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26 pages, 4155 KiB  
Review
Enhancing Sensitivity and Selectivity: Current Trends in Electrochemical Immunosensors for Organophosphate Analysis
by Yin Shen, Shichao Zhao, Fei Chen, Yanfei Lv and Li Fu
Biosensors 2024, 14(10), 496; https://doi.org/10.3390/bios14100496 - 12 Oct 2024
Viewed by 143
Abstract
This review examines recent advancements in electrochemical immunosensors for the detection of organophosphate pesticides, focusing on strategies to enhance sensitivity and selectivity. The widespread use of these pesticides has necessitated the development of rapid, accurate, and field-deployable detection methods. We discuss the fundamental [...] Read more.
This review examines recent advancements in electrochemical immunosensors for the detection of organophosphate pesticides, focusing on strategies to enhance sensitivity and selectivity. The widespread use of these pesticides has necessitated the development of rapid, accurate, and field-deployable detection methods. We discuss the fundamental principles of electrochemical immunosensors and explore innovative approaches to improve their performance. These include the utilization of nanomaterials such as metal nanoparticles, carbon nanotubes, and graphene for signal amplification; enzyme-based amplification strategies; and the design of three-dimensional electrode architectures. The integration of these sensors into microfluidic and lab-on-a-chip devices has enabled miniaturization and automation, while screen-printed and disposable electrodes have facilitated on-site testing. We analyze the challenges faced in real sample analysis, including matrix effects and the stability of biological recognition elements. Emerging trends such as the application of artificial intelligence for data interpretation and the development of aptamer-based sensors are highlighted. The review also considers the potential for commercialization and the hurdles that must be overcome for widespread adoption. Future research directions are identified, including the development of multi-analyte detection platforms and the integration of sensors with emerging technologies like the Internet of Things. This comprehensive overview provides insights into the current state of the field and outlines promising avenues for future development in organophosphate pesticide detection. Full article
(This article belongs to the Special Issue State-of-the-Art Biosensors in China (2nd Edition))
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<p>A schematic representation of an electrochemical immunosensor.</p>
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<p>(<b>A</b>) Fabrication of Au-SPEs/SAM/AChE. Reprinted with permission from Ref. [<a href="#B35-biosensors-14-00496" class="html-bibr">35</a>]. 2024, Elsevier. (<b>B</b>) GCE/NBCQDs@GO/mAb3C9 antibody/phage-mimotope M31/anti-M13 mAb-HRP. Reprinted with permission from Ref. [<a href="#B36-biosensors-14-00496" class="html-bibr">36</a>]. 2024, Elsevier.</p>
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<p>Scheme of fabrication procedure and sensing mechanism of cross-linked PVA/gelatin–AuNP NFM-based immunosensor for quinalphos detection. Reprinted with permission from Ref. [<a href="#B42-biosensors-14-00496" class="html-bibr">42</a>]. 2024, Elsevier.</p>
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<p>Scheme of fabrication procedure and sensing mechanism of cross-linked PVA/CA NFM-based immunosensor for parathion detection. Reprinted with permission from Ref. [<a href="#B43-biosensors-14-00496" class="html-bibr">43</a>]. 2024, Elsevier.</p>
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<p>Scheme of electrochemical immunoassay for CPF detection. Reprinted with permission from Ref. [<a href="#B47-biosensors-14-00496" class="html-bibr">47</a>]. 2024, Elsevier.</p>
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<p>Scheme of the fabrication process of FTO-AuNPs-chl-Ab for CPF detection. Reprinted with permission from Ref. [<a href="#B56-biosensors-14-00496" class="html-bibr">56</a>]. 2024, Elsevier.</p>
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<p>Scheme of the fabrication process of Fe<sub>3</sub>O<sub>4</sub> at TiO<sub>2</sub> magnetic nanoparticles for BChE detection. Reprinted with permission from Ref. [<a href="#B60-biosensors-14-00496" class="html-bibr">60</a>]. 2024, Elsevier.</p>
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<p>Scheme of immunosensing platform for measurement of enzyme activity and OP exposure. Reprinted with permission from Ref. [<a href="#B63-biosensors-14-00496" class="html-bibr">63</a>]. 2024, ACS.</p>
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<p>Detection of monocrotophos using an immunosensor with randomly layered GO. Reprinted with permission from Ref. [<a href="#B69-biosensors-14-00496" class="html-bibr">69</a>]. 2024, Elsevier.</p>
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<p>SEM image of (<b>A</b>) MOF/ITO (porous morphology). Reprinted with permission from Ref. [<a href="#B73-biosensors-14-00496" class="html-bibr">73</a>]. 2024, Elsevier. (<b>B</b>) three-dimensional gold nanoclusters. Reprinted with permission from Ref. [<a href="#B74-biosensors-14-00496" class="html-bibr">74</a>]. 2024, Elsevier. (<b>C</b>) Zr-MOF/ZrO<sub>2</sub>/MWCNT ternary composite.</p>
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<p>Fabrication procedure for graphene FET device for CPF detection. Reprinted with permission from Ref. [<a href="#B81-biosensors-14-00496" class="html-bibr">81</a>]. 2024, Springer.</p>
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<p>Scheme of the direct competitive immunosensor for the detection of IMD on AuNP-SPEs using monoclonal antibodies. Reprinted with permission from Ref. [<a href="#B85-biosensors-14-00496" class="html-bibr">85</a>]. 2024, Elsevier.</p>
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<p>Infographic summarizing the current challenges and future perspectives of electrochemical immunosensors for OP analysis.</p>
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17 pages, 8874 KiB  
Article
Grain Structure Engineering in Screen-Printed Silver Flake-Based Inks for High-Temperature Printed Electronics Applications
by Arjun Wadhwa, Mohammad Saadati, Jaime Benavides-Guerrero, Martin Bolduc and Sylvain G. Cloutier
Materials 2024, 17(20), 4966; https://doi.org/10.3390/ma17204966 - 11 Oct 2024
Viewed by 300
Abstract
We extensively studied serigraphic screen-printed commercial silver flake inks loaded with silicon inclusions in order to achieve pinning at the grain boundaries. Based on grain size measurements using electron backscattered diffraction (EBSD), commercial silver ink with silicon microparticle content of 5 wt.% shows [...] Read more.
We extensively studied serigraphic screen-printed commercial silver flake inks loaded with silicon inclusions in order to achieve pinning at the grain boundaries. Based on grain size measurements using electron backscattered diffraction (EBSD), commercial silver ink with silicon microparticle content of 5 wt.% shows significant grain growth retardation compared to pristine silver ink, which stabilizes electrical conductivity up to 700 °C via a Zener pinning mechanism. The modified silicon-loaded silver ink experiences a two-times increase in grain size when heated up to 700 °C, compared to a seven-times increase for pristine silver ink. In turn, this enables operation temperatures significantly higher than the conventional operational window of microparticle-based silver inks, which are usually limited to 400 °C. Using isothermal exposures of 10 min up to 4 h, this phenomenon is observed at temperatures ranging from 250 °C to 900 °C. The electrical conductivity stability, grain size evolution and oxide contents were studied up to 4 h. The activation energy of silver ink with silicon inclusions is 54% lower than for pristine silver ink due to the pining effect, which retards grain growth via the Zener mechanism. Most importantly, the electrical resistivity remains stable up to 700 °C, which is more than twice the operation limit for off-the-shelf screen-printable silver flake inks. Hence, we demonstrate that adding controlled amounts of silicon particles to silver inks for grain structure engineering can open new vistas of possibilities for screen-printed metallic inks. Full article
(This article belongs to the Section Electronic Materials)
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Figure 1
<p>(<b>a</b>) Schematic of the screen printing process; (<b>b</b>) thermal cycling ramp profile.</p>
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<p>(<b>a</b>) Raman spectra of pristine and modified (Ag–Si) ink; (<b>b</b>) particle size distribution of Si nanoparticles as purchased; (<b>c</b>) thermogalvanometric analysis of pristine and modified (Ag–Si) ink.</p>
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<p>SEM micrographs of (<b>a</b>) pristine Ag ink and (<b>b</b>) EDX map of (Ag–Si) ink sintered at 250°C with Si particles (highlighted in red and black arrows).</p>
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<p>Electrical conductivity of (<b>a</b>) pristine Ag and modified (Ag–Si) inks with (<b>b</b>) 3 wt.%, (<b>c</b>) 5 wt.%, (<b>d</b>) 7 wt.% and (<b>e</b>) 10 wt.% silver inks treated at incremental temperatures for 1 h of isothermal exposure. Electrical conductivity of pristine Ag and modified (Ag-5 wt.% Si) inks thermally treated at (<b>f</b>) 500 °C, (<b>g</b>) 500 °C, (<b>h</b>) 600 °C, (<b>i</b>) 700 °C, (<b>j</b>) 800 °C and (<b>k</b>) 900 °C over 10 min and 1–4 h isothermal exposure.</p>
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<p>Grain size evolution of pristine Ag and modified (Ag-5wt.% Si) inks post thermal treatment between 250 °C and 900 °C for (<b>a</b>) 10 min, (<b>b</b>) 1 h, (<b>c</b>) 2 h, (<b>d</b>) 3 h, (<b>e</b>) 4 h of isothermal exposure.</p>
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<p>SEM micrographs of pristine Ag ink thermally treated at (<b>a</b>) 400 °C, (<b>b</b>) 500 °C, (<b>c</b>) 600 °C, (<b>d</b>) 700 °C, (<b>e</b>) 800 °C and (<b>f</b>) 900 °C for 1 h.</p>
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<p>EBSD micrographs of pristine Ag ink thermally treated at (<b>a</b>) 400 °C, (<b>b</b>) 500 °C, (<b>c</b>) 600 °C, (<b>d</b>) 700 °C, (<b>e</b>) 800 °C and (<b>f</b>) 900 °C for 1 h.</p>
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<p>SEM micrographs of 5 wt.% modified (Ag-5 wt.% Si) ink thermally treated at (<b>a</b>) 400 °C, (<b>b</b>) 500 °C, (<b>c</b>) 600 °C, (<b>d</b>) 700 °C, (<b>e</b>) 800 °C and (<b>f</b>) 900 °C for 1 h.</p>
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<p>EBSD micrographs of 5 wt.% modified (Ag-5 wt.% Si) ink thermally treated at (<b>a</b>) 400 °C, (<b>b</b>) 500 °C, (<b>c</b>) 600 °C, (<b>d</b>) 700 °C, (<b>e</b>) 800 °C and (<b>f</b>) 900 °C for 1 h.</p>
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<p>SEM and EDX micrographs exhibiting the effects of (<b>a</b>,<b>c</b>) large Si particles (highlighted with red circles) and (<b>b</b>,<b>d</b>) smaller Si particles (highlighted with red arrows) on the morphology of printed films.</p>
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<p>XPS analysis of the silver ink samples after annealing. (<b>a</b>) % Oxygen concentration in silver oxide species for the pristine silver ink samples after a 3 h of isothermal annealing; (<b>b</b>) % oxygen concentration in silver oxide species for the pristine silver ink samples after a 4 h of isothermal annealing. (<b>c</b>) % Oxygen in silicon oxide and total silicon oxide in the modified (Ag–Si) ink samples after 3 h and 4 h of isothermal annealing.</p>
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<p>Arrhenius plot of the k parameter versus isothermal exposure temperature.</p>
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17 pages, 4461 KiB  
Article
A Novel Wearable Sensor for Measuring Respiration Continuously and in Real Time
by Amjad Ali, Yang Wei, Yomna Elsaboni, Jack Tyson, Harry Akerman, Alexander I. R. Jackson, Rod Lane, Daniel Spencer and Neil M. White
Sensors 2024, 24(20), 6513; https://doi.org/10.3390/s24206513 - 10 Oct 2024
Viewed by 329
Abstract
In this work, a flexible textile-based capacitive respiratory sensor, based on a capacitive sensor structure, that does not require direct skin contact is designed, optimised, and evaluated using both computational modelling and empirical measurements. In the computational study, the geometry of the sensor [...] Read more.
In this work, a flexible textile-based capacitive respiratory sensor, based on a capacitive sensor structure, that does not require direct skin contact is designed, optimised, and evaluated using both computational modelling and empirical measurements. In the computational study, the geometry of the sensor was examined. This analysis involved observing the capacitance and frequency variations using a cylindrical model that mimicked the human body. Four designs were selected which were then manufactured by screen printing multiple functional layers on top of a polyester/cotton fabric. The printed sensors were characterised to detect the performance against phantoms and impacts from artefacts, normally present whilst wearing the device. A sensor that has an electrode ratio of 1:3:1 (sensor, reflector, and ground) was shown to be the most sensitive design, as it exhibits the highest sensitivity of 6.2% frequency change when exposed to phantoms. To ensure the replicability of the sensors, several batches of identical sensors were developed and tested using the same physical parameters, which resulted in the same percentage frequency change. The sensor was further tested on volunteers, showing that the sensor measures respiration with 98.68% accuracy compared to manual breath counting. Full article
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Figure 1
<p>(<b>a</b>) The layout of the designed sensor. (<b>b</b>) The structure of the four sensor designs and ratio combinations of the sensor, reflector, and ground electrode.</p>
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<p>Diagram of simulation methodology conducted to obtain electric field distribution around each sensor design.</p>
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<p>(<b>a</b>) The computed vertical electric field is (1) below the ground electrode, (2) between the ground and reflector electrode (has a high electric field which reaches up to 75,000 v/m due to a thin dielectric layer), (3) between the sensor and phantom (design 1: vertical electrical field peak is 50 v/m higher than the rest of the design), and (4) within the phantom (the phantom is a glass cylinder of 80 mm diameter set to a dielectric constant of 5 with a glass wall thickness of 2.5 mm and filled with water having dielectric constant of 80). (<b>b</b>) The computed horizontal electric field distribution across the four sensor designs.</p>
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<p>The sensor capacitance was recorded when the phantom was located at z = 1, 5, 10, 15, 20, and 25 mm distances. The electric field distribution of the final sensor designs across the perpendicular plane and the parallel plane. The fringing field effect is present at the corners between the sensor and ground electrodes.</p>
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<p>Simulation capacitance results were obtained with 3 phantoms: muscle, acetone, and water. (<b>a</b>) shows the capacitance of each design between the sensor and ground electrodes, which is referred to as Csg and given a blue colour along with its scale on the left side of each graph. The capacitance between the sensor and the object is referred to as Cso, which is given an orange colour along with its orange scales on the right side of each graph. (<b>b</b>) shows each design’s total capacitance toward the phantom.</p>
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<p>(<b>a</b>) The final printed sensor in four designs. (<b>b</b>) SEM images show the different layers and their corresponding average thickness (showing the thickness of each layer).</p>
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<p>(<b>a</b>) Empirical setup to evaluate the sensor response toward phantoms. (<b>b</b>) The equivalent circuit model of the respiratory rate sensor and interfacing circuit.</p>
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<p>Frequency variation measurements obtained empirically when testing 3 different phantoms.</p>
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<p>(<b>a</b>) Design 2’s identical replicas (Sample 1, 2, and 3) from three different batches of screen printing, and (<b>b</b>) their consistently similar %f-c toward mowing away water phantom.</p>
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<p>(<b>a</b>) Humidity variations ranging from 40% to 80% RH at 24 °C cause an average standard deviation of 0.19 in the design 2 response. (<b>b</b>) Temperature variations ranging from 18 °C to 35 °C at 60% relative humidity (RH) impact the response of design 2, resulting in an average standard deviation of 0.34.</p>
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<p>(<b>a</b>) The results of the flexing durability test conducted empirically on the four designs wrapped on cylinders of multiple diameters. (<b>b</b>) The graph shows the four designs’ responses to increasing pressure. (<b>c</b>) The graph shows the impact of rubbing on sensor response.</p>
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<p>(<b>a</b>) The left image shows the sensor that is attached to the lower part of the chest of the test subject in a sedentary position. The middle image shows how the test subject’s torso was divided into nine positions. (<b>b</b>) The sensor was attached to each position and measured the corresponding breathing rate for one minute. Precise frequency peaks corresponding to the breathing rate can be seen when the sensor is attached at positions 4, 7, 8, and 9. (<b>c</b>) shows the sensor’s response for a random breathing rate of 11 and 22 in one minute. (<b>d</b>) The sensor is attached at position 8, while the test subject is in standing posture and took 11 breaths in one minute.</p>
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13 pages, 3048 KiB  
Article
Paper-Based DNA Biosensor for Rapid and Selective Detection of miR-21
by Alexander Hunt, Sri Ramulu Torati and Gymama Slaughter
Biosensors 2024, 14(10), 485; https://doi.org/10.3390/bios14100485 - 8 Oct 2024
Viewed by 562
Abstract
Cancer is the second leading cause of death globally, with 9.7 million fatalities in 2022. While routine screenings are vital for early detection, healthcare disparities persist, highlighting the need for equitable solutions. Recent advancements in cancer biomarker identification, particularly microRNAs (miRs), have improved [...] Read more.
Cancer is the second leading cause of death globally, with 9.7 million fatalities in 2022. While routine screenings are vital for early detection, healthcare disparities persist, highlighting the need for equitable solutions. Recent advancements in cancer biomarker identification, particularly microRNAs (miRs), have improved early detection. MiR-21 is notably overexpressed in various cancers and can be a valuable diagnostic tool. Traditional detection methods, though accurate, are costly and complex, limiting their use in resource-limited settings. Paper-based electrochemical biosensors offer a promising alternative, providing cost-effective, sensitive, and rapid diagnostics suitable for point-of-care use. This study introduces an innovative electrochemical paper-based biosensor that leverages gold inkjet printing for the quantitative detection of miR-21. The biosensor, aimed at developing cost-effective point-of-care devices for low-resource settings, uses thiolated self-assembled monolayers to immobilize single-stranded DNA-21 (ssDNA-21) on electrodeposited gold nanoparticles (AuNPs) on the printed gold surface, facilitating specific miR-21 capture. The hybridization of ssDNA-21 with miR-21 increases the anionic barrier density, impeding electron transfer from the redox probe and resulting in a current suppression that correlates with miR-21 concentration. The biosensor exhibited a linear detection range from 1 fM to 1 nM miR-21 with a sensitivity of 7.69 fM µA−1 cm2 and a rapid response time (15 min). With a low detection limit of 0.35 fM miR-21 in serum, the biosensor also demonstrates excellent selectivity against interferent species. This study introduces an electrochemical paper-based biosensor that uses gold inkjet printing to precisely detect miR-21, a key biomarker overexpressed in various cancers. This innovative device highlights the potential for cost-effective, accessible cancer diagnostics in underserved areas. Full article
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Figure 1
<p>Schematic illustration of (<b>A</b>) electrochemical PhP-Au/AuNPs biosensor fabrication process and (<b>B</b>) ssDNA-21 immobilization and hybridization with target miR-21 sensing process. Electrode fabrication is further detailed in the <a href="#app1-biosensors-14-00485" class="html-app">Supplemental Information</a>.</p>
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<p>SEM microgrphs of (<b>A</b>) PhP-Au before sintering, (<b>B</b>) after sintering for 30 min at 140 °C, and (<b>C</b>) after electrodeposition. White arrows highlight insulating gaps.</p>
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<p>Cyclic voltammogram (CV) of PhP-Au (i), PhP-Au/AuNPs (ii), PhP-Au/AuNPs/ss-DNA (iii), PhP-Au/AuNPs/ss-DNA/miR-21 (iv) electrode. Voltammograms were obtained in 5 mM (K<sub>3</sub>Fe(CN)<sub>6</sub><sup>4−/3−</sup>) + 0.1 M KCl with a scan rate of 100 mV s<sup>−1</sup>.</p>
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<p>CV response of (<b>A</b>) PhP-Au/AuNPs electrode and (<b>C</b>) PhP-Au/AuNPs/ssDNA electrode from varying scan rates (a–h: 10–150 mV s<sup>−1</sup>) with (<b>B</b>,<b>D</b>) corresponding linearity plot of peak anodic and cathodic current densities vs. square root of scan rates (ν). Voltammograms were obtained in 5 mM (K<sub>3</sub>Fe(CN)<sub>6</sub><sup>4−/3−</sup>) + 0.1 M KCl. A dashed line indicates the baseline current.</p>
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<p>(<b>A</b>) Change in current density (Δ<span class="html-italic">j</span>) vs. various ssDNA-21 concentrations and (<b>B</b>) Δ<span class="html-italic">j</span> vs. various miR-21 hybridization times. Voltammograms were obtained in 5 mM (K<sub>3</sub>Fe(CN)<sub>6</sub><sup>4−/3−</sup>) + 0.1 M KCl. Hybridization experiments were conducted in duplicates.</p>
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<p>(<b>A</b>) SWV of varying target miR-21 concentrations (a: 0 M, b: 1fM, c: 10 fM, d: 100 fM, e: 1 pM, f: 10 pM, g: 100 pM, h: 1 nM) and (<b>B</b>) corresponding calibration curve. Voltammograms were obtained in 5 mM (K<sub>3</sub>Fe(CN)<sub>6</sub><sup>4−/3−</sup>) + 0.1 M KCl. Experiments were conducted in duplicates.</p>
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<p>Selectivity and stability of the electrochemical biosensor. (<b>A</b>) % Activity of miR-21 biosensor against non-complementary miRs. (<b>B</b>) % Stability of PhP-Au/AuNPs/ssDNA vs. days of storage. Experiments were conducted in duplicates.</p>
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<p>(<b>A</b>) SWV of varying target miR-21 concentrations (a: 0 M, b: 1fM, c: 10 fM, d: 100 fM, e: 1 pM, f: 10 pM, g: 100 pM, h: 1 nM) and (<b>B</b>) corresponding calibration curve of the target miR-21 concentrations in serum diluted 1000-fold. Voltammograms were obtained in 5 mM (K<sub>3</sub>Fe(CN)<sub>6</sub><sup>4−/3−</sup>) + 0.1 M KCl. Experiments were conducted in duplicates.</p>
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15 pages, 74974 KiB  
Article
Characterization of Silver Conductive Ink Screen-Printed Textile Circuits: Effects of Substrate, Mesh Density, and Overprinting
by Hyobin Im and Jung-Sim Roh
Materials 2024, 17(19), 4898; https://doi.org/10.3390/ma17194898 - 6 Oct 2024
Viewed by 434
Abstract
This study explores the intricate interaction between the properties of textile substrates and screen-printing parameters in shaping fabric circuits using silver conductive ink. Via analyzing key variables such as fabric type, mesh density, and the number of overprinted layers, the research revealed how [...] Read more.
This study explores the intricate interaction between the properties of textile substrates and screen-printing parameters in shaping fabric circuits using silver conductive ink. Via analyzing key variables such as fabric type, mesh density, and the number of overprinted layers, the research revealed how the porous structure, large surface area, and fiber morphology of textile substrates influence ink absorption, ultimately enhancing the electrical connectivity of the printed circuits. Notably, the hydrophilic cotton staple fibers fabric effectively absorbed the conductive ink into the fabric substrate, demonstrating superior electrical performance compared with the hydrophobic polyester filament fabric after three overprinting, unlike the results observed after a single print. As mesh density decreased and the number of prints increased, the electrical resistance of the circuit gradually reduced, but ink bleeding on the fabric surface became more pronounced. Cotton fabric, via absorbing the ink deeply, exhibited less surface bleeding, while polyester fabric showed more noticeable ink spreading. These findings provide valuable insights for improving screen printing technology for textile circuits and contribute to the development of advanced fabric circuits that enhance the functionality of smart wearable technology. Full article
(This article belongs to the Special Issue Properties of Textiles and Fabrics and Their Processing)
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<p>Screen printing process: (<b>a</b>) control system, (<b>b</b>) digital screen making, and (<b>c</b>) screen printing, (<b>d</b>) IR drying.</p>
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<p>SEM images of the cross-section of substrate fabrics: (<b>a</b>) cotton fabric (150×), (<b>b</b>) polyester fabric (150×), (<b>c</b>) printed circuit on cotton fabric (#1, 120G, single screen-printed, 200×), and (<b>d</b>) printed circuit (#1) on polyester fabric (#1, 120G, single screen-printed, 200×).</p>
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<p>Thickness of conductive layer (#1).</p>
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<p>Size increases in width (<b>a</b>) and length (<b>b</b>) directions between the screen-printed circuits and original circuit designs.</p>
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<p>Electrical resistance of single screen-printed textile circuits depending on mesh density, substrate properties, and circuit pattern: (<b>a</b>) polyester film substrate, (<b>b</b>) cotton fabric substrate, and (<b>c</b>) polyester fabric substrate.</p>
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<p>Electrical resistance of two overprinting screen-printed textile circuits dependent on mesh density, substrate properties, and circuit pattern: (<b>a</b>) cotton fabric substrate and (<b>b</b>) polyester fabric substrate.</p>
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<p>Electrical resistance of three overprinting screen-printed textile circuits dependent on mesh density, substrate properties, and circuit pattern: (<b>a</b>) cotton fabric substrate and (<b>b</b>) polyester fabric substrate.</p>
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13 pages, 2510 KiB  
Article
Sandwich-Type Electrochemical Aptasensor with Supramolecular Architecture for Prostate-Specific Antigen
by Anabel Villalonga, Raúl Díaz, Irene Ojeda, Alfredo Sánchez, Beatriz Mayol, Paloma Martínez-Ruiz, Reynaldo Villalonga and Diana Vilela
Molecules 2024, 29(19), 4714; https://doi.org/10.3390/molecules29194714 - 5 Oct 2024
Viewed by 372
Abstract
A novel sandwich-type electrochemical aptasensor based on supramolecularly immobilized affinity bioreceptor was prepared via host–guest interactions. This method utilizes an adamantane-modified, target-responsive hairpin DNA aptamer as a capture molecular receptor, along with a perthiolated β-cyclodextrin (CD) covalently attached to a gold-modified electrode surface [...] Read more.
A novel sandwich-type electrochemical aptasensor based on supramolecularly immobilized affinity bioreceptor was prepared via host–guest interactions. This method utilizes an adamantane-modified, target-responsive hairpin DNA aptamer as a capture molecular receptor, along with a perthiolated β-cyclodextrin (CD) covalently attached to a gold-modified electrode surface as the transduction element. The proposed sensing strategy employed an enzyme-modified aptamer as the signalling element to develop a sandwich-type aptasensor for detecting prostate-specific antigen (PSA). To achieve this, screen-printed carbon electrodes (SPCEs) with electrodeposited reduced graphene oxide (RGO) and gold nanoferns (AuNFs) were modified with the CD derivative to subsequently anchor the adamantane-modified anti-PSA aptamer via supramolecular associations. The sensing mechanism involves the affinity recognition of PSA molecules on the aptamer-enriched electrode surface, followed by the binding of an anti-PSA aptamer–horseradish peroxidase complex as a labelling element. This sandwich-type arrangement produces an analytical signal upon the addition of H2O2 and hydroquinone as enzyme substrates. The aptasensor successfully detected the biomarker within a concentration range of 0.5 ng/mL to 50 ng/mL, exhibiting high selectivity and a detection limit of 0.11 ng/mL in PBS. Full article
(This article belongs to the Special Issue Nano-Functional Materials for Sensor Applications)
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Figure 1
<p>Representative FE-SEM images of bare SPCE (<b>A</b>), rGO/SPCE (<b>B</b>), AuNFs/rGO/SPCE (<b>C</b>), CD–AuNFs/rGO/SPCE (<b>D</b>), Apt–ADA/CD–AuNFs/rGO/SPCE (<b>E</b>), MCH/Apt–ADA/CD–AuNFs/rGO/SPCE (<b>F</b>).</p>
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<p>Cyclic voltammograms (<b>A</b>) and Nyquist plots (<b>B</b>) of SPCE before (a) and after sequential modification with rGO (b), AuNFs (c), CD (d), Apt–ADA (e), and MCH (f). Cyclic voltammograms (<b>C</b>) and Nyquist plots (<b>D</b>) of the sensor (a) and further incubation with PSA (b) and Apt–HRP (c). Measured in 0.1 M KCl solution containing 5 mM K<sub>3</sub>[Fe(CN)<sub>6</sub>]/K<sub>4</sub>[Fe(CN)<sub>6</sub>] (1:1), (<b>A</b>,<b>C</b>) scan rate  =  50 mV·s<sup>−1</sup>. Conditions for EIS (<b>B</b>,<b>D</b>): frequency range of 0.01 to 106 Hz at a fixed potential.</p>
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<p>Nyquist plots of Apt–ADA/CD-AuNFs/rGO/SPCE electrode (<b>A</b>) before (a) and after sequential incubation with NaOH (b), MCH (c), and PSA (d). Nyquist plots of Apt–ADA/CD–AuNFs/rGO/SPCE electrode (<b>B</b>) before (a) and after sequential incubation with ADA-COOH in NaOH (b), MCH (c) and PSA (d). Measured in 0.100 M KCl solution containing 5 mM K<sub>3</sub>[Fe(CN)<sub>6</sub>]/K<sub>4</sub>[Fe(CN)<sub>6</sub>] (1:1).</p>
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<p>Amperometric responses (<b>A</b>) and relative amperometric analytical signal (<b>B</b>) of the aptasensor, previously incubated with NaOH (grey) or ADA-COOH in NaOH (red), towards PSA.</p>
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<p>(<b>A</b>) Calibration plot for the aptasensor towards PSA in 0.1 M sodium phosphate buffer, pH 7.0. (<b>B</b>) Relative amperometric response of the aptasensor toward 50 ng·mL<sup>−1</sup> PSA and 100 ng·mL<sup>−1</sup> of CEA, HSA, IgG, and TBA, respectively. (<b>C</b>) Relative amperometric response of the aptasensor toward PSA and mixtures with other potential interfering proteins at the same concentration cited above.</p>
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<p>Schematic representation of the processes involved in the assembly (<b>A</b>) and method of use (<b>B</b>) of the aptasensor for PSA.</p>
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32 pages, 6198 KiB  
Review
A Review on Preparation of Palladium Oxide Films
by Petre Badica and Adam Lőrinczi
Coatings 2024, 14(10), 1260; https://doi.org/10.3390/coatings14101260 - 1 Oct 2024
Viewed by 595
Abstract
Fabrication aspects of PdO thin films and coatings are reviewed here. The work provides and organizes the up-to-date information on the methods to obtain the films. In recent years, the interest in Pd oxide for different applications has increased. Since Pd can be [...] Read more.
Fabrication aspects of PdO thin films and coatings are reviewed here. The work provides and organizes the up-to-date information on the methods to obtain the films. In recent years, the interest in Pd oxide for different applications has increased. Since Pd can be converted into PdO, it is instructive to pay attention to the preparation of the pure and the alloyed Pd films, heterostructures, and nanoparticles synthesized on different substrates. The development of PdO films is presented from the early reports on coatings’ formation by oxidation of Pd foils and wires to present technologies. Modern synthesis/growth routes are gathered into chemical and physical categories. Chemical methods include hydrothermal, electrochemical, electroless deposition, and coating methods, such as impregnation, precipitation, screen printing, ink jet printing, spin or dip coating, chemical vapor deposition (CVD), and atomic layer deposition (ALD), while the physical ones include sputtering and cathodic arc deposition, laser ablation, ion or electron beam-induced deposition, evaporation, and supersonic cluster beam deposition. Analysis of publications indicates that many as-deposited Pd or Pd-oxide films are granular, with a high variety of morphologies and properties targeting very different applications, and they are grown on different substrates. We note that a comparative assessment of the challenges and quality among different films for a specific application is generally missing and, in some cases, it is difficult to make a distinction between a film and a randomly oriented, powder-like (granular), thin compact material. Textured or epitaxial films of Pd or PdO are rare and, if orientation is observed, in most cases, it is obtained accidentally. Some practical details and challenges of Pd oxidation toward PdO and some specific issues concerning application of films are also presented. Full article
(This article belongs to the Special Issue Advances of Nanoparticles and Thin Films)
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<p>Arbitrary classification of the technological routes to obtain Pd and PdO coatings.</p>
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<p>Adapted from [<a href="#B98-coatings-14-01260" class="html-bibr">98</a>]. (<b>a</b>) Electrochemical gas sensor arrangement (30 mL glass cell): RE—reference electrode; MFC—mass flow controller and the inlet for the gas covered with fluorinated ethylene propylene (FEP) H<sub>2</sub> gas-permeable membrane; WE—working electrode, PdO thin film of 1 μm thickness on ITO substrate; CE—counter electrode, Pt rod. (<b>b</b>) Room-temperature response by using the sensing arrangement from (<b>a</b>) when passing a H<sub>2</sub> gas (10%–70% in Ar) into the cell for 200 s and for a constant potential on electrodes of 1 V.</p>
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<p>Reproduced with permission from [<a href="#B106-coatings-14-01260" class="html-bibr">106</a>]. PdO sensor resistance at different ozone concentrations as a function of time at an operating temperature of 220 °C. SA denotes synthetic air. Note that ozone (O<sub>3</sub>) is harmful to human health, similar to other oxidizing gases, such as NO<sub>x</sub>, SO<sub>2</sub>, and Cl<sub>2</sub>. It is a by-product of many modern technologies, and its interaction under sunlight with volatile hydrocarbons produces many toxic organic compounds.</p>
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<p>Reproduced with permission from [<a href="#B121-coatings-14-01260" class="html-bibr">121</a>]. (<b>i</b>) TEM images taken on (<b>a</b>,<b>b</b>) ZnO and (<b>c</b>,<b>d</b>) ZnO-PdO. (<b>ii</b>) Response to toluene and ethanol of the structures from (<b>i</b>) at different operating temperatures.</p>
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<p>Reproduced with permission from [<a href="#B124-coatings-14-01260" class="html-bibr">124</a>]. (<b>a</b>–<b>c</b>) SEM images of Pd/PdO films obtained by thermolysis in air, low vacuum, and N<sub>2</sub>. (<b>d</b>–<b>f</b>) SEM images of films from (<b>a</b>–<b>c</b>) were taken at higher magnification. (<b>g</b>–<b>i</b>) SEM images on cross-sections of the films from (<b>a</b>–<b>c</b>).</p>
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<p>Reproduced with permission from [<a href="#B167-coatings-14-01260" class="html-bibr">167</a>]. (<b>a</b>) SEM image of the porous Pd thin film on AAO substrate prepared by <span class="html-italic">dc</span> magnetron sputtering and post-annealed at 200 °C, and (<b>b</b>) room-temperature response at various hydrogen concentrations in nitrogen carrier gas. On the Pd film, Au electrodes (10 mm × 3 mm) were deposited by thermal evaporation.</p>
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<p>Reproduced with permission from [<a href="#B176-coatings-14-01260" class="html-bibr">176</a>]. SEM images of reactively sputtered films in different oxygen atmospheres: (<b>a</b>) 15%, (<b>b</b>) 20%, (<b>c</b>) 25%, and (<b>d</b>) 30%.</p>
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<p>Reproduced with permission from [<a href="#B185-coatings-14-01260" class="html-bibr">185</a>]. (<b>a</b>) Optical sensor arrangement based on optical absorbance of the sample when irradiated from a source of a halogen lamp in the spectral range of 400–800 nm. (<b>b</b>) Response time (calculated as the average time to change from 5% to 95% of the absorbance) at room temperature of the samples with different thicknesses to 5 vol.% H<sub>2</sub> gas in nitrogen.</p>
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<p>Reproduced with permission from [<a href="#B225-coatings-14-01260" class="html-bibr">225</a>]. Fabrication of a typical Pd/MOS (MOS—metal oxide semiconductor) capacitor hydrogen sensor. The hydrogen diffuses from the metal Pd gate (active element) and creates a dipole layer at the (Pd/SiO<sub>2</sub>) interface that changes the work function of the active element. The response, R (%) = (C<sub>H</sub> − C<sub>N</sub>)/C<sub>N</sub> × 100, where C<sub>H</sub> and C<sub>N</sub> are the capacitance of the sensor in hydrogen gas and pure nitrogen, respectively. The carrier gas is nitrogen, argon, and air.</p>
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<p>Reproduced with permission from [<a href="#B245-coatings-14-01260" class="html-bibr">245</a>]. SEM images showing the morphology of Ir<sub>(1−x)</sub>Pd<sub>x</sub>O<sub>y</sub> films deposited on 316 SS substrates for: (<b>a</b>) x = 0.14, (<b>b</b>) x = 0.50, (<b>c</b>) x = 0.90, and (<b>d</b>) x = 0.95. Map of morphology summarizing results from (<b>a</b>–<b>d</b>) depending on the composition of the Ir<sub>(1−x)</sub>Pd<sub>x</sub>O<sub>y</sub> films (<b>e</b>).</p>
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11 pages, 3574 KiB  
Article
Charged Microdroplets Deposition for Nanostructured-Based Electrode Surface Modification
by Rosaceleste Zumpano, Marco Agostini, Franco Mazzei, Anna Troiani, Chiara Salvitti, Marta Managò, Alessia Di Noi, Andreina Ricci and Federico Pepi
Surfaces 2024, 7(4), 801-811; https://doi.org/10.3390/surfaces7040052 - 1 Oct 2024
Viewed by 459
Abstract
Accelerated synthesis of gold nanoparticles (AuNPs) in charged microdroplets produced by electrospray ionization (ESI) was exploited to modify the surface of graphite screen-printed electrodes (GSPEs). The deposited AuNPs were then functionalized by the charged microdroplets deposition of 6-ferrocenyl-hexanethiol (6Fc-ht) solutions that act as [...] Read more.
Accelerated synthesis of gold nanoparticles (AuNPs) in charged microdroplets produced by electrospray ionization (ESI) was exploited to modify the surface of graphite screen-printed electrodes (GSPEs). The deposited AuNPs were then functionalized by the charged microdroplets deposition of 6-ferrocenyl-hexanethiol (6Fc-ht) solutions that act as reducing and stabilizing agents and provide electrochemical properties for the modified electrodes. The morphology and composition of the AuNPs were characterized by scanning electron microscopy (SEM). Cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) were used to investigate the electrochemical behavior of the modified electrodes. The results showed that the ESI microdroplets deposition technique produces uniform and well-dispersed AuNPs on GSPE, and optimal conditions for deposition were identified, enhancing GSPE electrocatalytic performance. Further functionalization by ESI microdroplets of AuNPs with 6Fc-ht demonstrated improved redox properties compared with the conventional self-assembled monolayer (SAM) method, highlighting the technique’s potential for the easy and fast functionalization of electrochemical sensors. Full article
(This article belongs to the Special Issue Recent Advances in Catalytic Surfaces and Interfaces)
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<p>SEM images: (<b>a</b>,<b>d</b>) 2 min of deposition; (<b>b</b>,<b>e</b>) 4 min of deposition; (<b>c</b>,<b>f</b>) 10 min of deposition.</p>
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<p>(<b>a</b>) CV measurements of AuNPs-GSPE surfaces modified under different deposition times, performed in K<sub>4</sub>[Fe(CN)<sub>6</sub>]/K<sub>3</sub>[Fe(CN)<sub>6</sub>] 1 mM, KCl 0.1 M, between −0.4 and 0.6 V vs. Ag/AgCl<sub>sat.</sub>, rate = 10 mV/s. (<b>b</b>) EIS measurements of AuNPs-GSPE surfaces under different deposition times, performed in K<sub>4</sub>[Fe(CN)<sub>6</sub>]/K<sub>3</sub>[Fe(CN)<sub>6</sub>] 5 mM, KCl 0.1 M, E<sub>DC</sub> = 0.215 V, E<sub>AC</sub> = 0.01 V, νmax = 100,000 Hz, νmin = 0.1 Hz. The dotted lines represent experimental data, and the solid lines represent the fit lines. Inset: Randles (R(Q[RW])) and R(QR)(Q[RW]) circuits employed for the fitting procedure.</p>
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<p>Bode plots (<b>a</b>) |Z| and (<b>b</b>) phase angle behavior in the function of applied ν.</p>
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<p>DPV measurements of AuNPs-GSPE surfaces under different deposition times, performed in K<sub>4</sub>[Fe(CN)<sub>6</sub>]/K<sub>3</sub>[Fe(CN)<sub>6</sub>] 1 mM, KCl 0.1 M, E<sub>DC</sub> = 0.215 V, E<sub>AC</sub> = 0.01 V, νmax = 100,000 Hz, νmin = 0.1 Hz.</p>
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<p>(<b>a</b>) CV measurements of GSPE surfaces functionalized with AuNPs at different HAuCl<sub>4</sub> deposition times, modified with 6Fc-ht through the SAM procedure performed in KCl 0.1 M, between 0 and 0.85 V vs. Ag/AgCl<sub>sat.</sub>, rate = 10 mV/s. 6Fc-ht oxidation signals (1, 2, and 3) and gold oxidation signals (4, 5); (<b>b</b>) CV measurements of GSPE surfaces functionalized with AuNPs at different HAuCl<sub>4</sub> deposition times, modified with 6Fc-ht through the ESI technique performed in KCl 0.1 M between −0.2 and 0.5 V vs. Ag/AgCl<sub>sat.</sub>, rate = 10 mV/s.</p>
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<p>DPV measurements of GSPE surfaces functionalized with AuNPs at different HAuCl<sub>4</sub> deposition times, modified with 6Fc-ht through the SAM procedure (<b>a</b>,<b>b</b>) and ESI microdroplets deposition technique (<b>c</b>,<b>d</b>), performed in KCl 0.1 M, E<sub>DC</sub> = 0.215 V, E<sub>AC</sub> = 0.01 V, νmax = 100,000 Hz, and νmin = 0.1 Hz.</p>
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<p>(<b>a</b>) DPV curves collected in the absence and presence of increasing concentrations of H<sub>2</sub>O<sub>2</sub> in the range 0–300 μM in PBS 0.01 M, KCl 0.1 M. In the inset are reported the ΔI (I-I<sub>0</sub>) over the analyzed H<sub>2</sub>O<sub>2</sub> concentration range; (<b>b</b>) sensor calibration line.</p>
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13 pages, 2703 KiB  
Article
Portable Electrochemical System and Platform with Point-of-Care Determination of Urine Albumin-to-Creatinine Ratio to Evaluate Chronic Kidney Disease and Cardiorenal Syndrome
by Shuenn-Yuh Lee, Ding-Siang Ciou, Hao-Yun Lee, Ju-Yi Chen, Yi-Chieh Wei and Meng-Dar Shieh
Biosensors 2024, 14(10), 463; https://doi.org/10.3390/bios14100463 - 27 Sep 2024
Viewed by 444
Abstract
Abstract: The urine albumin (Alb)-to-creatinine (Crn) ratio (UACR) is a sensitive and early indicator of chronic kidney disease (CKD) and cardiorenal syndrome. This study developed a portable and wireless electrochemical-sensing platform for the sensitive and accurate determination of UACR. The developed platform consists [...] Read more.
Abstract: The urine albumin (Alb)-to-creatinine (Crn) ratio (UACR) is a sensitive and early indicator of chronic kidney disease (CKD) and cardiorenal syndrome. This study developed a portable and wireless electrochemical-sensing platform for the sensitive and accurate determination of UACR. The developed platform consists of a carbon nanotube (CNT)-2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid)(ABTS)-based modified UACR sensor, a miniaturised potentiostat, a cup holder embedded with a magnetic stirrer and a smartphone app. The UACR sensing electrode is composed of two screen-printed carbon working electrodes, one screen-printed carbon counter electrode and a screen-printed AgCl reference electrode. The miniaturised potentiostat, which is controlled by the developed app, performs cyclic voltammetry and amperometry to detect Alb and Crn, respectively. Clinical trials of the proposed system by using spot urine samples from 30 diabetic patients indicate that it can accurately classify all three CKD risk statuses within 30 min. The high accuracy of our proposed sensing system exhibits satisfactory agreement with the commercial biochemical analyser TBA-25FR (Y = 0.999X, R2 = 0.995). The proposed UACR sensing system offers a convenient, reliable and affordable solution for personal mobile health monitoring and point-of-care urinalysis. Full article
(This article belongs to the Special Issue Electrochemical Biosensors for Disease Detection)
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<p>(<b>a</b>) Layered graph of the customised electrode. (<b>b</b>) Proposed electrochemical UACR dual working sensor.</p>
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<p>Proposed electrochemical detection system.</p>
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<p>Design of the potentiostat for performing the CA and CV programmes.</p>
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<p>(<b>a</b>) Proposed portable UACR electrochemical system and platform. (<b>b</b>) UACR examination process of the proposed portable electrochemical system and platform.</p>
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<p>(<b>a</b>) CV responses of the SPE(W<sub>1</sub>)|CNT-ABTS<sub>(CV)</sub> to Alb of various concentrations. (<b>b</b>) Calibration curve of the proposed albumin sensor in urine with known concentrations of 0.08, 0.1, 0.18, 0.54, 0.8, 0.94, 0.98, 5.14, 6.1, and 19.2 mg/dL, respectively. (<b>c</b>) Regression analysis of C<sub>Alb</sub> in five urine samples determined using TBA-25FR and the SPE(W<sub>1</sub>)|CNT-ABTS<sub>(CV)</sub> electrode is shown in red; The deviation percentage in the C<sub>Alb</sub> values determined by TBA™-25FR and SPE(W<sub>1</sub>)|CNT-ABTS<sub>(CV)</sub> electrode is shown in blue.</p>
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<p>(<b>a</b>) CA responses of the SPE(W<sub>2</sub>)|CNT-ABTS|Nafion electrode to various Crn concentrations. (<b>b</b>) Calibration curve of the proposed Crn sensor in urine with known concentrations of 1.67, 11.55, 20.10, 31.22, 41.80 and 58.62 mg/dL, respectively. (<b>c</b>) Regression analysis of C<sub>Crn</sub> in five urine samples determined by TBA-25FR and SPE(W<sub>2</sub>)|CNT-ABTS|Nafion is shown in red; The deviation percentage in the C<sub>Crn</sub> values determined by TBA™-25FR and SPE(W<sub>2</sub>)|CNT-ABTS|Nafion electrode is shown in blue.</p>
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<p>(<b>a</b>) Regression analysis of the C<sub>Alb</sub> of 30 spot urine samples determined using TBA-25FR and the SPE(W<sub>1</sub>)|CNT-ABTS<sub>(CV)</sub> electrode (<b>b</b>) Regression analysis of the C<sub>Crn</sub> of 30 spot urine samples determined using TBA-25FR and the SPE(W<sub>2</sub>)|CNT-ABTS|Nafion electrode. (<b>c</b>) Regression analysis of the UACR value of 30 spot urine samples calculated using the Alb and Crn results of TBA-25FR and the proposed UACR sensing system and platform.</p>
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18 pages, 2504 KiB  
Article
Characteristics and Source Profiles of Volatile Organic Compounds (VOCs) by Several Business Types in an Industrial Complex Using a Proton-Transfer-Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS)
by Kyoung-Chan Kim, Byeong-Hun Oh, Jeong-Deok Baek, Chun-Sang Lee, Yong-Jae Lim, Hung-Soo Joo and Jin-Seok Han
Atmosphere 2024, 15(10), 1156; https://doi.org/10.3390/atmos15101156 - 27 Sep 2024
Viewed by 574
Abstract
Volatile organic compounds (VOCs) are one of significant contributors to air pollution and have profound effects on human health and the environment. This study introduces a detailed analysis of VOC emissions from various industries within an industrial complex using a high-resolution measurement instrument. [...] Read more.
Volatile organic compounds (VOCs) are one of significant contributors to air pollution and have profound effects on human health and the environment. This study introduces a detailed analysis of VOC emissions from various industries within an industrial complex using a high-resolution measurement instrument. This study aimed to identify the VOC profiles and their concentrations across 12 industries. Sampling was conducted across 99 facilities in an industrial complex in South Korea, and VOC analysis was performed based on measurement data using a Proton-Transfer-Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS). The results indicated that the emission of oxygenated VOCs (OVOCs) was dominant in most industries. Aromatic hydrocarbons were also dominant in most industries, except in screen printing (SP), lubricating oil and grease manufacturing (LOG), and industrial laundry services (ILS) industries. Chlorinated VOCs (Cl-VOCs) showed a relatively higher level in the metal plating (MP) industry than those in other industries and nitrogen-containing VOCs (N-VOCs) showed high levels in general paints and similar product manufacturing (PNT), MP, and ILS industries, respectively. The gravure printing industry was identified as the highest emitter of VOCs, with the highest daily emissions reaching 5934 mg day−1, primarily consisting of ethyl acetate, toluene, butyl acetate, and propene. The findings suggest that the VOC emissions from the gravure printing and plastic synthetic leather industries should be primarily reduced, and it would be the most cost-effective approach to improving air quality. This study can provide the fundamental data for developing effective reduction technologies and policies of VOC, ultimately contributing to enhanced atmospheric models and regulatory measures. Full article
(This article belongs to the Special Issue Novel Insights into Air Pollution over East Asia (Second Edition))
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<p>Negative pressure sampling with a vacuum chamber. The red-bordered and blue-bordered arrows indicate the direction of sample inflow and the direction of air outflow from the chamber by the pump, respectively.</p>
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<p>Source profiles of VOC groups by industries.</p>
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<p>Radial charts for patterns of VOC groups by industries.</p>
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<p>Characteristics of VOC species emitted from various industries.</p>
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<p>Emissions of VOCs by industries. Numbers above each box represents the emissions of VOCs for each industry (mg day<sup>−1</sup>).</p>
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12 pages, 272 KiB  
Review
Clinical Application of 3D-Printed Artificial Vertebral Body (3DP AVB): A Review
by Roman Kiselev and Aleksander Zheravin
J. Pers. Med. 2024, 14(10), 1024; https://doi.org/10.3390/jpm14101024 - 26 Sep 2024
Viewed by 337
Abstract
Introduction: The choice of prosthesis for vertebral body reconstruction (VBR) remains a controversial issue due to the lack of a reliable solution. The subsidence rate of the most commonly used titanium mesh cages (TMC) ranges from 42.5% to 79.7%. This problem is [...] Read more.
Introduction: The choice of prosthesis for vertebral body reconstruction (VBR) remains a controversial issue due to the lack of a reliable solution. The subsidence rate of the most commonly used titanium mesh cages (TMC) ranges from 42.5% to 79.7%. This problem is primarily caused by the differences in the elastic modulus between the TMC and bone. This review aims to summarize the clinical and radiological outcomes of new 3D-printed artificial vertebral bodies (3DP AVB). Methods: A literature search of PubMed, Scopus and Google Scholar was conducted to extract relevant studies. After screening the titles and abstracts, a total of 50 articles were selected for full-text analysis. Results: Preliminary data suggest fewer implant-related complications with 3DP AVB. Most comparative studies indicate significantly lower subsidence rates, reduced operation times and decreased intraoperative blood loss. However, the scarcity of randomized clinical trials and the high variability of the results warrant caution. Conclusion: Most literature data show an advantage of 3DP AVB in terms of the operation time, intraoperative blood loss and subsidence rate. However, long manufacturing times, high costs and regulatory issues are this technology’s main drawbacks. Full article
11 pages, 3081 KiB  
Article
Ratiometric Electrochemical Detection of Interleukin-6 Using Electropolymerized Methylene Blue and a Multi-Walled Carbon-Nanotube-Modified Screen-Printed Carbon Electrode
by Zhuo Liu, Fengyu Liu, Chaofan Wang, Hongjuan Li, Yongqian Xu and Shiguo Sun
Biosensors 2024, 14(10), 457; https://doi.org/10.3390/bios14100457 - 25 Sep 2024
Viewed by 521
Abstract
Herein, we report a ratio-based electrochemical biosensor for the detection of interleukin-6 (IL-6). We electropolymerized methylene blue (MB) on the surface of screen-printed carbon electrodes; introduced an internal reference signal probe; modified the carboxylate multi-walled carbon nanotubes on the electrode surface to increase [...] Read more.
Herein, we report a ratio-based electrochemical biosensor for the detection of interleukin-6 (IL-6). We electropolymerized methylene blue (MB) on the surface of screen-printed carbon electrodes; introduced an internal reference signal probe; modified the carboxylate multi-walled carbon nanotubes on the electrode surface to increase the electrochemically active area; and finally linked the amino-modified IL-6 aptamer to the electrode surface through the Schiff base reaction, with bovine serum albumin (BSA) added to mask non-specific adsorption. After adding IL-6 to the samples, the signal of IMB remained almost unchanged, while the signal of I[Fe(CN)6]3−/4− decreased with increasing IL-6 concentration. Thus, a novel ratiometric electrochemical sensor with a linear range of 0.001~1000.0 ng/mL and a low detection limit of 0.54 pg/mL was successfully developed. The sensor had high repeatability, stability, sensitivity, and practicability. It provides a new method for constructing proportional electrochemical sensors and detecting IL-6. Full article
(This article belongs to the Special Issue State-of-the-Art Biosensors in China (2nd Edition))
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<p>SEM images of (<b>A</b>) bare SPCE, (<b>B</b>) SPCE modified with pMB, (<b>C</b>) MWCNTs, and (<b>D</b>) CS/MWCNTs.</p>
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<p>(<b>A</b>) CV curves (scan rate 50 mV s<sup>−1</sup>) and (<b>B</b>) EIS curves of different treated electrodes in 0.1 M KCl containing 5 mM [Fe(CN)<sub>6</sub>]<sup>3−/4−</sup>: (a) the bare SPCE, (b) SPCE-pMB, (c) SPCE-pMB-CS/MWCNTs, (d) SPCE-pMB-CS/MWCNTs-apt, (e) SPCE-pMB-CS/MWCNTs-apt-BSA, (f) 1 ng/mL-IL-6.</p>
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<p>CV of MB (<b>A</b>) and the peak current of the modified electrode in potassium ferricyanide solution (<b>B</b>).</p>
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<p>Effects of CS/MWCNTs loading (<b>A</b>), aptamer incubation time (<b>B</b>) and concentration (<b>C</b>), and IL-6 protein incubation time (<b>D</b>) on electrical signals (<span class="html-italic">n</span> = 3).</p>
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<p>(<b>A</b>) DPV plot of the electrochemical sensor at different IL-6 concentrations (From the top to the bottom of the corresponding concentration: 0 ng/mL, 0.001 ng/mL, 0.01 ng/mL, 0.1 ng/mL, 1 ng/mL, 10 ng/mL, 100 ng/mL, 1000 ng/mL.) and (<b>B</b>) standard curve of current difference versus negative logarithmic value of IL-6 concentration (<span class="html-italic">n</span> = 3).</p>
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<p>Electrical signal response of IL-6 and other interfering proteins during detection (<span class="html-italic">n</span> = 3).</p>
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<p>Stability (<b>A</b>) and reproducibility (<b>B</b>) of the electrochemical sensor. (<b>C</b>) The change of current difference when the same batch of sensors detected IL-6 (<span class="html-italic">n</span> = 3).</p>
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9 pages, 1685 KiB  
Article
Study on the Rheological Behaviors, Thixotropy, and Printing Characteristics of Screen Printing Slurry for Nd-Fe-B
by Xiaojun Sun, Xiao Lin, Yang Luo, Dunbo Yu, Wenlong Yan, Hongbin Zhang, Zilong Wang, Chaofan Zhang, Jiyuan Guo, Wendi Zhang, Weiguo Gao and Shan Huang
Materials 2024, 17(18), 4626; https://doi.org/10.3390/ma17184626 - 20 Sep 2024
Viewed by 361
Abstract
The rheological behavior and printing characteristics of the screen-printing slurry for Nd-Fe-B grain boundary diffusion are key factors that determine the quality of printing and magnetic performance. However, few studies have focused on the organic medium, a crucial material for slurry. In this [...] Read more.
The rheological behavior and printing characteristics of the screen-printing slurry for Nd-Fe-B grain boundary diffusion are key factors that determine the quality of printing and magnetic performance. However, few studies have focused on the organic medium, a crucial material for slurry. In this paper, the rheology, thixotropy, and thermal decomposition behavior of the organic vehicle in Nd-Fe-B screen printing slurry were studied. The results show that the organic vehicle formed by terpineol and polyvinyl butyral (PVB) exhibits typical non-Newtonian fluid characteristics, with excellent rheology and thixotropy, ensuring that the slurry prepared from it has excellent static stability and printing consistency. Additionally, the carbon residue of the organic vehicle formed by terpineol and PVB is less than 0.1% at 900 °C, avoiding excessive carbon entering the magnet during the diffusion process. Moreover, studying the rheology and thixotropy of the organic vehicle through a rheometer can quickly screen the slurry system. This work provides valuable guidance for designing an organic vehicle for screen-printing slurry for Nd-Fe-B grain boundary diffusion in future research. Full article
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<p>Schematic diagram of the preparation process.</p>
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<p>Shear rate-viscosity curves of different organic solvents.</p>
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<p>Schematic diagram of three-stage shear test.</p>
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<p>(<b>a</b>) Thixotropic curves of terpineol with different resins added, (<b>b</b>) localized enlarged view under high-speed shear state.</p>
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<p>Recovery ratio of organic vehicles within the specified time in the three-stage shear test.</p>
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<p>Thixotropic curves of PPH with PVB added.</p>
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<p>(<b>a</b>) PPH and (<b>b</b>) terpineol system slurries after 30 days of standing.</p>
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<p>Statistics of supernatant, dispersion, and precipitation layer volume fraction.</p>
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10 pages, 4783 KiB  
Article
Rotating Droplet Hydrodynamic Electrochemistry for Water Toxicity Bioassay Based on Electron-Transfer Mediator
by Kazuto Sazawa, Yeasna Shanjana, Kazuharu Sugawara and Hideki Kuramitz
Electrochem 2024, 5(3), 370-379; https://doi.org/10.3390/electrochem5030024 - 19 Sep 2024
Viewed by 773
Abstract
An electrochemical bioassay based on rotating droplet electrochemistry by using an electron-transfer mediator was developed for the evaluation of a wide variety of pollutants such as antibiotics, heavy metals, and pesticides in the water environment. Ferricyanide was used as an electron-transfer mediator for [...] Read more.
An electrochemical bioassay based on rotating droplet electrochemistry by using an electron-transfer mediator was developed for the evaluation of a wide variety of pollutants such as antibiotics, heavy metals, and pesticides in the water environment. Ferricyanide was used as an electron-transfer mediator for obtaining the catalytic response of Escherichia coli. The electrochemical response of E. coli was measured via hydrodynamic chronoamperometry in a microdroplet on a screen-printed carbon electrode (SPCE). The constructed electrode system successfully evaluates the catalytic response of E. coli solution in the presence of ferricyanide. An assay for antibiotic toxicity on E. coli was carried out. The EC50 for ampicillin, sulfamonomethoxine, chlorotetracycline, tetracycline, and oxytetracycline evaluated by the pre-incubation method were 0.26, 0.77, 5.25, 18.5, and 19.0 µM, respectively. The toxicity order was ampicillin > sulfamonomethoxine > chlorotetracycline > tetracycline > oxytetracycline. The proposed method can be used to evaluate the antibiotic toxicities in different real samples, such as pond water, powder, and raw milk. Recoveries were found in the range of 90 and 99%. The developed methods do not require additional incubation time to evaluate toxicity. Full article
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<p>Principle of electrochemical bioassay using mediator.</p>
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<p>The experimental set-up for the hydrodynamic electrochemistry for water toxicity bioassay using an electron-transfer mediator, and the hydrodynamic chronoamperograms is expected to be obtained.</p>
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<p>The catalytic response of <span class="html-italic">E. coli</span> in the presence of a ferricyanide mediator by using hydrodynamic chronoamperometry. The hydrodynamic chronoamperograms for 1 mM ferricyanide with (a) PBS buffer and (b) <span class="html-italic">E. coli</span>.</p>
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<p>Correlation between the mass-transfer limited current for the oxidation of ferrocyanide and the rotation of angular velocity (ω<sup>1/2</sup>). The hydrodynamic linear sweep voltammograms were obtained in a microdroplet solution comprising 10 µL ferrocyanide with 40 µL buffer solution (a) or buffer solution containing <span class="html-italic">E. coli</span> (b).</p>
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<p>The hydrodynamic chronoamperograms obtained from different concentrations of ferricyanide at 0.12, 0.25, 0.5, and 1.0 mM. Each concentration of ferricyanide (10 µL) was injected into 40 µL of <span class="html-italic">E. coli</span> solution (20 × 10<sup>9</sup> cells/mL). The measurements were performed by the RDE system at 300 mV applied potential with a rotation rate of 3000 rpm.</p>
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<p>Hanes–Woolf plots of ferricyanide in <span class="html-italic">E. coli</span> solution obtained by the RDE system at 300 mV applied potential with a rotation rate of 3000 rpm.</p>
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<p>(<b>a</b>) The hydrodynamic chronoamperograms for ferricyanide exposed to 40 µL of <span class="html-italic">E. coli</span> with different cell densities of 1.25 × 10<sup>9</sup>, 2.5 × 10<sup>9</sup>, 5 × 10<sup>9</sup>, 10 × 10<sup>9</sup>, and 20 × 10<sup>9</sup> cells/mL. The measurements were carried out by the RDE at an applied potential of 300 mV. (<b>b</b>) Relationship between the current reaction velocity and the cell density of <span class="html-italic">E. coli</span>.</p>
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<p>The dose–response curves for 5 antibiotics (ampicillin, chlorotetracycline, tetracycline, oxytetracycline, and sulfamonomethoxine). The measurements were performed by the RDE system at 300 mV applied potential with a rotation rate of 3000 rpm.</p>
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14 pages, 5959 KiB  
Article
Impact of Glow-Discharge Nitriding Technology on the Properties of 3D-Printed Grade 2 Titanium Alloy
by Janusz Kamiński, Ryszard Sitek, Bogusława Adamczyk-Cieślak and Krzysztof Kulikowski
Materials 2024, 17(18), 4592; https://doi.org/10.3390/ma17184592 - 19 Sep 2024
Viewed by 431
Abstract
This study presents a comparative analysis of the corrosion resistance of nitrided layers on conventional Grade 2 titanium alloy and those produced by direct metal laser sintering (DMLS). Low-temperature glow-discharge nitriding of the tested materials was carried out using conventional glow-discharge nitriding (so-called [...] Read more.
This study presents a comparative analysis of the corrosion resistance of nitrided layers on conventional Grade 2 titanium alloy and those produced by direct metal laser sintering (DMLS). Low-temperature glow-discharge nitriding of the tested materials was carried out using conventional glow-discharge nitriding (so-called nitriding at the cathode potential—TiN/CP) and with the use of an “active screen” (nitriding at the plasma potential—TiN/PP). The TiN + Ti2N + Ti(N) layers were characterized by their microstructure, nanohardness profile distribution, surface topography, and corrosion resistance. The reduction in the cathodic sputtering phenomenon in the process using the active screen allowed the creation of surface layers that retained the topography of the base material. The parameters of the glow-discharge treatment led to grain growth in the printed substrates. This did not adversely affect corrosion resistance. The corrosion resistance of nitrided layers on the printed titanium alloy is only slightly lower than that of layers on the conventional Grade 2 alloy. Iron precipitates at grain boundaries facilitate increased nitrogen diffusion, resulting in reduced nitrogen concentration in the surface layer, slight changes in corrosion potential values, and increased nitrogen concentration in the Ti(N) diffusion layer. Full article
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<p>Diagram of devices used in glow-discharge treatments: 1—sample, 2—electrical insulator, 3—active screen made of perforated titanium sheet.</p>
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<p>Microstructures of the nitrided layers DMLS-TiN/PP (<b>a</b>) and DMLS-TiN/CP (<b>b</b>) produced on a printed Grade 2 titanium alloy in the etched and unetched states with Kroll’s reagent. Inset: the distribution of iron and eutectoid lamellae in the Ti<sub>2</sub>N layer is marked with arrows.</p>
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<p>Phase compositions of the nitrided layers DMLS-TiN/PP (<b>a</b>) and DMLS-TiN/CP (<b>b</b>) produced on a printed Grade 2 titanium alloy.</p>
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<p>Phase compositions of the nitrided layers DMLS-TiN/PP (<b>a</b>) and DMLS-TiN/CP (<b>b</b>) produced on a printed Grade 2 titanium alloy.</p>
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<p>Microstructure of the printed (DMLS) Grade 2 alloy in the initial state (<b>a</b>) and post-glow-discharge treatment (<b>b</b>). Inset: the distribution of iron.</p>
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<p>Nanohardness as a function of depth measured along cross-sections of the nitrided (TiN/PP (<b>a</b>) and TiN/CP (<b>b</b>)) DMLS specimens.</p>
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<p>Nanohardness as a function of depth measured along cross-sections of the nitrided (TiN/PP (<b>a</b>) and TiN/CP (<b>b</b>)) DMLS and Grade 2 specimens.</p>
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<p>Microstructure of the nitrided layer (TiN/CP) produced on a printed titanium alloy (DMLS) (<b>b</b>) compared to the conventional Grade 2 titanium alloy (<b>a</b>). Inset: orange arrow—the extent of the diffusive Ti(N) layer in the Grade 2 titanium alloy.</p>
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<p>Topographies of layers created at the plasma (TiN/PP) and cathode potentials (TiN/CP) on printed (DMLS) and conventional (Grade 2) substrates.</p>
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<p>Bode plots of nitrided layers produced at plasma (TiN/PP) or cathode potential (TiN/CP) on printed (<b>a</b>) and classic (<b>b</b>) substrates compared to the starting materials (IS). Date—dotted line; fit—solid line.</p>
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<p>Potentiodynamic curves of glow-discharge layers formed on titanium Grade 2 (DMLS (<b>a</b>) and conventional (<b>b</b>)) exposed in a Ringer’s solution at 37 °C.</p>
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<p>Topography of the nitrided TiN/PP (<b>a</b>) and TiN/CP (<b>b</b>) layers produced on the 3D-printed Grade 2 titanium alloy after corrosion tests in Ringer’s solution at 37 °C.</p>
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