from Ref. [<a href="#B90-chemosensors-10-00136" class="html-bibr">90</a>] Copyright (2020), with permission from American Chemical Society. (<b>c</b>) SEM images of the Ag-coated AuNPs array before (top) and after (bottom) the H<sub>2</sub>S detection; calibration curve for H<sub>2</sub>S detection with inset showing the LR; device responses to possible interfering agents. Adapted from Ref. [<a href="#B91-chemosensors-10-00136" class="html-bibr">91</a>] Copyright (2020), with permission from American Chemical Society. (<b>d</b>) SEM image of the Al nanodisk honeycomb array sustaining two high-quality SLRs in the visible and NIR ranges at the same time; associated experimental transmission spectrum; simulated electric field magnitude and phase profile of the Γ<sub>2</sub> mode. Adapted from Ref. [<a href="#B95-chemosensors-10-00136" class="html-bibr">95</a>] Copyright (2019), with permission from American Chemical Society.</p>
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<p>(<b>a</b>) Schematics of SLRs excitation in direct geometry over the Au nanodot lattices, together with their SEM images; single-particle array RI calibration curves for medium-related (red line) and substrate-related (blue line) modes in direct geometry; double-particle array RI calibration curves for medium-related (red lines) and substrate-related (blue lines) modes in ATR geometry (solid lines refers to measurements at the total internal reflection (TIR) angle while dotted lines to measurements before TIR). Adapted from Ref. [<a href="#B86-chemosensors-10-00136" class="html-bibr">86</a>] Copyright (2017), with permission from Elsevier B.V. (<b>b</b>) Schematics of the hexagonal array of hydrogel-coated AuNPs on glass substrate in the case of a (quasi-)symmetric environment; absorbance spectra for arrays with increasing lattice constants in the case of a (quasi-)symmetric environment; experimental peak wavelengths (filled and empty black circles) and <span class="html-italic">Q</span>-factors (filled and empty red circles) as a function of Δ<span class="html-italic">λ</span> = <span class="html-italic">λ</span><sub>diffraction</sub> − <span class="html-italic">λ</span><sub>LSPR</sub> in the case of a (quasi-)symmetric environment (grey area corresponds to the region where SLRs do not occur, i.e., there are only LSPRs). Adapted from Ref. [<a href="#B90-chemosensors-10-00136" class="html-bibr">90</a>] Copyright (2020), with permission from American Chemical Society. (<b>c</b>) SEM images of the Ag-coated AuNPs array before (top) and after (bottom) the H<sub>2</sub>S detection; calibration curve for H<sub>2</sub>S detection with inset showing the LR; device responses to possible interfering agents. Adapted from Ref. [<a href="#B91-chemosensors-10-00136" class="html-bibr">91</a>] Copyright (2020), with permission from American Chemical Society. (<b>d</b>) SEM image of the Al nanodisk honeycomb array sustaining two high-quality SLRs in the visible and NIR ranges at the same time; associated experimental transmission spectrum; simulated electric field magnitude and phase profile of the Γ<sub>2</sub> mode. Adapted from Ref. [<a href="#B95-chemosensors-10-00136" class="html-bibr">95</a>] Copyright (2019), with permission from American Chemical Society.</p>
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<p>Detection scheme of a colorimetric immunosensor based on a colloidal solution of antibody-functionalized nanoparticles. (<b>a</b>) No optical change is measured if the analytes are not recognized by functionalized nanoparticles. (<b>b</b>) Small analytes act as linkers due to multiple binding sites allowing the functionalized nanoparticles to aggregate. (<b>c</b>) Large analytes are surrounded by functionalized nanoparticles promoting their plasmon coupling.</p>
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<p>(<b>a</b>) Absorption spectra at different human IgG concentrations; dynamic light scattering (DLS) measurements at different human IgG concentrations; visual colour change from pink to purple induced by the aggregation of AuNPs; representative SEM images at different human IgG concentrations; calibration curve for human IgG. Adapted from Ref. [<a href="#B101-chemosensors-10-00136" class="html-bibr">101</a>]. Copyright (2018), American Chemical Society. This article is distributed under a Creative Commons Attribution (CC-BY-NC-ND) license. (<b>b</b>) Absorption spectra at different E2 concentrations; DLS measurements at different E2 concentrations; visual colour change from pink to purple induced by the aggregation of AuNPs; representative TEM images at different E2 concentrations; calibration curve for E2. Adapted from Ref. [<a href="#B105-chemosensors-10-00136" class="html-bibr">105</a>]. Copyright (2020), with permission from Elsevier B.V. (<b>c</b>) Schematic illustration of the rationale behind the SARS-CoV-2-directed colorimetric immunosensor; optical density (OD) of the colloidal suspension at 560 nm as a function of the PCR cycle threshold measured in 50 positive and 50 negative specimens; calibration curve for SARS-CoV-2 viruses. Adapted from Ref. [<a href="#B109-chemosensors-10-00136" class="html-bibr">109</a>]. Copyright (2020), with permission from American Chemical Society. (<b>d</b>) Schematic illustration of the nanoparticle-virus aggregation mechanism as a function of the virus concentrations; simulated extinction spectra as a function of the virus concentration; OD readings at different excitation wavelengths. Adapted from Ref. [<a href="#B110-chemosensors-10-00136" class="html-bibr">110</a>]. Copyright (2021), Author(s). This article is distributed under a Creative Commons Attribution (CC-BY) license.</p>
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<p>(<b>a</b>) Absorption spectra at different human IgG concentrations; dynamic light scattering (DLS) measurements at different human IgG concentrations; visual colour change from pink to purple induced by the aggregation of AuNPs; representative SEM images at different human IgG concentrations; calibration curve for human IgG. Adapted from Ref. [<a href="#B101-chemosensors-10-00136" class="html-bibr">101</a>]. Copyright (2018), American Chemical Society. This article is distributed under a Creative Commons Attribution (CC-BY-NC-ND) license. (<b>b</b>) Absorption spectra at different E2 concentrations; DLS measurements at different E2 concentrations; visual colour change from pink to purple induced by the aggregation of AuNPs; representative TEM images at different E2 concentrations; calibration curve for E2. Adapted from Ref. [<a href="#B105-chemosensors-10-00136" class="html-bibr">105</a>]. Copyright (2020), with permission from Elsevier B.V. (<b>c</b>) Schematic illustration of the rationale behind the SARS-CoV-2-directed colorimetric immunosensor; optical density (OD) of the colloidal suspension at 560 nm as a function of the PCR cycle threshold measured in 50 positive and 50 negative specimens; calibration curve for SARS-CoV-2 viruses. Adapted from Ref. [<a href="#B109-chemosensors-10-00136" class="html-bibr">109</a>]. Copyright (2020), with permission from American Chemical Society. (<b>d</b>) Schematic illustration of the nanoparticle-virus aggregation mechanism as a function of the virus concentrations; simulated extinction spectra as a function of the virus concentration; OD readings at different excitation wavelengths. Adapted from Ref. [<a href="#B110-chemosensors-10-00136" class="html-bibr">110</a>]. Copyright (2021), Author(s). This article is distributed under a Creative Commons Attribution (CC-BY) license.</p>
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<p>(<b>a</b>) Scheme of IAV detection by anti-hemagglutinin f-AuNPs; TEM images of AuNPs (in black) around IAV; absorption spectra of AuNPs colloidal solutions with IAV concentrations in the range of 0–400 HAU (see inset for solution colour changes); calibration curve with inset showing the LR. Adapted from Ref. [<a href="#B111-chemosensors-10-00136" class="html-bibr">111</a>] Copyright (2015), with permission from The Royal Society of Chemistry. (<b>b</b>) Detection scheme for ZIKV-E and salivary proteins of vector mosquitos <span class="html-italic">Aedes aegypti</span> and <span class="html-italic">albopictus</span> by aptamer-conjugated AuNPs; photograph showing visual colour changes of AuNPs conjugated with different concentrations of aptamers when ZIKV-E concentrations lied in the range of 0.4–100 nM; photograph showing the degree of precipitation induced by different amounts of ZIKV at three time points. Adapted from Ref. [<a href="#B112-chemosensors-10-00136" class="html-bibr">112</a>] Copyright (2019) The Royal Society of Chemistry. This article is distributed under a Creative Commons Attribution (CC-BY-NC) license.</p>
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<p>Example of colloidal behaviours exhibited by DNA-modified nanostructures in a medium of high ionic strength. While single-stranded, mismatched and overhang DNA increase electrostatic and steric repulsion and, hence, sustain a colloidal dispersion state, fully matched DNA entail the aggregation of ligand-modified nanostructures. Reproduced from Ref. [<a href="#B118-chemosensors-10-00136" class="html-bibr">118</a>] Copyright (2016), with permission from Wiley-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.</p>
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<p>(<b>a</b>) Schematic representation of the detection mechanisms for PPase activity and NaF inhibition efficiency; kinetic plots of A<sub>650</sub>/A<sub>522</sub> values and initial rate of enzymatic reaction (<span class="html-italic">v</span><sub>0</sub>) as a function of PPase activity (the inset shows the visual colour change of the suspension); absorption spectra and kinetic plots of A<sub>650</sub>/A<sub>522</sub> as a function of the NaF concentration (the inset shows the visual colour change of the suspension). Adapted from Ref. [<a href="#B119-chemosensors-10-00136" class="html-bibr">119</a>] Copyright (2013), with permission from American Chemical Society. (<b>b</b>) Scheme of the end-to-end self-assembly mechanism (the insets show SEM micrographs of synthesised AuNRs and their branch patterning after analyte addition); absorption spectra and calibration curve as a function of cholinesterase (ChE) concentration; absorption spectra and calibration curve as a function of parathion concentration. Adapted from Ref. [<a href="#B120-chemosensors-10-00136" class="html-bibr">120</a>] Copyright (2015), with permission from American Chemical Society.</p>
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<p>(<b>a</b>) Schematic illustration of the detection mechanism for telomerase activity by using TS-modified AuNPs; visual colour change of the solution from blue to purple and corresponding absorption spectra; Calibration curve (A<sub>520</sub>/A<sub>650</sub> vs. number of HeLa cells) for the telomerase activity (the inset shows the LR). Reproduced from Ref. [<a href="#B123-chemosensors-10-00136" class="html-bibr">123</a>] Copyright (2012), with permission from Wiley-VCH Verlag GmbH &amp; Co. KGaA, Weinheim. (<b>b</b>) Schematic illustration of the detection mechanism for telomerase activity by using TC-modified AuNPs; ratiometric response A<sub>520</sub>/A<sub>680</sub> as a function of the number of HeLa cells from which telomerase was extracted (the insets show the visual colour change from blue to purple and the LR range); inhibition of telomerase activity by using curcumin (the inset shows the visual colour change of the solution from red to blue). Adapted from Ref. [<a href="#B124-chemosensors-10-00136" class="html-bibr">124</a>] Copyright (2014), with permission from The Royal Society of Chemistry. (<b>c</b>) Schematic illustration of the detection mechanism for telomerase activity by using TP-modified AuNPs; ratiometric response A<sub>520</sub>/A<sub>680</sub> as a function of the number of HL-60 cells from which telomerase was extracted (the inset shows the visual colour difference between a control sample and a positive sample); Calibration curve (A<sub>520</sub>/A<sub>680</sub> vs. number of HL-60 cells). Adapted from Ref. [<a href="#B125-chemosensors-10-00136" class="html-bibr">125</a>] Copyright (2015), with permission from Elsevier B.V.</p>
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<p>Schematic representation of destabilization-induced aggregation method for measuring enzymatic activity. The aggregation of peptide-capped nanoparticles is induced by cleaving the capping peptides thereby reducing the electrosteric stabilization.</p>
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<p>(<b>a</b>) Detection mechanism of DPP-IV by using GPDC- or VPED-DC-capped AuNPs; absorption spectra and calibration curve as a function of DPP-IV activity (referred to GPDC-capped AuNPs) (the inset shows the visual change from red to purple). Adapted from Ref. [<a href="#B126-chemosensors-10-00136" class="html-bibr">126</a>] Copyright (2017), with permission from Elsevier B.V. (<b>b</b>) Scheme of the working principle for the detection of cathepsin B; absorption spectra at different cathepsin B concentrations acquired after 2 h reaction time (the inset depicts the visual colour change of the solution); evaluation of inhibition efficiencies of leupeptin, antipain, chymostatin. Adapted from Ref. [<a href="#B127-chemosensors-10-00136" class="html-bibr">127</a>] Copyright (2014), with permission from American Chemical Society. (<b>c</b>) Schematic illustration of naked-eye detection mechanism of SARS-CoV-2 RNA mediated by ASO-modified AuNPs; normalized absorption spectra before and after RNA addition (the insets show the visual colour change of the solution: purple with SARS-CoV-2 viral RNA, blue after the addition of RNaseH, colourless due to the precipitation of nanoparticle aggregates); A<sub>660</sub> values measured at different conditions (control, RNA from non-infected Vero cells, Vero cells infected with MERS-CoV, and Vero cells infected with SARS-CoV-2 virus. Adapted from Ref. [<a href="#B128-chemosensors-10-00136" class="html-bibr">128</a>] Copyright (2020), with permission from American Chemical Society. (<b>d</b>) Schematic illustration of colorimetric detection strategy of AFB1 by using gelatine-modified AuNPs; absorption spectra as a function of AFB1 concentration (the inset shows the visual colour change); calibration curve (A<sub>525</sub> vs. AFB1 concentration). Adapted from Ref. [<a href="#B129-chemosensors-10-00136" class="html-bibr">129</a>] Copyright (2021), with permission from IOP Publishing Ltd.</p>
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<p>Schematic representation of analyte detection through a label-free colorimetric aptasensors. The functionalization of nanoparticles with aptamers is realized in a medium of high ionic strength. (<b>a</b>) Aptamer capping prevents nanoparticle salt-induced aggregation if the analytes are not recognized by functionalized nanoparticles. (<b>b</b>) The presence of analytes of interest causes the detachment of aptamers from the nanoparticle surface leading to the salt-induced aggregation of bare nanoparticles.</p>
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<p>(<b>a</b>) Detection scheme of E2 by using AuNPs functionalized with split aptamers; absorption spectra as a function of the E2 concentration; calibration curve for E2; specificity assay. Reproduced from Ref. [<a href="#B135-chemosensors-10-00136" class="html-bibr">135</a>] Copyright (2014), Scientific Reports. This article is distributed under a Creative Commons Attribution (CC-BY-NC-SA) license. (<b>b</b>) Schematic illustration of the aptasensor working principle for detecting E2; Ratiometric response of the aptasensor for E2 in spiked rat urine by using 35 mer and 75-mer aptamers; specificity assay. Adapted from Ref. [<a href="#B138-chemosensors-10-00136" class="html-bibr">138</a>] Copyright (2015), with permission from American Chemical Society. (<b>c</b>) Detection mechanism for revealing E2 by means of aptamer-capped AuNPs; absorption spectra and calibration curve for E2 (the inset shows the colour change from pink to purple); specificity assay (the inset shows the visual response of the aptasensor). Adapted from Ref. [<a href="#B139-chemosensors-10-00136" class="html-bibr">139</a>] Copyright (2020), with permission from Elsevier Ltd. (<b>d</b>) Detection scheme of the aptasensor; calibration curves for ALP in different concentration regimes (the insets show the visual response of the biosensor). Adapted from Ref. [<a href="#B140-chemosensors-10-00136" class="html-bibr">140</a>] Copyright (2012), with permission from Elsevier B.V.</p>
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<p>(<b>a</b>) Schematic representation of the fabrication of FeS<sub>2</sub>NPs and detection mechanisms for and GSH; absorption spectra as a function of H<sub>2</sub>O<sub>2</sub> concentration; calibration curve for H<sub>2</sub>O<sub>2</sub> (the inset shows the visual colour change from colourless to deep-blue); absorption spectra as a function of GSH concentration; calibration curve for GSH (the inset shows the visual colour change from deep-blue to colourless). Adapted from Ref. [<a href="#B34-chemosensors-10-00136" class="html-bibr">34</a>] Copyright (2019), with permission from Elsevier B.V. (<b>b</b>) Working principle of aptamer-modified MoS<sub>2</sub>-NSs for carcinoembryonic antigen (CEA) protein detection; absorption spectra at different CEA concentrations; calibration curve for CEA; visual colour change from greenish to colourless as a function of CEA concentrations. Adapted from Ref. [<a href="#B160-chemosensors-10-00136" class="html-bibr">160</a>] Copyright (2020), with permission from The Royal Society of Chemistry. (<b>c</b>) Working principle of NL-MnCaO<sub>2</sub> for detecting glucose; absorption spectra at different glucose concentrations; calibration curve for glucose. Adapted from Ref. [<a href="#B161-chemosensors-10-00136" class="html-bibr">161</a>] Copyright (2020), with permission from Elsevier B.V.</p>
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<p>(<b>a</b>) Schematic illustration of the detection mechanism for hydroquinone (HQ) and H<sub>2</sub>O<sub>2</sub> by using FeCo@C; absorption spectra at different concentrations of H<sub>2</sub>O<sub>2</sub> concentration; calibration curve for H<sub>2</sub>O<sub>2</sub>; absorption spectra at different HQ concentrations; calibration curve for HQ. Adapted from Ref. [<a href="#B162-chemosensors-10-00136" class="html-bibr">162</a>] Copyright (2019), with permission from Elsevier B.V. (<b>b</b>) Detection scheme for cholesterol by using cholesterol oxidase and Mo-CQDs; absorption spectra and calibration curve for H<sub>2</sub>O<sub>2</sub> and cholesterol (the insets shows the visual colour change from colourless to greenish). Reproduced from Ref. [<a href="#B168-chemosensors-10-00136" class="html-bibr">168</a>] Copyright (2019), with permission from The Royal Society of Chemistry. (<b>c</b>) Schematic representation of the tetra-enzyme mimetic activities of Co<sub>3</sub>O<sub>4</sub> nanoflowers and working principle for detecting ACP and H<sub>2</sub>O<sub>2</sub>; calibration curve for H<sub>2</sub>O<sub>2</sub>; calibration curve for ACP. Adapted from Ref. [<a href="#B169-chemosensors-10-00136" class="html-bibr">169</a>] Copyright (2020), with permission from Elsevier B.V.</p>
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<p>(<b>a</b>) Schematic illustration of the etching mechanism for the detection of telomerase activity; TEM images of the AuNBP etching process after incubation with telomerase extracted from different number of HeLa cells (0–2000 cells); visual colour change and absorption spectra of the solution after incubation with telomerase extracted from HeLa cells (0–2000 cells); calibration curve and LR for telomerase activity. Adapted from Ref. [<a href="#B35-chemosensors-10-00136" class="html-bibr">35</a>] Copyright (2019), with permission from Elsevier B.V. (<b>b</b>) Rationale behind the signal amplification achieved with aptamer-modified magnetic beads and AuNBP@MnO<sub>2</sub>NSs as etching substrate for detecting exosomes; absorption spectra at different exosome concentration obtained with high-AR AuNBPs (the insets show the visual colour change of the solution and two representative TEM images of AuNBP@MnO<sub>2</sub>NSs and etched AuNBPs); calibration curve and LR for exosome by using high-AR AuNBPs. Adapted from Ref. [<a href="#B176-chemosensors-10-00136" class="html-bibr">176</a>] Copyright (2020), with permission from American Chemical Society.</p>
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<p>(<b>a</b>) Schematic illustration of label-free detection of PARP-1 activity with AuNRs; visual colour change and corresponding absorption spectra measured at different PARP-1 activities (0–2 U); calibration curve and LR for PARP-1 activity. Adapted from Ref. [<a href="#B181-chemosensors-10-00136" class="html-bibr">181</a>] Copyright (2020), with permission from Elsevier B.V. (<b>b</b>) Rationale behind the double signal amplification achieved with Ab–GOx–MBs and AgNPRs as etching substrate for detecting PSA; visual colour change and corresponding absorption spectra measured at different PSA concentrations (0–10<sup>6</sup> fg/mL); calibration curve for PSA. Adapted from Ref. [<a href="#B182-chemosensors-10-00136" class="html-bibr">182</a>] Copyright (2015), with permission from Elsevier B.V.</p>
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<p>(<b>a</b>) Detection scheme for pAP by the seed-mediated growth of AgNPs; Spectra at different concentrations of pAP in human urine (<b>left</b> graph) and paracetamol (<b>right</b> graph), with insets showing the standard addition dose-response curves for addition of pAP; example of visual colour changes while increasing pAP concentration. Adapted from Ref. [<a href="#B187-chemosensors-10-00136" class="html-bibr">187</a>], Copyright (2021), with permission from Elsevier B.V. (<b>b</b>) Detection scheme for EA by the seed-mediated growth of Au@AgNRs, together with TEM images before (<b>left</b>) and after (<b>right</b>) the Ag growth; (<b>b</b>) normalized extinction spectra of AuNRs (black line) and Au@AgNRs at increasing EA concentrations; calibration curve for EA with inset showing the LR when AgNO<sub>3</sub> concentration was 100 mM, pH 11.4 and the reaction time 20 min. Adapted from Ref. [<a href="#B188-chemosensors-10-00136" class="html-bibr">188</a>], Copyright (2017) with permission from Elsevier B.V.</p>
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<p>(<b>a</b>) Working principle of the enzyme-mediated growth-based immunosensor for detecting H<sub>5</sub>N<sub>1</sub> virus; visual colour change, TEM images and absorption spectra as a function of the analyte concentration; calibration curve for H<sub>5</sub>N<sub>1</sub> virus (the inset shows the LR). Adapted from Ref. [<a href="#B191-chemosensors-10-00136" class="html-bibr">191</a>] Copyright (2016), with permission from American Chemical Society. (<b>b</b>) Schematic representation of the growth-based mechanism for the detection of small molecules; calibration curve and corresponding visual colour change for E2, cocaine and ochratoxin (OTA). Representative TEM image of AuNPs before (<b>top</b>) and after (<b>bottom</b>) the growth. Adapted from Ref. [<a href="#B193-chemosensors-10-00136" class="html-bibr">193</a>] Copyright (2015), with permission from American Chemical Society.</p>
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<p>Classification of on-platform-based and colloid-based (aggregation-based and non-aggregation-based) plasmonic colorimetric biosensors. The illustration for on-platform biosensors was adapted from Ref. [<a href="#B12-chemosensors-10-00136" class="html-bibr">12</a>]. Copyright (2021) The Authors. Advanced Materials Interfaces published by Wiley-VCH GmbH. This article is distributed under a Creative Commons Attribution (CC-BY) license. The illustration for nanozyme biosensors was adapted from [<a href="#B34-chemosensors-10-00136" class="html-bibr">34</a>] Copyright (2019), with permission from Elsevier B.V. The illustration for etching-based biosensors was adapted from Ref. [<a href="#B35-chemosensors-10-00136" class="html-bibr">35</a>] Copyright (2019), with permission from Elsevier B.V.</p>
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17 pages, 4307 KiB  
Article
In2O3 Based Hybrid Materials: Interplay between Microstructure, Photoelectrical and Light Activated NO2 Sensor Properties
by Abulkosim Nasriddinov, Sergey Tokarev, Olga Fedorova, Ivan Bozhev and Marina Rumyantseva
Chemosensors 2022, 10(4), 135; https://doi.org/10.3390/chemosensors10040135 - 4 Apr 2022
Cited by 11 | Viewed by 3211
Abstract
In this work, organic–inorganic hybrids based on nanocrystalline indium oxide and ruthenium (II) heteroleptic complexes were used as sensitive materials for room temperature light-activated NO2 detection. In2O3 was obtained by chemical precipitation method and then annealed at three different [...] Read more.
In this work, organic–inorganic hybrids based on nanocrystalline indium oxide and ruthenium (II) heteroleptic complexes were used as sensitive materials for room temperature light-activated NO2 detection. In2O3 was obtained by chemical precipitation method and then annealed at three different temperatures (T = 300, 500, 700 °C) in order to investigate the influence of the microstructure of indium oxide on sensor characteristics of hybrid materials and on kinetics of the rise and fall of photoconductivity. The results of the X-ray phase analysis demonstrated that the obtained materials are single-phase with a cubic bixbyite structure. The Ru (II) heteroleptic complex, which was used as a photosensitizer, made it possible to shift the optical sensitivity range of the hybrids to the low energy region of the spectrum and to use a low-power LED (λmax = 470 nm) source for the photoactivation process. The sensor properties were investigated toward NO2 at sub-ppm range at room temperature. It was found that for pure oxides, the sensor signal correlates with a specific surface area, while for hybrid materials, both the sensor signal and photoresponse increase with increasing the matrix crystallinity. In this case, the main role is played by traps of nonequilibrium charge carriers, which are structural defects in the matrix. Full article
(This article belongs to the Special Issue Functionalized Materials for Chemosensor Applications)
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<p>Microelectronic hotplate (<b>a</b>) before and (<b>b</b>) after deposition of a thick semiconductor film on the substrate and (<b>c</b>) after sensitization with a Ru(II) heteroleptic complex; SEM images of the sensitive layer deposited on the substrate, (<b>d</b>) side view and (<b>e</b>) top view.</p>
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<p>X-ray diffraction patterns (<b>a</b>) and Raman spectra (<b>b</b>) of nanocrystalline In<sub>2</sub>O<sub>3</sub> samples.</p>
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<p>TPR-H<sub>2</sub> curves (<b>a</b>) and FTIR spectra (<b>b</b>) of nanocrystalline In<sub>2</sub>O<sub>3</sub> samples with different annealing temperatures.</p>
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<p>Temperature dependence of conductivity of the In<sub>2</sub>O<sub>3</sub>(300), In<sub>2</sub>O<sub>3</sub>(500) and In<sub>2</sub>O<sub>3</sub>(700) samples in Mott coordinates in the temperature range of 140–25 °C.</p>
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<p>Optical absorption spectra (<b>a</b>,<b>b</b>) and normalized spectral dependences of the photoconductivity (<b>c</b>,<b>d</b>) of pure semiconductors and hybrid materials.</p>
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<p>Change in the conductivity of pure In<sub>2</sub>O<sub>3</sub> with different grain sizes (<b>a</b>) and hybrid materials (<b>b</b>) under dark and irradiation conditions.</p>
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<p>Photoresponse of synthesized samples.</p>
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<p>Change in resistance of the pure oxides and hybrid materials under periodic illumination with blue LED in the presence of various NO<sub>2</sub> concentrations for (<b>a</b>) In<sub>2</sub>O<sub>3</sub>(300) based, (<b>b</b>) In<sub>2</sub>O<sub>3</sub>(500) based, (<b>c</b>) In<sub>2</sub>O<sub>3</sub>(700) based samples.</p>
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<p>Dependence of the sensor signal (<b>a</b>) and photoresponse (<b>b</b>) of In<sub>2</sub>O<sub>3</sub>(300), In<sub>2</sub>O<sub>3</sub>(500), In<sub>2</sub>O<sub>3</sub>(700) samples and hybrid materials based on them on the concentration of NO<sub>2</sub>.</p>
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<p>Dependence of the sensor signal of In<sub>2</sub>O<sub>3</sub>(300), In<sub>2</sub>O<sub>3</sub>(700) samples and hybrid materials based on them on the NO<sub>2</sub> concentration at different air humidity (relative humidity at 25 °C RH = 25, 45, 65%).</p>
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11 pages, 4299 KiB  
Article
Microbiological Risk Assessment of Ready-to-Eat Leafy Green Salads via a Novel Electrochemical Sensor
by Simone Grasso, Maria Vittoria Di Loreto, Alyexandra Arienzo, Valentina Gallo, Anna Sabatini, Alessandro Zompanti, Giorgio Pennazza, Laura De Gara, Giovanni Antonini and Marco Santonico
Chemosensors 2022, 10(4), 134; https://doi.org/10.3390/chemosensors10040134 - 1 Apr 2022
Cited by 5 | Viewed by 3660
Abstract
Nowadays, the growing interest in a healthy lifestyle, to compensate for modern stressful habits, has led to an increased demand for wholesome products with quick preparation times. Fresh and ready-to-eat leafy green vegetables are generally perceived as salutary and safe, although they have [...] Read more.
Nowadays, the growing interest in a healthy lifestyle, to compensate for modern stressful habits, has led to an increased demand for wholesome products with quick preparation times. Fresh and ready-to-eat leafy green vegetables are generally perceived as salutary and safe, although they have been recognized as a source of food poisoning outbreaks worldwide. The reason is that these products retain much of their indigenous microflora after minimal industrial processing, and are expected to be consumed without any additional treatment by consumers. Microbiological safety requires a systematic approach that encompasses all aspects of production, processing and distribution. Nevertheless, the most common laboratory techniques used for the detection of pathogens are expensive, time consuming, need laboratory professionals and are not able to provide prompt results, required to undertake effective corrective actions. In this context, the solution proposed in this work is a novel electrochemical sensing system, able to provide real-time information on microbiological risk, which is also potentially embeddable in an industrial production line. The results showed the sensor ability to detect leafy green salad bacterial contaminations with adequate sensibility, even at a low concentration. Full article
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<p>Step-by-step procedure for the preparation and measurement of artificially contaminated romaine lettuce samples.</p>
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<p>Voltammograms registered for the eight microorganisms at the concentration of 3 Log CFU/mL.</p>
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<p>voltammograms registered for each of the eight microorganisms at the concentration level of 10<sup>3</sup> CFU.</p>
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<p>Analyzed vs. predicted concentration values of bacteria admixtures.</p>
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<p>Scores Plot of the first two Principal Components for bacteria strain at 10<sup>−1</sup> dilution in saline solution. Gram-positive and gram-negative species can be identified by cyan and violet, respectively.</p>
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<p>Scores Plot of the first two Principal Components for contaminated and uncontaminated samples. (<b>a</b>) Overall distinction between control and contaminated salads at the highest concentration tested; (<b>b</b>) distinction between control and contaminated salads at 10<sup>−3</sup> microbial dilution; (<b>c</b>) distinction between control and contaminated salads at 10<sup>−5</sup> microbial dilution; (<b>d</b>) distinction between control and contaminated salads at 10<sup>−7</sup> microbial dilution.</p>
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14 pages, 4933 KiB  
Article
Excellent Cooperation between Carboxyl-Substituted Porphyrins, k-Carrageenan and AuNPs for Extended Application in CO2 Capture and Manganese Ion Detection
by Camelia Epuran, Ion Fratilescu, Ana-Maria Macsim, Anca Lascu, Catalin Ianasi, Mihaela Birdeanu and Eugenia Fagadar-Cosma
Chemosensors 2022, 10(4), 133; https://doi.org/10.3390/chemosensors10040133 - 1 Apr 2022
Cited by 7 | Viewed by 3346
Abstract
Significant tasks of the presented research are the development of multifunctional materials capable both to detect/capture carbon dioxide and to monitor toxic metal ions from waters, thus contributing to maintaining a sustainable and clean environment. The purpose of this work was to synthesize, [...] Read more.
Significant tasks of the presented research are the development of multifunctional materials capable both to detect/capture carbon dioxide and to monitor toxic metal ions from waters, thus contributing to maintaining a sustainable and clean environment. The purpose of this work was to synthesize, characterize (NMR, FT-IR, UV-Vis, Fluorescence, AFM) and exploit the optical and emission properties of a carboxyl-substituted A3B porphyrin, 5-(4-carboxy-phenyl)-10,15,20-tris-(4-methyl-phenyl)–porphyrin, and based on it, to develop novel composite material able to adsorb carbon dioxide. This porphyrin-k-carrageenan composite material can capture CO2 in ambient conditions with a performance of 6.97 mmol/1 g adsorbent. Another aim of our research was to extend this porphyrin- k-carrageenan material’s functionality toward Mn2+ detection from polluted waters and from medical samples, relying on its synergistic partnership with gold nanoparticles (AuNPs). The plasmonic porphyrin-k-carrageenan-AuNPs material detected Mn2+ in the range of concentration of 4.56 × 10−5 M to 9.39 × 10−5 M (5–11 mg/L), which can be useful for monitoring health of humans exposed to polluted water sources or those who ingested high dietary manganese. Full article
(This article belongs to the Special Issue Organic-Inorganic Hybrid Chemo- and Bio-Sensors)
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<p>Structures of 5-(4-carboxyphenyl)-10,15,20-tris-(4-methyl-phenyl)-porphyrin (5-COOH-3MPP) (<b>a</b>) and of k-carrageenan (<b>b</b>).</p>
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<p>Hydrolysis reaction of porphyrin ester (5-COOCH3-3MPP) to carboxyl substituted derivative (5-COOH-3MPP).</p>
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<p>Overlapped UV-Vis spectra for the (5-COOH-3MPP)-k-carrageenan composite gel diluted with only DMF (1) and with DMF: water = 2:3 (<span class="html-italic">v/v</span>) mixture (2).</p>
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<p>UV-Vis absorption spectra during CO<sub>2</sub> gas capture in the sol containing (5-COOH-3MPP)-k-carrageenan composite, in DMF:water = 2:3 (<span class="html-italic">v/v</span>) mixture.</p>
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<p>Linear dependence between the intensity of absorption of (5-COOH-3MPP)-k-carrageenan composite read at 420 nm and the concentration of CO<sub>2</sub> in the sol, realized during 60 min of CO<sub>2</sub> exposure, flow rate of 10 mL/min.</p>
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<p>Overlapped emission spectra showing the quenching of the fluorescence due to interaction between (5-COOH-3MPP)-k-carrageenan and CO<sub>2</sub> gas, λex = 432 nm, excitation slit = 10 nm, emission slit = 7.5 nm and scan speed = 1200 nm/min.</p>
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<p>Linear dependence between the intensity of emission measured at 660 nm for the (5-COOH-3MPP)-k-carrageenan during 60 min of CO<sub>2</sub> gas exposure (flow rate of 10 mL/min).</p>
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<p>The 2D and 3D AFM images of (5-COOCH3-3MPP) deposited from THF (<b>a</b>); (5-COOH-3MPP) deposited from THF (<b>b</b>); (5-COOH-3MPP)-k-carrageenan composite material deposited from DMF-water mixture (<b>c</b>); (5-COOH-3MPP)-k-carrageenan composite material after capturing CO<sub>2</sub> gas, in liquid DMF-water mixture (<b>d</b>).</p>
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<p>Overlapped UV-Vis spectra: gold colloid (1); (5-COOH-3MPP)-k-carrageenan composite material (2); acidified porphyrin-k-carrageenan composite material showing the diprotonated form of porphyrin (3); 5-COOH-3MPP porphyrin-k-carrageenan-AuNPs material (4).</p>
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<p>Overlapped UV-Vis spectra for the detection of Mn<sup>2+</sup> using (5-COOH-3MPP)-k-carrageenan-AuNPs hybrid material, in DMF/water.</p>
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<p>Linear dependence between the intensity of absorption of (5-COOH-3MPP)-k-carrageenan-AuNPs hybrid material measured at 659 nm and the Mn<sup>2+</sup> ion concentration.</p>
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<p>(5-COOH-3MPP)-k-carrageenan-AuNPs hybrid material deposited from DMF-water mixture (<b>a</b>); (5-COOH-3MPP)-k-carrageenan-AuNPs hybrid material after Mn<sup>2+</sup> detection, deposited from DMF-water mixture (<b>b</b>).</p>
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<p>The graphical representation of the average percentage errors produced by several interfering ions in the detection of Mn<sup>2+</sup>.</p>
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15 pages, 6257 KiB  
Article
Au-Decorated 1D SnO2 Nanowire/2D WS2 Nanosheet Composite for CO Gas Sensing at Room Temperature in Self-Heating Mode
by Jae-Hun Kim, Isao Sakaguchi, Shunich Hishita, Taku T. Suzuki and Noriko Saito
Chemosensors 2022, 10(4), 132; https://doi.org/10.3390/chemosensors10040132 - 1 Apr 2022
Cited by 12 | Viewed by 3176
Abstract
We have designed a new ternary structure to enhance the sensing properties of WS2 nanosheet (NS)-based gas sensors at room temperature (RT) in self-heating mode. SnO2 nanowires (NWs, 10–30 wt%) were added to WS2 NSs and then Au nanoparticles (NPs) [...] Read more.
We have designed a new ternary structure to enhance the sensing properties of WS2 nanosheet (NS)-based gas sensors at room temperature (RT) in self-heating mode. SnO2 nanowires (NWs, 10–30 wt%) were added to WS2 NSs and then Au nanoparticles (NPs) were deposited on the surface of the resulting composites by UV irradiation. The Au-decorated 10 wt% SnO2–WS2 composition showed the highest gas sensing properties. The presence of SnO2 NWs on the WS2 NSs effectively enhanced the diffusion and adsorption of gas species into deeper parts of the gas sensor. Furthermore, the chemical sensitization of Au (increase in oxygen ionosorption; spillover effect and catalytic effect towards CO) contributed to an enhanced response to CO gas. Gas sensing tests performed in the self-heating mode demonstrated the possibility of realizing a low-voltage, low-power-consumption CO gas sensor based on the Au-decorated 10 wt% SnO2–WS2. The sensor response under 60% relative humidity (RH) conditions was 84% of that under dry conditions, which shows that CO sensing is possible in wet environments at room temperature operation. Full article
(This article belongs to the Section Nanostructures for Chemical Sensing)
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<p>SEM images of (<b>a</b>) pristine WS<sub>2</sub> and (<b>b</b>) 10 wt% SnO<sub>2</sub>–WS<sub>2</sub> composite.</p>
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<p>TEM analyses of (<b>a</b>–<b>c</b>) Au-decorated WS<sub>2</sub> NSs and (<b>d</b>–<b>f</b>) Au-decorated SnO<sub>2</sub>–WS<sub>2</sub> composites.</p>
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<p>Comparison between the responses and base resistance of different gas sensors to 50 ppm CO at 20 °C under 1 V applied voltage.</p>
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<p>(<b>a</b>–<b>d</b>) Normalized dynamic resistance plots of different gas sensors to 50 ppm CO at room temperature (20 °C) under 1 V applied voltage. Comparison between the (<b>e</b>) sensor response and (<b>f</b>) base resistance of WS<sub>2</sub> NS, 10 wt% SnO<sub>2</sub>–WS<sub>2</sub>, 30 wt% SnO<sub>2</sub>–WS<sub>2</sub>, and SnO<sub>2</sub> NS gas sensors with Au NPs decoration in air and N<sub>2</sub> atmosphere.</p>
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<p>Selectivity pattern of Au-decorated 10 wt% SnO<sub>2</sub>–WS<sub>2</sub> composite gas sensor without and with Au NPs measured under 1 V applied voltage at 20 °C.</p>
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<p>Hysteresis study for Au-decorated 10 wt% SnO<sub>2</sub>–WS<sub>2</sub> composite gas sensor (<b>a</b>) dynamic resistance plots under 1 V applied voltages during the increasing and decreasing of the temperature. (<b>b</b>) Comparison between the response of sensors at the same temperatures during increasing and decreasing of the temperature.</p>
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<p>(<b>a</b>) Sensor response versus applied voltage for Au-decorated 10 wt% SnO<sub>2</sub>–WS<sub>2</sub> gas sensor at 20 °C to 50 ppm CO gas. (<b>b</b>) Corresponding base resistance and power consumption versus applied voltage. (<b>c</b>) Dynamic resistance curves of 10 wt% SnO<sub>2</sub>–WS<sub>2</sub> gas sensor to 50 ppm of different gases at 20 °C and under fixed 6.8 V applied voltage. (<b>d</b>) Corresponding selectivity pattern.</p>
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<p>(<b>a</b>) Dynamic resistance curves of Au-decorated 10 wt% SnO<sub>2</sub>–WS<sub>2</sub> gas sensor to 50 ppm CO gas under 6.8 V external voltage at different RH. Corresponding (<b>b</b>) sensor response, (<b>c</b>) response and recovery times as a function of RH.</p>
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<p>(<b>a</b>) UPS spectra of WS<sub>2</sub> NSs. (<b>b</b>) Corresponding energy cut off values of WS<sub>2</sub> NSs. (<b>c</b>) Band structures of WS<sub>2</sub> NSs and Au NPs before and after intimate contact.</p>
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<p>Gas sensing mechanism in chemical sensitization effects due to decorate the Au NPs.</p>
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27 pages, 10139 KiB  
Article
Development of a Portable and Modular Gas Generator: Application to Formaldehyde Analysis
by Anaïs Becker, Nathaly Lohmann, Christophe A. Serra and Stéphane Le Calvé
Chemosensors 2022, 10(4), 131; https://doi.org/10.3390/chemosensors10040131 - 31 Mar 2022
Cited by 3 | Viewed by 3829
Abstract
This work aims at developing and validating under laboratory-controlled conditions a gas mixture generation device designed for easy on-site or laboratory calibration of analytical instruments dedicated to air monitoring, such as analysers or sensors. This portable device, which has been validated for formaldehyde, [...] Read more.
This work aims at developing and validating under laboratory-controlled conditions a gas mixture generation device designed for easy on-site or laboratory calibration of analytical instruments dedicated to air monitoring, such as analysers or sensors. This portable device, which has been validated for formaldehyde, is compact and is based on the diffusion of liquid formaldehyde through a short microporous interface with an air stream to reach non-Henry equilibrium gas–liquid dynamics. The geometry of the temperature-controlled assembly has been optimised to allow easy change of the aqueous solution, keeping the microporous tube straight. The formaldehyde generator has been coupled to an on-line formaldehyde analyser to monitor the gas concentration generated as a function of the liquid formaldehyde concentration, the temperature, the air gas flow rate, and the microporous tube length. Our experimental results show that the generated gaseous formaldehyde concentration increase linearly between 10 and 1740 µg m−3 with that of the aqueous solution ranging between 0 and 200 mg L−1 for all the gas flow rates studied, namely 25, 50 and 100 mL min−1. The generated gas phase concentration also increases with increasing temperature according to Henry’s law and with increasing the gas–liquid contact time either by reducing the gas flow rate from 100 to 25 mL min−1 or increasing the microporous tube length from 3.5 to 14 cm. Finally, the performances of this modular formaldehyde generator are compared and discussed with those reported in the scientific literature or commercialised by manufacturers. The technique developed here is the only one allowing to operate with a low flow rate such as 25 to 100 mL min−1 while generating a wide range of concentrations (10–1000 µg m−3) with very good accuracy. Full article
(This article belongs to the Special Issue Advances in Chemosensors Technologies for Monitoring and Diagnostics)
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<p>Device used for the generation of gaseous formaldehyde from a liquid solution. This device integrates a cylinder of pure air, a mass flow controller, a glass reactor containing the aqueous formaldehyde solution in which the microporous tube and its fixing system are immersed, an incubator to regulate the temperature. At the outlet of the device, the formaldehyde analyser monitored the gaseous formaldehyde concentration and the relative humidity in the gas mixture.</p>
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<p>Support pictures of the microporous tube either designed by CAD (left) or manufactured in ABS by 3D printing. A: 3D support of the microporous tube; B: microporous tube of 7 cm long; C: bevelled stainless-steel tube serving as a connector for the microporous tube; D: 1/16-inch Teflon tube; E: GL 45 bottle cap.</p>
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<p>Fluorescence signal of the formaldehyde analyser (µF1, Chromatotec, Val-de-Virvée, France) obtained at various gaseous formaldehyde concentrations: (A) 3.4 µg m<sup>−3</sup> (2.7 ppb), (B) 17.5 µg m<sup>−3</sup> (14.0 ppb), (C) 73.6 µg m<sup>−3</sup> (58.9 ppb), (D) 192.8 µg m<sup>−3</sup> (154.4 ppb), (E) 304.6 µg m<sup>−3</sup> (243.9 ppb), (F) 432.1 µg m<sup>−3</sup> (346.1 ppb) with F<sub>gas</sub> = 50 mL min<sup>−1</sup>, T = 10.7 °C, L = 7 cm, a photomultiplier gain set at 50% and [HCHO]<sub>liq</sub> = 2.5–200 mg L<sup>−1</sup>. Red data mean that the formaldehyde gas mixture generated by the source was previously diluted with pure air prior to analysis, so a correction has been applied to obtain the real values. (<b>a</b>) Raw fluorescence signal of the formaldehyde analyser for the concentrations A–F (reconstructed plot, see text); (<b>b</b>) Calibration of the formaldehyde analyser: fluorescence signal vs. gaseous formaldehyde concentrations generated by the gas generator shown in <a href="#chemosensors-10-00131-f003" class="html-fig">Figure 3</a>a and measured by the ISO 16000-3 reference method. The quoted error bars on the concentration are calculated from uncertainties of the MFC, the sampling volume and the HPLC analysis of DNPH tubes. Vertical error bars correspond to two times the standard deviation, but they are too small to be visible.</p>
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<p>Concentration of gaseous formaldehyde ([HCHO]<sub>gas</sub>) and relative humidity measured with the formaldehyde analyser (µF1, Chromatotec, Val-de-Virvée, France) vs. the liquid formaldehyde concentration with F<sub>gas</sub> = 50 mL min<sup>−1</sup>, T = 10.7 °C, L = 7 cm, a photomultiplier gain set at 50% and [HCHO]<sub>liq</sub> = 0–200 mg L<sup>−1</sup>. The horizontal error bars correspond to the uncertainties calculated from the preparation of the liquid formaldehyde solution. The vertical error bars correspond to two times the standard deviation, but they are too small to be visible. Red circles and black triangles mean that the generated gaseous formaldehyde mixture has been diluted prior to analysis, so a correction has been applied to obtain the real values of [HCHO]<sub>gas</sub> and RH.</p>
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<p>Concentration of the generated gaseous formaldehyde and relative humidity measured with the formaldehyde analyser (µF1, Chromatotec, Val-de-Virvée, France) vs. the liquid formaldehyde concentration for three different gas flow rates (25 mL min<sup>−1</sup> in green, 50 mL min<sup>−1</sup> in blue and 100 mL min<sup>−1</sup> in purple). The other parameters were fixed as follows: T = 10.7 °C, L = 7 cm, photomultiplier gain = 50%. The liquid formaldehyde concentrations were in the ranges: (<b>a</b>) 0–200 mg L<sup>−1</sup> and (<b>b</b>) 0–50 mg L<sup>−1</sup>. The horizontal error bars correspond to the uncertainties calculated from the preparation of the liquid formaldehyde solution. The vertical error bars correspond to two times the standard deviation, but they are too small to be visible. Red circles and black triangles mean that the generated gaseous formaldehyde mixture has been diluted prior to analysis, so a correction has been applied to obtain the real values of [HCHO]<sub>gas</sub> and RH.</p>
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<p>Generated concentration of gaseous formaldehyde and relative humidity obtained with a formaldehyde analyser (µF1, Chromatotec, Val-de-Virvée, France) vs. the liquid formaldehyde concentration for two different temperatures (10.7 °C in blue and 21.8 °C in purple), [HCHO]<sub>liq</sub> = 0–200 mg L<sup>−1</sup>, F<sub>gas</sub> = 50 mL min<sup>−1</sup>, L = 7 cm, photomultiplier gain = 50%. The horizontal error bars correspond to the uncertainties calculated from the preparation of the liquid formaldehyde solution. The vertical error bars correspond to two times the standard deviation, but they are too small to be visible. Red circles and black triangles mean that the generated gaseous formaldehyde mixture has been diluted prior to analysis, so a correction has been applied to obtain the real values of [HCHO]<sub>gas</sub> and RH.</p>
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<p>Relative humidity measured with the formaldehyde analyser (µF1, Chromatotec, Val-de-Virvée, France) vs. the gas flow rate applied in the microporous tube using pure water. T = 5.8, 10.7, 15.4 and 21.8 °C, F<sub>gas</sub> = 25, 50, 60, 80 and 100 mL min<sup>−1</sup>.</p>
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<p>Generated gaseous formaldehyde concentration and relative humidity measured with a formaldehyde analyser (µF1, Chromatotec, Val-de-Virvée, France) for different tube lengths (L = 3.5 cm in purple, L = 7 cm in blue and L = 14 cm in green), with [HCHO]<sub>liq</sub> = 0–100 mg L<sup>−1</sup>, F<sub>gas</sub> = 100 mL min<sup>−1</sup>, T = 10.7 °C, photomultiplier gain = 50%. The horizontal error bars correspond to the uncertainties calculated from the preparation of the liquid formaldehyde solution. The vertical error bars correspond to two times the standard deviation, but they are too small to be visible. (<b>a</b>) [HCHO]<sub>gas</sub> vs. [HCHO]<sub>liq</sub> for L = 3.5, 7 and 14 cm; (<b>b</b>) [HCHO]<sub>gas</sub> vs. the microporous tube length for [HCHO]<sub>liq</sub> = 10–10 mg L<sup>−1</sup>.</p>
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<p>Pictures of the 5 microporous tube configurations of different tube lengths and positions. (<b>A</b>): L = 20 cm, coiled; (<b>B</b>): L = 14 cm, coiled; (<b>C</b>): L = 14 cm, straight; (<b>D</b>): L = 7 cm, straight; (<b>E</b>): L = 3.5 cm, straight.</p>
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<p>Raw fluorescence signal of the formaldehyde analyser measured with the 5 studied configurations: A: L = 20 cm, coiled; B: L = 14 cm, coiled; C: L = 14 cm, straight; D: L = 7 cm, straight; E: L = 3.5 cm, straight. The other parameters were fixed as follows: [HCHO]<sub>liq</sub> = 20 mg L<sup>−1</sup>, F<sub>gas</sub> = 50 mL min<sup>−1</sup>, T = 10.7 °C, photomultiplier gain = 50%.</p>
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<p>Autonomy (t<sub>autonomy</sub>) vs. liquid formaldehyde concentration for a gas flow rate of 25, 50 and 100 mL min<sup>−1</sup>. The autonomy (t<sub>autonomy</sub>) is the time required for a loss of 1% of the mole number present in the formaldehyde solution at 10 °C, with a volume of liquid solution of 300 mL and for liquid formaldehyde concentration in the range 2.5–200 mg L<sup>−1</sup>.</p>
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<p>Comparison of gaseous formaldehyde concentrations generated vs. gas flow rate using the different dynamic generation methods reported in the literature and this work. A: permeation tube with paraformaldehyde, Andrawes et al, (1984) [<a href="#B54-chemosensors-10-00131" class="html-bibr">54</a>]; B: pump motor driven syringe, Andrawes et al, (1984) [<a href="#B54-chemosensors-10-00131" class="html-bibr">54</a>]; C: vaporization with nebulizer of aqueous formaldehyde solution, Lindahl et al, (1996) [<a href="#B56-chemosensors-10-00131" class="html-bibr">56</a>]; D: permeation tube with paraformaldehyde, Aoyagi et al, (2012) [<a href="#B59-chemosensors-10-00131" class="html-bibr">59</a>]; E: Dynamic evaporation of aqueous formaldehyde solution, Zhu et al, (2019) [<a href="#B60-chemosensors-10-00131" class="html-bibr">60</a>]; F: Commercial instrument, Permeation tube with an aqueous solution of formaldehyde, Permeater PD1-B, Gastec, Japan [<a href="#B77-chemosensors-10-00131" class="html-bibr">77</a>]; G: Commercial instrument, permeation tube with paraformaldehyde, Chromatotec [<a href="#B76-chemosensors-10-00131" class="html-bibr">76</a>]; H: This work.</p>
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14 pages, 2302 KiB  
Article
Photonics of Viburnum opulus L. Extracts in Microemulsions with Oxygen and Gold Nanoparticles
by Anna Tcibulnikova, Evgeniia Zemliakova, Dmitry Artamonov, Vasily Slezhkin, Liubov Skrypnik, Ilia Samusev, Andrey Zyubin, Artemy Khankaev, Valery Bryukhanov and Ivan Lyatun
Chemosensors 2022, 10(4), 130; https://doi.org/10.3390/chemosensors10040130 - 30 Mar 2022
Cited by 1 | Viewed by 2273
Abstract
In this paper, the optical properties of viburnum extract flavonoids in the visible region of the spectrum were investigated and their use as a potential photosensitizer of singlet oxygen for photodynamic therapy was evaluated. The presence of long-lived excited states in the extract [...] Read more.
In this paper, the optical properties of viburnum extract flavonoids in the visible region of the spectrum were investigated and their use as a potential photosensitizer of singlet oxygen for photodynamic therapy was evaluated. The presence of long-lived excited states in the extract molecules was established by spectral methods and time-resolved spectroscopy methods and the dependences of the absorption capacity and luminescence intensity of the extract molecules on the concentrations of oxygen and ablative nanoparticles of the gold in the reverse micelles of AOT (sodium dioctyl sulfosuccinate) were established. The plasmonic enhancement of the luminescence of the extract molecules and the processes of their complexation with oxygen were also established. Furthermore, the rate constants of the processes of conversion of exciting energy in complexes were determined. Full article
(This article belongs to the Special Issue Optical Chemical Sensors and Spectroscopy)
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<p>The IR spectrum and interpretation of the peaks of the water–Eth <span class="html-italic">Viburnum opulus</span> L. extract in the KBr pellet.</p>
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<p>Optical characteristics. (<b>a</b>) Absorption spectrum of water–Eth VO extract with Au NPs of various concentrations C<sub>1</sub> = 1 × 10<sup>−10</sup>, C<sub>2</sub> =0. 75 × 10<sup>−10</sup>, C<sub>3</sub> = 0.5 × 10<sup>−10</sup>, C<sub>4</sub> = 0.25 × 10<sup>−10</sup>, C<sub>5</sub> = 0.125 × 10<sup>−10</sup> M. (<b>b</b>) Absorption spectrum of Au NPs in water (green curve) and in microemulsion (black curve), inset—SEM image of ablative Au NPs and size distributions. (<b>c</b>) Luminescence spectrum of water–Eth extract with Au NPs. (<b>d</b>) The dynamics of changes in the optical density and luminescence intensity of the extract on the concentration of Au NPs in the AOT reverse micelles at a wavelength of 480 nm.</p>
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<p>Absorption spectra of microemulsion with Au NPs with oxygen C<sub>3</sub>[O<sub>2</sub>]—black curve, VO microemulsion with Au nanoparticles (C = 10<sup>−10</sup> M) without and with oxygen of different concentrations (C<sub>1</sub> = 2 × 10<sup>−4</sup> M, C<sub>2</sub> = 3.5 × 10<sup>−4</sup> M, C<sub>3</sub> = 8.5 × 10<sup>−4</sup> M) (<b>a</b>). The dependences of changes in luminescence intensity and luminescence lifetimes on oxygen concentrations at λ = 480 nm under photoexcitation with λ = 400 nm (<b>b</b>).</p>
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<p>(<b>a</b>) Kinetic decay curves of the luminescence from the VO extract microemulsion with Au NPs (C = 10<sup>−10</sup> M) at a wavelength of 420 nm under photoexcitation with wavelength of 400 nm at different oxygen concentrations (C<sub>1</sub>, C<sub>2</sub>, C<sub>3</sub>), inset—without oxygen. (<b>b</b>) Kinetics decay of extract molecule triplet states with Au NPs with oxygen of different concentrations (C<sub>1</sub>, C<sub>2</sub>, C<sub>3</sub>) registered at a wavelength of 680 nm with photoexcitation of 530 nm (triplet states), inset—without oxygen. C<sub>1</sub> = 2 × 10<sup>−4</sup> M, C<sub>2</sub> = 3.5 × 10<sup>−4</sup> M, C<sub>3</sub> = 8.5 × 10<sup>−4</sup> M.</p>
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12 pages, 2340 KiB  
Article
Spectroscopic Study of Phytosynthesized Ag Nanoparticles and Their Activity as SERS Substrate
by Volodymyr Dzhagan, Oleksandr Smirnov, Mariia Kovalenko, Nazar Mazur, Oleksandr Hreshchuk, Nataliya Taran, Svitlana Plokhovska, Yaroslav Pirko, Alla Yemets, Volodymyr Yukhymchuk and Dietrich R. T. Zahn
Chemosensors 2022, 10(4), 129; https://doi.org/10.3390/chemosensors10040129 - 29 Mar 2022
Cited by 14 | Viewed by 3144
Abstract
The affordable and scalable synthesis of noble metal nanoparticles that are biocompatible without additional functionalization steps has been a growing field of research, stimulated by numerous prospective applications of these NPs. In the case of phytosynthesized or biogenic noble metal NPs, the mechanism [...] Read more.
The affordable and scalable synthesis of noble metal nanoparticles that are biocompatible without additional functionalization steps has been a growing field of research, stimulated by numerous prospective applications of these NPs. In the case of phytosynthesized or biogenic noble metal NPs, the mechanism of NP stabilization by biomolecules contained in each particular plant extract or living organism determines the possible applications of these NPs. In this work, we investigated Ag NPs synthesized in water with plant extracts of common toothwort (Lathraea squamaria) and two species of pepper (Capsicum annuum and Capsicum chinense). From FTIR and XPS, we drew conclusions about the composition of the functional groups and molecules that stabilize NPs in each extract, such as polysaccharide compounds (pectins, cellulose, glycosides and phenolic acids). Distinct characteristic IR features of amide I and amide II proteins were observed, which are common in plant extracts, while features of amide III were not distinctly observed in our extracts. A Raman spectroscopy study revealed weak own-SERS activity of the biomolecules of the extract and high efficiency of the NPs in the enhancement of “external” analytes, such as dyes and antibodies. This is the first report of the efficient SERS application of phytosynthesized Ag NPs. Full article
(This article belongs to the Special Issue SERS: Analytical and Biological Challenges)
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<p>UV-vis absorption spectra (<b>a</b>) and SEM image (<b>b</b>) of Ag NPs phytosynthesized using aqueous extracts of common toothwort roots. The three curves in (<b>a</b>) correspond to different times after initiating the synthesis. The inset in (<b>a</b>) is a photograph of the final NP solution.</p>
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<p>High-resolution XPS spectra of the Ag NPs synthesized using pepper extracts: Ag (<b>a</b>), C (<b>b</b>), O (<b>c</b>), S (<b>d</b>), N (<b>e</b>).</p>
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<p>High-resolution XPS spectra of the Ag NPs synthesized with <span class="html-italic">Common toothwort</span> extract: Ag/K (<b>a</b>), C/K (<b>b</b>), O (<b>c</b>), S (<b>d</b>), N (<b>e</b>). A survey spectrum in the range of all elements is shown in (<b>f</b>).</p>
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<p>IR transmission spectra of phytosynthesized Ag NPs in the range of 500–1800 cm<sup>−1</sup> (<b>a</b>) and of 2500–3500 cm<sup>−1</sup> (<b>b</b>). The spectra shifted vertically for convenience. To avoid overloading the figure, the wavenumbers of absorption peaks are marked only in those spectra where they occur at the largest intensity or are most distinct.</p>
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<p>(<b>a</b>) Raman spectra of 10<sup>−4</sup> M rhodamine 6G (R6G) with two freshly prepared Ag NP–common toothwort (<span class="html-italic">L. squamaria</span>) samples (roots and flowers). The spectra of bare NPs and the same concentration of R6G on glass were measured for comparison (as reference spectra). (<b>b</b>) Raman spectra of 10<sup>−5</sup> M Rhodamine 6G (R6G) and crystal violet (CV) enhanced by the Ag NP common toothwort (root) after six months storage of the NP solution after synthesis. The spectra of bare NPs and the same concentration of R6G and CV on glass were measured for comparison (as reference spectra), as well as a 100 times higher concentration of R6G (10<sup>−3</sup>), at which the Raman peaks start to be detected without enhancement. (<b>c</b>) Raman spectra of 10<sup>−3</sup> M malachite green (MG) with two Ag NP–common toothwort samples (roots and flowers). (<b>d</b>) Raman spectra of <span class="html-italic">E.coli</span> antibody with Ag NP–common toothwort (roots), monitored with 1 s time intervals. The spectrum for the same antibody with ordinary Ag–citrate NPs is shown for comparison, illustrating that the same set of antibody-related features was observed. The schemes of the analyte molecule are shown for R6G (<b>a</b>), CV (<b>b</b>), and MG (<b>c</b>).</p>
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19 pages, 4412 KiB  
Review
The Role of Surface Enhanced Raman Scattering for Therapeutic Drug Monitoring of Antimicrobial Agents
by Stefano Fornasaro, Dana Cialla-May, Valter Sergo and Alois Bonifacio
Chemosensors 2022, 10(4), 128; https://doi.org/10.3390/chemosensors10040128 - 29 Mar 2022
Cited by 15 | Viewed by 4251
Abstract
The rapid quantification of antimicrobial agents is important for therapeutic drug monitoring (TDM), enabling personalized dosing schemes in critically ill patients. Highly sophisticated TDM technology is becoming available, but its implementation in hospitals is still limited. Among the various proposed techniques, surface-enhanced Raman [...] Read more.
The rapid quantification of antimicrobial agents is important for therapeutic drug monitoring (TDM), enabling personalized dosing schemes in critically ill patients. Highly sophisticated TDM technology is becoming available, but its implementation in hospitals is still limited. Among the various proposed techniques, surface-enhanced Raman scattering (SERS) stands out as one of the more interesting due to its extremely high sensitivity, rapidity, and fingerprinting capabilities. Here, we present a comprehensive review of various SERS-based novel approaches applied for direct and indirect detection and quantification of antibiotic, antifungal, and antituberculosis drugs in different matrices, particularly focusing on the challenges for successful exploitation of this technique in the development of assays for point-of-care tests. Full article
(This article belongs to the Special Issue SERS: Analytical and Biological Challenges)
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<p>(<b>A</b>) Antimicrobial concentration–time curves. (<b>B</b>) Pharmacokinetic and pharmacodynamic parameters of antimicrobials at steady state. %fT<sub>&gt;MIC</sub>, the percentage of time for which a drug’s concentration remains above the minimum inhibitory concentration (MIC) for a dosing period; C<sub>max</sub>/MIC, the ratio of the maximum antimicrobial concentration (C<sub>max</sub>) to MIC; fAUC/MIC, the ratio of the area under the concentration–time curve during a 24 h time period (AUC<sub>0–24 h</sub>) to MIC.</p>
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<p>PK/PD classification of most common antimicrobial agents in intensive care units.</p>
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<p>(<b>A</b>) SERS spectra for different amounts of cloxacillin deposited on the nanopillar substrate. SERS intensities were normalized to improve visual clarity. (<b>B</b>) The nonlinear calibration plot (<span class="html-italic">n</span> = 3). Each ratio of intensity was averaged over 121 spectra obtained in a 1 mm × 1 mm droplet footprint. Reproduced with permission from [<a href="#B79-chemosensors-10-00128" class="html-bibr">79</a>]. Copyright 2017 American Chemical Society.</p>
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<p>An example of urine sample preparation and LLE procedure. Reproduced with permission from [<a href="#B87-chemosensors-10-00128" class="html-bibr">87</a>]. Copyright 2022 Elsevier.</p>
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<p>Setup, vertical flow, and detection schematic. Vertical flow using a microporous membrane scheme separates the flucytosine from the serum. SEM of the inkjet-printed AgNPs on cellulose paper is shown. The SERS signal is read from the paper SERS sensors. Reproduced with permission from [<a href="#B52-chemosensors-10-00128" class="html-bibr">52</a>]. Copyright 2017 Elsevier.</p>
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<p>PLS prediction plots for spiked human urine samples (three individual, S1, S2 and S3, and three pooled urine samples, P0, P1 and P2) using seven concentrations for training (black scatter) and five (red scatter) for predicting. Reproduced with permission from [<a href="#B66-chemosensors-10-00128" class="html-bibr">66</a>]. Copyright 2016 American Chemical Society.</p>
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12 pages, 2966 KiB  
Article
Design and Characterization of a Microwave Transducer for Gas Sensing Applications
by Giovanni Gugliandolo, Krishna Naishadham, Giovanni Crupi and Nicola Donato
Chemosensors 2022, 10(4), 127; https://doi.org/10.3390/chemosensors10040127 - 29 Mar 2022
Cited by 10 | Viewed by 2979
Abstract
Gas sensors have wide applications in several fields, spanning diverse areas such as environmental monitoring, healthcare, defense, and the evaluation of personal and occupational exposure to hazardous chemicals. Different typologies of gas sensors have been proposed over the years, such as optical, electrochemical, [...] Read more.
Gas sensors have wide applications in several fields, spanning diverse areas such as environmental monitoring, healthcare, defense, and the evaluation of personal and occupational exposure to hazardous chemicals. Different typologies of gas sensors have been proposed over the years, such as optical, electrochemical, and metal oxide gas sensors. In this paper, a relatively new typology of gas sensors is explored: the microwave gas sensor. It consists of a combination of a microwave transducer with a nanostructured sensing material deposited on an interdigitated capacitor (IDC). The device is designed and fabricated on a Rogers substrate (RO4003C) using microstrip technology, and investigated as a microwave transducer over the frequency range from 1 GHz to 6 GHz by measuring the scattering (S) parameters in response to gas adsorption and desorption. The sensing material is based on a nano-powder of barium titanate oxalate with a coating of urea (BaTiO(C2O4)2/CO(NH2)2). It is deposited on the IDC surface by drop coating, thus creating a sensing film. The developed prototype has been tested toward different oxygen (O2) concentrations and exhibits a sensitivity of 28 kHz/%O2. Special attention has been devoted to the measurement process. Besides the canonical short-open-load-thru (SOLT) calibration of the measured S-parameters, a thru-reflect-line (TRL) calibration has been performed in order to get rid of the parasitic electromagnetic (EM) contributions of the board connectors and the feedlines, thus moving the measurement reference planes to the edges of the IDC. Full article
(This article belongs to the Special Issue Gas Sensors: Simulation, Modeling, and Characterization)
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<p>Microwave transducer prototype: (<b>a</b>) Sketch of the IDC with dimensions; (<b>b</b>) photo of the fabricated device.</p>
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<p>Boards fabricated using the prototype PCB milling machine: the IDC device and the thru, reflect and line standards.</p>
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<p>Comparison between simulations and measurements of the S-parameters for the three TRL standards in the frequency range from 1 GHz to 6 GHz: (<b>a</b>) Thru standard (S-parameters magnitude comparison); (<b>b</b>) Reflect standard (S-parameters magnitude comparison); (<b>c</b>) Line standard (S-parameters magnitude comparison); and (<b>d</b>) Line standard (<span class="html-italic">S</span><sub>21</sub> phase comparison).</p>
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<p>(<b>a</b>) Test chamber containing the IDC covered by the sensing material. Two holes of the chamber are used for the inlet and outlet gas pipes, additional two holes are used for the RF cables connections, while the other two apertures are sealed with leak-proof plugs. (<b>b</b>) Picture of the experimental measurement setup.</p>
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<p>Magnitude of <span class="html-italic">S</span><sub>11</sub> (<b>a</b>,<b>c</b>) and <span class="html-italic">S</span><sub>21</sub> (<b>b</b>,<b>d</b>) versus frequency for six different O<sub>2</sub> concentrations, ranging from 0% O<sub>2</sub> to 100% O<sub>2</sub>. The selected frequency range goes from 4.2 GHz to 4.6 GHz.</p>
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<p>Behavior of the resonant frequency, quality factor, and amplitude at the resonance for the studied sensor by considering six different O<sub>2</sub> concentrations. The plotted trends refer to the dips observed at about 4.4 GHz in (<b>a</b>) |<span class="html-italic">S</span><sub>11</sub>| and in (<b>b</b>) |<span class="html-italic">S</span><sub>21</sub>| (<b>b</b>). A linear interpolation has been carried out on the acquired points with a R<sup>2</sup> higher than 0.9.</p>
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<p>Phase behavior of <span class="html-italic">S</span><sub>11</sub> and <span class="html-italic">S</span><sub>21</sub> around the resonant frequency using 0% O<sub>2</sub> concentration as an example.</p>
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15 pages, 2305 KiB  
Communication
Comparative Analysis of Derivative Parameters of Chemoresistive Sensor Signals for Gas Concentration Estimation
by Nina K. Plugotarenko, Tatiana N. Myasoedova, Sergey P. Novikov and Tatiana S. Mikhailova
Chemosensors 2022, 10(4), 126; https://doi.org/10.3390/chemosensors10040126 - 29 Mar 2022
Cited by 2 | Viewed by 2875
Abstract
Signals from resistive gas sensors based on zirconium dioxide and silicon–carbon films have been extensively investigated to estimate gas concentration. In this study, the change in the normalized resistance of the sensor’s response under NO2 exposure is shown and the analysis of [...] Read more.
Signals from resistive gas sensors based on zirconium dioxide and silicon–carbon films have been extensively investigated to estimate gas concentration. In this study, the change in the normalized resistance of the sensor’s response under NO2 exposure is shown and the analysis of the first and second derivatives of the response curves were carried out. A signal-processing scheme, reducing the effect of noise and signal drift, is proposed. The extreme of the second derivative of the sensor response, the initial reaction rate, and the slope of the curve of the approximating line in the coordinates of the Elovich equation are proposed as calibration dependencies. The calibration curves built from the values of the maximum second derivative turned out to be the most stable, with the lowest relative error in estimating gas concentration compared to the traditional fixed-time point method. Full article
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<p>Schematic diagram of the measurement setup.</p>
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<p>The graphs of (<b>a</b>) the original signal and (<b>b</b>) the filtered signal (sensor working temperature, 80 °C).</p>
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<p>The real-time sensor response to various NO<sub>2</sub> concentrations: (<b>a</b>) Type 1 sensor (working temperature is 80 °C); (<b>b</b>) Type 2 sensor (working temperature is 22 °C).</p>
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<p>The kinetics (<b>a</b>) of the Type 1 gas sensor response <span class="html-italic">S</span>(<span class="html-italic">t</span>); (<b>b</b>) of the first derivative <span class="html-italic">S</span>(<span class="html-italic">t</span>); (<b>c</b>) of the second derivative <span class="html-italic">S</span>(<span class="html-italic">t</span>) at different NO<sub>2</sub> concentrations.</p>
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<p>The kinetics (<b>a</b>) of the Type 2 gas sensor response <span class="html-italic">S</span>(<span class="html-italic">t</span>); (<b>b</b>) of the first derivative <span class="html-italic">S</span>(<span class="html-italic">t</span>); (<b>c</b>) of the second derivative <span class="html-italic">S</span>(<span class="html-italic">t</span>) at different NO<sub>2</sub> concentrations.</p>
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<p>Calibration curves for NO<sub>2</sub> concentration estimation of Type 1 sensor (<b>a</b>) of the adsorption response Δ<span class="html-italic">S</span> at the saturation moment; (<b>b</b>) minimum of the first derivative <span class="html-italic">S</span>′(<span class="html-italic">t</span>); (<b>c</b>) maximum of the second derivative <span class="html-italic">S</span>″(<span class="html-italic">t</span>).</p>
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<p>Calibration curves for NO<sub>2</sub> concentration estimation of the Type 2 sensor: (<b>a</b>) of the adsorption response Δ<span class="html-italic">S</span> at the saturation moment; (<b>b</b>) minimum of the first derivative <span class="html-italic">S</span>′(<span class="html-italic">t</span>); (<b>c</b>) maximum of the second derivative <span class="html-italic">S</span>″(<span class="html-italic">t</span>).</p>
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<p>Calibration curves <span class="html-italic">S</span>′(<span class="html-italic">t</span>) at different moments: (<b>a</b>) Type 1 sensor; (<b>b</b>) Type 2 sensor.</p>
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<p>The dependences ∆<span class="html-italic">S</span> vs. <span class="html-italic">ln</span>(<span class="html-italic">t</span>): (<b>a</b>) Type 1 sensor; (<b>b</b>) Type 2 sensor.</p>
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<p>Calibration curve plotted from graphs ∆<span class="html-italic">S</span> vs. <span class="html-italic">ln</span>(<span class="html-italic">t</span>): (<b>a</b>) Type 1 sensor; (<b>b</b>) Type 2 sensor.</p>
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17 pages, 1623 KiB  
Article
Grape Cultivar Identification and Classification by Machine Olfaction Analysis of Leaf Volatiles
by Ali Khorramifar, Hamed Karami, Alphus Dan Wilson, Amir Hosein Afkari Sayyah, Anastasiia Shuba and Jesús Lozano
Chemosensors 2022, 10(4), 125; https://doi.org/10.3390/chemosensors10040125 - 29 Mar 2022
Cited by 26 | Viewed by 3544
Abstract
Development of electronic technologies for precise identification of fruit crop cultivars in agricultural production provides an effective means for assuring product quality and authentication. The capabilities of discriminating between grape (Vitis vinifera L.) cultivars is essential for assuring certification of varieties sold [...] Read more.
Development of electronic technologies for precise identification of fruit crop cultivars in agricultural production provides an effective means for assuring product quality and authentication. The capabilities of discriminating between grape (Vitis vinifera L.) cultivars is essential for assuring certification of varieties sold in world markets. Machine olfaction, based on electronic-nose (e-nose) technologies, is readily available for rapid identification of fruit and vegetative agricultural products. This technology relies on detection of and discrimination between volatile organic compound (VOC) emissions from plant parts. It may be used in all stages of agricultural production to facilitate crop maintenance, cultivation, and harvesting decisions prior to marketing. An experimental e-nose device was constructed and tested in combination with five chemometric methods, including PCA, LDA, QDA, SVM, and ANN, as rapid, non-destructive tools for identification and classification of grape cultivars. An e-nose instrument equipped with nine metal oxide semiconductor (MOS) sensors was utilized to identify and classify five grape cultivars based on leaf VOC emissions using supervised and non-supervised methods. Grape leaf samples were first identified as belonging to specific cultivar types using PCA analyses, which are non-supervised classification methods, with the first two principal components (PC-1 and PC-2) accounting for 89% of the total variance. Four supervised statistical methods were further tested, including DA, QDA, SVM, and ANN, and provided effective discrimination accuracies of 98%, 99%, 92%, and 99%, respectively. These findings confirmed the suitable applicability of an MOS e-nose sensor array with supervised methods for accurate identification of grape cultivars, which is useful for authentication of vine cultivar types for commercial markets. Full article
(This article belongs to the Special Issue Chemometrics for Multisensor Systems and Artificial Senses)
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<p>Aroma signatures (smellprint patterns) resulting from nine sensor-output responses of the MAU-9 electronic nose system to aroma VOC emissions of grape leaf samples. (<b>a</b>) Raw sensor array output response; (<b>b</b>) Normalized sensor output response (conductivity ratio represented by G-G0 on the <span class="html-italic">y</span>-axis).</p>
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<p>Radar plots of MOS e-nose sensor array output responses to VOC emissions of grape leaf volatiles derived from five different grape cultivars. Legend color scheme (for radial lines of e-nose plot data for grape varieties) are as follows: Join (light blue); Rasmi (green); Askari (red), Tokilgan (orange), and Keshmeshi (purple). Peripheral numbers on the plot indicate individual MOS sensor numbers.</p>
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<p>Results of aroma plots for discrimination between five grape cultivars. (<b>a</b>) Two-dimensional PCA data plots; (<b>b</b>) loading diagram showing the effectiveness of individual MOS sensors in contributing to discrimination between grape cultivars.</p>
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<p>Results of linear analysis for detection of grape cultivars using (<b>a</b>) LDA and (<b>b</b>) QDA.</p>
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<p>Results of the SVM method for detection of five grape cultivars. Axes are given numbered C labels, given on both <span class="html-italic">x</span>- and <span class="html-italic">y</span>-axes, which refer to the name of the sensor variable, with the number following the C indicating the sensor number to which the sensor variable corresponds.</p>
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<p>Average performance parameters of four different models for classification of 5 grape cultivars.</p>
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31 pages, 7931 KiB  
Article
Visible and Near Infrared Image Fusion Using Base Tone Compression and Detail Transform Fusion
by Dong-Min Son, Hyuk-Ju Kwon and Sung-Hak Lee
Chemosensors 2022, 10(4), 124; https://doi.org/10.3390/chemosensors10040124 - 25 Mar 2022
Cited by 11 | Viewed by 2846
Abstract
This study aims to develop a spatial dual-sensor module for acquiring visible and near-infrared images in the same space without time shifting and to synthesize the captured images. The proposed method synthesizes visible and near-infrared images using contourlet transform, principal component analysis, and [...] Read more.
This study aims to develop a spatial dual-sensor module for acquiring visible and near-infrared images in the same space without time shifting and to synthesize the captured images. The proposed method synthesizes visible and near-infrared images using contourlet transform, principal component analysis, and iCAM06, while the blending method uses color information in a visible image and detailed information in an infrared image. The contourlet transform obtains detailed information and can decompose an image into directional images, making it better in obtaining detailed information than decomposition algorithms. The global tone information is enhanced by iCAM06, which is used for high-dynamic range imaging. The result of the blended images shows a clear appearance through both the compressed tone information of the visible image and the details of the infrared image. Full article
(This article belongs to the Section Analytical Methods, Instrumentation and Miniaturization)
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<p>Principal component analysis fusion block diagram.</p>
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<p>Directional detail image extraction using the contourlet filter.</p>
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<p>Result of the base and edge images decomposed by contourlet transform: (<b>a</b>) base and (<b>b</b>) edge images (eight directions).</p>
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<p>Aligned visible and NIR images: (<b>a</b>) visible and NIR images taken by the proposed beam splitter camera device; (<b>b</b>) example of the homography theory using the scale-invariant feature transform algorithm; and (<b>c</b>) result of the homography theory visible and NIR image alignment.</p>
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<p>Aligned visible and NIR images: (<b>a</b>) visible and NIR images taken by the proposed beam splitter camera device; (<b>b</b>) example of the homography theory using the scale-invariant feature transform algorithm; and (<b>c</b>) result of the homography theory visible and NIR image alignment.</p>
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<p>Proposed beam splitter camera device: (<b>a</b>) plate beam splitter description and (<b>b</b>) CMOS camera module with a beam splitter.</p>
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<p>NIR, visible, and fused images: (<b>a</b>) bright surround input and fused images and (<b>b</b>) dim surround input and fused images.</p>
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<p>Block diagram of the proposed method: (<b>a</b>) luminance channel fusion algorithm and (<b>b</b>) XYZ channel fusion algorithm.</p>
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<p>iCAM06 brief block diagram.</p>
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<p>Input pair and result images: (<b>a</b>) visible image; (<b>b</b>) IR image; (<b>c</b>) Laplacian pyramid entropy fusion; (<b>d</b>) Laplacian pyramid PCA fusion; (<b>e</b>) low-rank fusion; (<b>f</b>) dense fusion; (<b>g</b>) proposed method (luminance channel fusion); and (<b>h</b>) proposed method (XYZ channel fusion).</p>
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<p>Input pair and result images: (<b>a</b>) visible image; (<b>b</b>) IR image; (<b>c</b>) Laplacian pyramid entropy fusion; (<b>d</b>) Laplacian pyramid PCA fusion; (<b>e</b>) low-rank fusion; (<b>f</b>) dense fusion; (<b>g</b>) proposed method (luminance channel fusion); and (<b>h</b>) proposed method (XYZ channel fusion).</p>
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<p>Input pair and result images: (<b>a</b>) visible image; (<b>b</b>) IR image; (<b>c</b>) Laplacian pyramid entropy fusion; (<b>d</b>) Laplacian pyramid PCA fusion; (<b>e</b>) low-rank fusion; (<b>f</b>) dense fusion; (<b>g</b>) proposed method (luminance channel fusion); and (<b>h</b>) proposed method (XYZ channel fusion).</p>
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<p>Input pair images and result images: (<b>a</b>) Visible image, (<b>b</b>) IR image, (<b>c</b>) Laplacian pyramid entropy fusion, (<b>d</b>) Laplacian pyramid PCA fusion, (<b>e</b>) Low rank fusion, (<b>f</b>) dense fusion, (<b>g</b>) Proposed method (Luminance channel fusion), (<b>h</b>) Proposed method (XYZ channel fusion).</p>
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<p>Input pair images and result images: (<b>a</b>) Visible image, (<b>b</b>) IR image, (<b>c</b>) Laplacian pyramid entropy fusion, (<b>d</b>) Laplacian pyramid PCA fusion, (<b>e</b>) Low rank fusion, (<b>f</b>) dense fusion, (<b>g</b>) Proposed method (Luminance channel fusion), (<b>h</b>) Proposed method (XYZ channel fusion).</p>
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<p>Input pair images and result images: (<b>a</b>) Visible image, (<b>b</b>) IR image, (<b>c</b>) Laplacian pyramid entropy fusion, (<b>d</b>) Laplacian pyramid PCA fusion, (<b>e</b>) Low rank fusion, (<b>f</b>) dense fusion, (<b>g</b>) Proposed method (Luminance channel fusion), (<b>h</b>) Proposed method (XYZ channel fusion).</p>
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<p>Comparison of the result images of the fusion methods. (Images available at <a href="https://www.epfl.ch/labs/ivrl/research/downloads/rgb-nir-scene-dataset/" target="_blank">https://www.epfl.ch/labs/ivrl/research/downloads/rgb-nir-scene-dataset/</a> (accessed on 21 March 2022) [<a href="#B31-chemosensors-10-00124" class="html-bibr">31</a>]).</p>
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<p>Comparison of the result images of the fusion methods. (Images available at <a href="https://www.epfl.ch/labs/ivrl/research/downloads/rgb-nir-scene-dataset/" target="_blank">https://www.epfl.ch/labs/ivrl/research/downloads/rgb-nir-scene-dataset/</a> (accessed on 21 March 2022) [<a href="#B31-chemosensors-10-00124" class="html-bibr">31</a>]).</p>
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<p>Metric scores: (<b>a</b>) BRISQUE score; (<b>b</b>) VIFF score; (<b>c</b>) Entropy score; (<b>d</b>) Cross entropy score; (<b>e</b>) CPBD score; (<b>f</b>) S3 score; (<b>g</b>) Spatial frequency score; (<b>h</b>) Average gradient score; and (<b>i</b>) Edge intensity score.</p>
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<p>Metric scores: (<b>a</b>) BRISQUE score; (<b>b</b>) VIFF score; (<b>c</b>) Entropy score; (<b>d</b>) Cross entropy score; (<b>e</b>) CPBD score; (<b>f</b>) S3 score; (<b>g</b>) Spatial frequency score; (<b>h</b>) Average gradient score; and (<b>i</b>) Edge intensity score.</p>
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<p>Metric scores: (<b>a</b>) BRISQUE score; (<b>b</b>) VIFF score; (<b>c</b>) Entropy score; (<b>d</b>) Cross entropy score; (<b>e</b>) CPBD score; (<b>f</b>) S3 score; (<b>g</b>) Spatial frequency score; (<b>h</b>) Average gradient score; and (<b>i</b>) Edge intensity score.</p>
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<p>Metric scores: (<b>a</b>) BRISQUE score; (<b>b</b>) VIFF score; (<b>c</b>) Entropy score; (<b>d</b>) Cross entropy score; (<b>e</b>) CPBD score; (<b>f</b>) S3 score; (<b>g</b>) Spatial frequency score; (<b>h</b>) Average gradient score; and (<b>i</b>) Edge intensity score.</p>
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17 pages, 1505 KiB  
Review
Advances in Nucleic Acid Amplification-Based Microfluidic Devices for Clinical Microbial Detection
by Thi Ngoc Diep Trinh and Nae Yoon Lee
Chemosensors 2022, 10(4), 123; https://doi.org/10.3390/chemosensors10040123 - 25 Mar 2022
Cited by 16 | Viewed by 5054
Abstract
Accurate and timely detection of infectious pathogens is urgently needed for disease treatment and control of possible outbreaks worldwide. Conventional methods for pathogen detection are usually time-consuming and labor-intensive. Novel strategies for the identification of pathogenic nucleic acids are necessary for practical application. [...] Read more.
Accurate and timely detection of infectious pathogens is urgently needed for disease treatment and control of possible outbreaks worldwide. Conventional methods for pathogen detection are usually time-consuming and labor-intensive. Novel strategies for the identification of pathogenic nucleic acids are necessary for practical application. The advent of microfluidic technology and microfluidic devices has offered advanced and miniaturized tools to rapidly screen microorganisms, improving many drawbacks of conventional nucleic acid amplification-based methods. In this review, we summarize advances in the microfluidic approach to detect pathogens based on nucleic acid amplification. We survey microfluidic platforms performing two major types of nucleic acid amplification strategies, namely, polymerase chain reaction (PCR) and isothermal nucleic acid amplification. We also provide an overview of nucleic acid amplification-based platforms including studies and commercialized products for SARS-CoV-2 detection. Technologically, we focus on the design of the microfluidic devices, the selected methods for sample preparation, nucleic acid amplification techniques, and endpoint analysis. We also compare features such as analysis time, sensitivity, and specificity of different platforms. The first section of the review discusses methods used in microfluidic devices for upstream clinical sample preparation. The second section covers the design, operation, and applications of PCR-based microfluidic devices. The third section reviews two common types of isothermal nucleic acid amplification methods (loop-mediated isothermal amplification and recombinase polymerase amplification) performed in microfluidic systems. The fourth section introduces microfluidic applications for nucleic acid amplification-based detection of SARS-CoV-2. Finally, the review concludes with the importance of full integration and quantitative analysis for clinical microbial identification. Full article
(This article belongs to the Special Issue Microfluidic Biosensing Platform)
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<p>Microfluidic technologies for clinical microbial detection.</p>
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<p>PCR-based microfluidic devices.</p>
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<p>Examples of PCR-based microfluidic devices and systems used for pathogen detection. Reproduced from [<xref ref-type="bibr" rid="B47-chemosensors-10-00123">47</xref>,<xref ref-type="bibr" rid="B51-chemosensors-10-00123">51</xref>,<xref ref-type="bibr" rid="B57-chemosensors-10-00123">57</xref>].</p>
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<p>Examples of microfluidic devices used for isothermal nucleic acid amplification for pathogen detection. Reproduced from [<xref ref-type="bibr" rid="B58-chemosensors-10-00123">58</xref>,<xref ref-type="bibr" rid="B62-chemosensors-10-00123">62</xref>,<xref ref-type="bibr" rid="B65-chemosensors-10-00123">65</xref>].</p>
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11 pages, 18265 KiB  
Article
High-Performance Bidirectional Chemical Sensor Platform Using Double-Gate Ion-Sensitive Field-Effect Transistor with Microwave-Assisted Ni-Silicide Schottky-Barrier Source/Drain
by Yeong-Ung Kim and Won-Ju Cho
Chemosensors 2022, 10(4), 122; https://doi.org/10.3390/chemosensors10040122 - 24 Mar 2022
Cited by 4 | Viewed by 3167
Abstract
This study proposes a bidirectional chemical sensor platform using ambipolar double-gate ion-sensitive field-effect transistors (ISFET) with microwave-assisted Ni-silicide Schottky-barrier (SB) source and drain (S/D) on a fully depleted silicon-on-insulator (FDSOI) substrate. The microwave-assisted Ni-silicide SB S/D offer bidirectional turn-on characteristics for both p- [...] Read more.
This study proposes a bidirectional chemical sensor platform using ambipolar double-gate ion-sensitive field-effect transistors (ISFET) with microwave-assisted Ni-silicide Schottky-barrier (SB) source and drain (S/D) on a fully depleted silicon-on-insulator (FDSOI) substrate. The microwave-assisted Ni-silicide SB S/D offer bidirectional turn-on characteristics for both p- and n-type channel operations. The p- and n-type operations are characterized by high noise resistance as well as improved mobility and excellent drift performance, respectively. These features enable sensing regardless of the gate voltage polarity, thus contributing to the use of detection channels based on various target substances, such as cells, antigen-antibodies, DNA, and RNA. Additionally, the capacitive coupling effect existing between the top and bottom gates help achieve self-amplified pH sensitivity exceeding the Nernst limit of 59.14 mV/pH without any additional amplification circuitry. The ambipolar FET sensor performance was evaluated for bidirectional electrical characteristics, pH detection in the single-gate and double-gate modes, and reliability in continuous and repetitive operations. Considering the excellent characteristics confirmed through evaluation, the proposed ambipolar chemical sensor platform is expected to be applicable to various fields including biosensors. And through linkage with subsequent studies, various medical applications and precision detector operations for specific markers will be possible. Full article
(This article belongs to the Collection pH Sensors, Biosensors and Systems)
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<p>(<bold>a</bold>) Schematic and (<bold>b</bold>) microscopic image of ambipolar DG ISFET with Ni-silicide SB S/Ds on an SOI substrate. (<bold>c</bold>) Schematic and (<bold>d</bold>) photograph of the fabricated EG unit.</p>
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<p>Simplified schematics of the DG ISFET sensor platform.</p>
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<p>(<bold>a</bold>) Sheet resistance (Rs) and (<bold>b</bold>) XRD patterns of the microwave-assisted Ni-silicides formed under various MWI powers. (<bold>c</bold>) The characterization of Schottky contact of S/D.</p>
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<p>Transfer characteristic (V<sub>G</sub>–I<sub>D</sub>) curves of the bipolar DG ISFETs operated by the top- or bottom-gate voltages in the (<bold>a</bold>) <italic>p</italic> and <italic>n</italic> regions. (<bold>b</bold>) Output characteristic (V<sub>D</sub>–I<sub>D</sub>) curves of the bipolar DG ISFETs operated by the top- or bottom-gate voltages in the <italic>p</italic> and <italic>n</italic> regions, respectively.</p>
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<p>Transfer characteristic (V<sub>G</sub>–I<sub>D</sub>) curves of the ambipolar DG ISFET for different pH buffer solutions. SG mode sensing in the (<bold>a</bold>) <italic>p</italic> region and (<bold>b</bold>) <italic>n</italic> region. DG mode sensing in the (<bold>c</bold>) <italic>p</italic> region and (<bold>d</bold>) <italic>n</italic> region.</p>
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<p>Reference voltage shift (ΔV<sub>REF</sub>) in the (<bold>a</bold>) <italic>p</italic>- and (<bold>b</bold>) <italic>n</italic>-region operations as a function of the pH value. The symbols and lines represent the experimental data and linear fits, respectively.</p>
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<p>Hysteresis effect of the ambipolar DG ISFET in the (<bold>a</bold>) <italic>p</italic> region and (<bold>b</bold>) <italic>n</italic> region for three different buffer solutions with pH values of 4, 7, and 10. The open and closed circles represent ΔV<sub>REF</sub> in the SG and DG sensing modes, respectively.</p>
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<p>Drift effects of the ambipolar DG ISFET in the (<bold>a</bold>) <italic>p</italic> region and (<bold>b</bold>) <italic>n</italic> region when the sensing membrane is immersed in a pH 7 buffer for 10 h. ΔV<sub>REF</sub> was monitored in the SG and DG sensing modes.</p>
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13 pages, 4965 KiB  
Article
Adsorption Properties of ZSM-5 Molecular Sieve for Perfluoroisobutyronitrile Mixtures and Its Fluorocarbon Decomposition Products
by Wei Liu, Xinjie Qiu, Xiaoxing Zhang, Shuangshuang Tian, Zian Yuan and Weihao Liu
Chemosensors 2022, 10(4), 121; https://doi.org/10.3390/chemosensors10040121 - 24 Mar 2022
Cited by 7 | Viewed by 3140
Abstract
Perfluoroisobutyronitrile (C4F7N), an environment-friendly insulating gas, has excellent insulating properties and has the potential to be used in gas-insulated equipment when mixed with CO2. Selecting suitable adsorption materials to adsorb the decomposition products of the C4 [...] Read more.
Perfluoroisobutyronitrile (C4F7N), an environment-friendly insulating gas, has excellent insulating properties and has the potential to be used in gas-insulated equipment when mixed with CO2. Selecting suitable adsorption materials to adsorb the decomposition products of the C4F7N mixture can ensure the safe and stable operation of the gas-insulated equipment and the personal safety of the operators in the electric power industry. The adsorption characteristics of the ZSM-5 molecular sieve on C4F7N and its five fluorocarbon decomposition products were investigated by adsorption experiments. The results show that the ZSM-5 molecular sieve has a certain adsorption effect on six fluorocarbon gases; the adsorption performance of C3F6 and C3F8 are the best, with an adsorption efficiency over 85%, while the concentration of CO2 and C4F7N is affected by the ZSM-5 molecular sieve. At the same time, the paper based on the Metropolis Monte Carlo simulation of Materials Studio software found that the ZSM-5 molecular sieve has the strongest adsorption effect on C4F7N molecules and the weakest adsorption effect on CO2 molecules. The stronger the polarity of the gas molecule, the more obvious the adsorption effect of molecular sieve structure on it. As a result, the ZSM-5 molecular sieve could be used in tail gas purification of insulated equipment, as well as to provide solutions for the development and production of protective equipment. Full article
(This article belongs to the Special Issue The State-of-the-Art Gas Sensor)
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<p>Adsorption experimental device.</p>
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<p>The concentration of fluorocarbon gases before and after the experiment.</p>
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<p>Concentration variation of standard gases of C<sub>4</sub>F<sub>7</sub>N and CO<sub>2</sub> before and after the experiment. (<b>a</b>) 15% C<sub>4</sub>F<sub>7</sub>N−85% He Infrared spectrometry before and after the experiment; (<b>b</b>) 15% CO<sub>2</sub>−85% He Infrared spectrometry before and after the experiment.</p>
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<p>The characteristic peak area and absorbance intensity of C<sub>4</sub>F<sub>7</sub>N and CO<sub>2</sub> before and after the adsorption experiment. (<b>a</b>) Area of characteristic peak; (<b>b</b>) Intensity of absorbance.</p>
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<p>Infrared spectra of 15% C<sub>4</sub>F<sub>7</sub>N−85% CO<sub>2</sub> gas mixtures before and after the experiment. (<b>a</b>) C<sub>4</sub>F<sub>7</sub>N; (<b>b</b>) CO<sub>2</sub>.</p>
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<p>NaZSM-5 molecular sieve model.</p>
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<p>Adsorbent molecular model (<b>a</b>) CF<sub>3</sub>H; (<b>b</b>) CF<sub>4</sub>; (<b>c</b>) C<sub>2</sub>F<sub>6</sub>; (<b>d</b>) C<sub>3</sub>F<sub>6</sub>; (<b>e</b>) C<sub>3</sub>F<sub>8</sub>; (<b>f</b>) CO<sub>2</sub>; (<b>g</b>) C<sub>4</sub>F<sub>7</sub>N.</p>
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<p>Distribution of possible adsorption sites in the structure of NaZSM-5 molecular sieve for five carbon-fluorine decomposition product gas molecules (<b>a</b>–<b>e</b>) and two main insulating gas molecules (<b>f</b>,<b>g</b>). (<b>a</b>) CF<sub>3</sub>H; (<b>b</b>) CF<sub>4</sub>; (<b>c</b>) C<sub>2</sub>F<sub>6</sub>; (<b>d</b>) C<sub>3</sub>F<sub>6</sub>; (<b>e</b>) C<sub>3</sub>F<sub>8</sub>; (<b>f</b>) CO<sub>2</sub>; (<b>g</b>) C<sub>4</sub>F<sub>7</sub>N.</p>
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<p>Probability distribution of adsorption heat of seven gas molecules on Nazsm-5 molecular sieve.</p>
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