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Nanomaterials, Volume 14, Issue 16 (August-2 2024) – 54 articles

Cover Story (view full-size image): Two-dimensional materials offering excellent properties are suitable for radiation-resistant devices because only a small volume of such materials interact negatively with radiation. Thus, understanding their radiation response is crucial for developing practical radiation-related electronic devices. In this study, the effects of γ-rays on electrical variations in MoS2 field-effect transistors with buried local back-gate structures were investigated, along with their related effects on Al2O3 gate dielectrics and MoS2/Al2O3 interfaces. Our study provides key insights into the impact of radiation on MoS2 devices and will guide their application in the space, defense, and nuclear domains, which involve radiation-sensitive environments. View this paper
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14 pages, 3783 KiB  
Article
Synthesis of Highly Porous Lignin-Sulfonate Sulfur-Doped Carbon for Efficient Adsorption of Sodium Diclofenac and Synthetic Effluents
by Glaydson S. dos Reis, Sarah Conrad, Eder C. Lima, Mu. Naushad, Gopinathan Manavalan, Francesco G. Gentili, Guilherme Luiz Dotto and Alejandro Grimm
Nanomaterials 2024, 14(16), 1374; https://doi.org/10.3390/nano14161374 - 22 Aug 2024
Viewed by 590
Abstract
Herein, a novel sulfur-doped carbon material has been synthesized via a facile and sustainable single-step pyrolysis method using lignin-sulfonate (LS), a by-product of the sulfite pulping process, as a novel carbon precursor and zinc chloride as a chemical activator. The sulfur doping process [...] Read more.
Herein, a novel sulfur-doped carbon material has been synthesized via a facile and sustainable single-step pyrolysis method using lignin-sulfonate (LS), a by-product of the sulfite pulping process, as a novel carbon precursor and zinc chloride as a chemical activator. The sulfur doping process had a remarkable impact on the LS-sulfur carbon structure. Moreover, it was found that sulfur doping also had an important impact on sodium diclofenac removal from aqueous solutions due to the introduction of S-functionalities on the carbon material’s surface. The doping process effectively increased the carbon specific surface area (SSA), i.e., 1758 m2 g−1 for the sulfur-doped and 753 m2 g−1 for the non-doped carbon. The sulfur-doped carbon exhibited more sulfur states/functionalities than the non-doped, highlighting the successful chemical modification of the material. As a result, the adsorptive performance of the sulfur-doped carbon was remarkably improved. Diclofenac adsorption experiments indicated that the kinetics was better described by the Avrami fractional order model, while the equilibrium studies indicated that the Liu model gave the best fit. The kinetics was much faster for the sulfur-doped carbon, and the maximum adsorption capacity was 301.6 mg g−1 for non-doped and 473.8 mg g−1 for the sulfur-doped carbon. The overall adsorption seems to be a contribution of multiple mechanisms, such as pore filling and electrostatic interaction. When tested to treat lab-made effluents, the samples presented excellent performance. Full article
(This article belongs to the Special Issue Degradation of Pollutants by Nanostructured Photocatalysts)
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<p>(<b>a</b>,<b>c</b>) XPS survey spectra for LS-carbon and LS-sulfur carbon samples and (<b>b</b>,<b>d</b>) deconvoluted S p2 peaks.</p>
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<p>Proposed carbon network structures: (<b>a</b>) LS-carbon and (<b>b</b>) LS-sulfur carbon samples.</p>
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<p>(<b>a</b>) N<sub>2</sub> isotherm curves for LS-carbon and LS-sulfur carbon, (<b>b</b>) pore size distribution curves, (<b>c</b>) SEM image of LS-carbon, (<b>d</b>) SEM image of LS-sulfur carbon, (<b>e</b>) Raman spectrum of LS-carbon, and (<b>f</b>) Raman spectrum of LS-sulfur carbon.</p>
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<p>(<b>a</b>) pH<sub>pzc</sub> of the LS-carbon and LS-sulfur carbon samples and (<b>b</b>) effect of the pH on DCF removal.</p>
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<p>Kinetic measurements for the adsorption of DCF onto (<b>a</b>) LS-carbon and (<b>b</b>) LS-sulfur carbon samples. Initial pH of DCF solution was 6.0.</p>
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<p>Isotherm curves for adsorption of DCF onto (<b>a</b>) LS-carbon and (<b>b</b>) LS-sulfur carbon samples. Initial pH of DCF solution was 6.0.</p>
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<p>Adsorption of lab-made drug effluents. (<b>a</b>) Effluent A; (<b>b</b>) Effluent B.</p>
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29 pages, 7083 KiB  
Article
Mechanical and Shape Memory Properties of Additively Manufactured Polyurethane (PU)/Halloysite Nanotube (HNT) Nanocomposites
by Wendy Triadji Nugroho, Yu Dong and Alokesh Pramanik
Nanomaterials 2024, 14(16), 1373; https://doi.org/10.3390/nano14161373 - 22 Aug 2024
Viewed by 723
Abstract
This paper investigates the impact of halloysite nanotube (HNT) content on mechanical and shape memory properties of additively manufactured polyurethane (PU)/HNT nanocomposites. The inclusion of 8 wt% HNTs increases their tensile strength by 30.4% when compared with that of virgin PU at 44.75 [...] Read more.
This paper investigates the impact of halloysite nanotube (HNT) content on mechanical and shape memory properties of additively manufactured polyurethane (PU)/HNT nanocomposites. The inclusion of 8 wt% HNTs increases their tensile strength by 30.4% when compared with that of virgin PU at 44.75 MPa. Furthermore, consistently significant increases in tensile modulus, compressive strength and modulus, as well as specific energy absorption are also manifested by 47.2%, 34.0%, 125% and 72.7% relative to neat PU at 2.29 GPa, 3.88 MPa, 0.28 GPa and 0.44 kJ/kg respectively. However, increasing HNT content reduces lateral strain due to the restricted mobility of polymeric chains, leading to a decrease in negative Poisson’s ratio (NPR). As such, shape recovery ratio and time of PU/HNT nanocomposites are reduced by 9 and 45% with the inclusion of 10 wt% HNTs despite an increasing shape fixity ratio up to 12% relative to those of neat PU. Full article
(This article belongs to the Section Nanocomposite Materials)
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<p>Urethane formation from isocyanate and polyol [<a href="#B12-nanomaterials-14-01373" class="html-bibr">12</a>].</p>
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<p>Chemical structure of PU [<a href="#B12-nanomaterials-14-01373" class="html-bibr">12</a>].</p>
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<p>CAD models on 3D printing build platform and final 3D printed (<b>a</b>) dog-bone, (<b>b</b>) strip-like and (<b>c</b>) RE structures.</p>
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<p>(<b>a</b>) A dog-bone structure with reference to ASTM D638 (type V), (<b>b</b>) RE structure with its dimensions, (<b>c</b>) a schematic diagram of compressive test for RE structure.</p>
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<p>Dimensional changes of RE sample during a shape memory test.</p>
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<p>(<b>a</b>) Tensile strength, (<b>b</b>) Pareto ANOVA and (<b>c</b>) sum of <span class="html-italic">S</span>/<span class="html-italic">N</span> ratios for 3D printed PU/HNT nanocomposite dog-bone samples based on <span class="html-italic">L</span><sub>18</sub> layout in DoE work [<a href="#B35-nanomaterials-14-01373" class="html-bibr">35</a>].</p>
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<p>(<b>a</b>) Stress–strain curve and influence of HNT content on (<b>b</b>) tensile strength, (<b>c</b>) elongation at break and (<b>d</b>) tensile modulus of PU/HNT nanocomposites.</p>
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<p>SEM micrographs of (<b>a</b>) PU and PU/HNT nanocomposites at different HNT contents: (<b>b</b>) 2 wt%, (<b>c</b>) 4 wt%, (<b>d</b>) 6 wt%, (<b>e</b>) 8 wt% and (<b>f</b>) 10 wt%.</p>
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<p>TEM micrographs showing HNT dispersion in PU/HNT nanocomposites at different HNT contents: (<b>a</b>) 2, (<b>b</b>) 4, (<b>c</b>) 6, (<b>d</b>) 8 and (<b>e</b>) 10 wt%.</p>
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<p>(<b>a</b>) compressive stress-strain curves and (<b>b</b>) energy absorption efficiency curves of RE structures.</p>
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<p>Effect of HNT addition on PRs for RE structures.</p>
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<p>Deformation mechanisms for (<b>a</b>) virgin PU and (<b>b</b>) PU/HNT nanocomposite samples.</p>
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<p>Deformation mechanisms for (<b>a</b>) virgin PU and (<b>b</b>) PU/HNT nanocomposite samples.</p>
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<p>(<b>a</b>) Recovery ratio and (<b>b</b>) recovery time of strip-like nanocomposites with respect to optimum factor-level combination and ultimate tensile strength.</p>
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14 pages, 5368 KiB  
Article
Functionalization of Polypropylene by TiO2 Photocatalytic Nanoparticles: On the Importance of the Surface Oxygen Plasma Treatment
by Karolina Zajac, Joanna Macyk, Konrad Szajna, Franciszek Krok, Wojciech Macyk and Andrzej Kotarba
Nanomaterials 2024, 14(16), 1372; https://doi.org/10.3390/nano14161372 - 22 Aug 2024
Viewed by 609
Abstract
A new two-step method for developing a nanocomposite of polypropylene (PP) decorated with photocatalytically active TiO2 nanoparticles (nTiO2) is proposed. This method involves the low-temperature plasma functionalization of polypropylene followed by the ultrasound-assisted anchoring of nTiO2. The nanoparticles, [...] Read more.
A new two-step method for developing a nanocomposite of polypropylene (PP) decorated with photocatalytically active TiO2 nanoparticles (nTiO2) is proposed. This method involves the low-temperature plasma functionalization of polypropylene followed by the ultrasound-assisted anchoring of nTiO2. The nanoparticles, polymeric substrate, and resultant nanocomposite were thoroughly characterized using nanoparticle tracking analysis (NTA), microscopic observations (SEM, TEM, and EDX), spectroscopic investigations (XPS and FTIR), thermogravimetric analysis (TG/DTA), and water contact angle (WCA) measurements. The photocatalytic activity of the nanocomposites was evaluated through the degradation of methyl orange. The individual TiO2 nanoparticles ranged from 2 to 6 nm in size. The oxygen plasma treatment of PP generated surface functional groups (mainly -OH and -C=O), transforming the surface from hydrophobic to hydrophilic, which facilitated the efficient deposition of nTiO2. Optimized plasma treatment and sonochemical deposition parameters resulted in an active photocatalytic nTiO2/PP system, degrading 80% of the methyl orange under UVA irradiation in 200 min. The proposed approach is considered versatile for the functionalization of polymeric materials with photoactive nanoparticles and, in a broader perspective, can be utilized for the fabrication of self-cleaning surfaces. Full article
(This article belongs to the Topic Preparation and Application of Polymer Nanocomposites)
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<p>Pristine polypropylene substrate: (<b>a</b>) SEM image and (<b>b</b>) ATR-FTIR spectrum indicating the main functional groups in the polypropylene structure.</p>
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<p>Titanium dioxide nanoparticles: (<b>a</b>) nanoparticle tracking analysis showing the hydrodynamic diameter; (<b>b</b>) SEM image of TiO<sub>2</sub>; (<b>c</b>) particle size distribution based on the SEM images; (<b>d</b>) TEM image showing that the observed SEM nanoparticles are agglomerates of smaller TiO<sub>2</sub> crystallites, with the insert presenting a high resolution (HR-TEM) image; (<b>e</b>) size distribution of individual TiO<sub>2</sub> crystallites; and (<b>f</b>) size distribution of agglomerates from TEM images.</p>
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<p>XPS results for polypropylene surface before and after oxygen plasma treatment. (<b>a</b>) XPS survey scans showing the increase in surface oxygen to carbon ratio with the plasma treatment time; (<b>b</b>) narrow XPS scan of the C 1<span class="html-italic">s</span> peak indicating the presence of hydroxyl (-OH) and carbonyl (C=O) groups, and the appearance of carboxyl bonds (O–C=O) upon plasma treatment.</p>
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<p>Changes in the water contact angle of the polypropylene surface as a function of oxygen plasma treatment time.</p>
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<p>Thermogravimetric analysis of pristine polypropylene and PP after plasma treatment: (<b>a</b>) loss of mass profile and the corresponding (<b>b</b>) differential thermal analysis.</p>
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<p>SEM images of the polypropylene substrate showing the effectiveness of TiO<sub>2</sub> nanoparticle deposition on untreated and plasma-treated substrates: (<b>a</b>) pristine polypropylene surface, (<b>b</b>) TiO<sub>2</sub> nanoparticles deposited on the untreated surface, and (<b>c</b>) TiO<sub>2</sub> nanoparticles deposited on the plasma-treated surface.</p>
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<p>SEM images of polypropylene substrate after deposition of TiO<sub>2</sub> from suspension with varying nanoparticle concentrations: (<b>a</b>) reference polypropylene substrate before nanoparticle deposition, (<b>b</b>) polypropylene surface after deposition from TiO<sub>2</sub> 0.1% suspension, and (<b>c</b>) polypropylene surface after deposition from 1% TiO<sub>2</sub> suspension.</p>
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<p>Photocatalytic activity of nTiO<sub>2</sub>/PP nanocomposite in methyl orange degradation under UVA irradiation: (<b>a</b>) absorbance decrease at 464 nm upon irradiation, (<b>b</b>) kinetic curves illustrating enhanced activity for plasma-treated PP composite, and (<b>c</b>) the linearized kinetic data together with the rate constants calculated based on first-order reaction kinetics.</p>
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<p>Schematic representation of the plasma treatment effect on the photocatalytic performance of the developed nTiO<sub>2</sub>/PP composite.</p>
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<p>The dye degradation process over five cycles of irradiation in the presence of the nTiO₂/PP nanocomposite.</p>
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<p>Optimization of sonochemical deposition parameters for enhanced photocatalytic activity: (<b>a</b>) effect of initial nTiO<sub>2</sub> suspension concentration, (<b>b</b>) effect of sonication time on methyl orange degradation using 0.1% TiO<sub>2</sub> suspension, (<b>c</b>) photocatalytic activity as a function of sonodeposition time, with 2 min identified as the optimal for maximum efficiency.</p>
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15 pages, 4359 KiB  
Article
Enhancing Slurry Stability and Surface Flatness of Silicon Wafers through Organic Amine-Catalyzed Synthesis Silica Sol
by Yi Xing, Weilei Wang, Weili Liu and Zhitang Song
Nanomaterials 2024, 14(16), 1371; https://doi.org/10.3390/nano14161371 - 22 Aug 2024
Viewed by 735
Abstract
The stability of slurries used for chemical mechanical polishing (CMP) is a crucial concern in industrial chip production, influencing both the quality and cost-effectiveness of polishing fluids. In silicon wafer polishing, the conventional use of commercial neutral silica sol combined with organic bases [...] Read more.
The stability of slurries used for chemical mechanical polishing (CMP) is a crucial concern in industrial chip production, influencing both the quality and cost-effectiveness of polishing fluids. In silicon wafer polishing, the conventional use of commercial neutral silica sol combined with organic bases often leads to slurry instability. To address this issue, this study proposes organic amines—specifically ethanolamine (MEA), ethylenediamine (EDA), and tetramethylammonium hydroxide (TMAOH)—as catalysts for synthesizing alkaline silica sol tailored for silicon wafer polishing fluids. Sol–gel experiments and zeta potential measurements demonstrate the efficacy of this approach in enhancing the stability of silica sol. The quantitative analysis of surface hydroxyl groups reveals a direct correlation between enhanced stability and increased hydroxyl content. The application of the alkaline silica sol in silicon wafer polishing fluids improves polishing rates and enhances surface flatness according to atomic force microscopy (AFM). In addition, electrochemical experiments validate the capability of this polishing solution to mitigate corrosion on silicon wafer surfaces. These findings hold significant implications for the advancement of chemical mechanical polishing techniques in the field of integrated circuit fabrication. Full article
(This article belongs to the Special Issue Advanced Porous Nanomaterials: Synthesis, Properties, and Application)
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<p>The variation in sol–gel time over pH in the control and experimental groups.</p>
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<p>The variation in zeta potential over pH in the control and experimental groups.</p>
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<p>The variation in hydroxyl content over pH in the control and experimental groups.</p>
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<p>Thermogravimetric analysis (TGA, black line) and derivative thermogravimetry (DTG, red line) curves of SiO<sub>2</sub> synthesized with different organic amine catalysts at pH = 10.50: (<b>a</b>) MEA, (<b>b</b>) EDA, and (<b>c</b>) TMAOH.</p>
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<p>Solid-state <sup>29</sup>Si NMR spectra of the SiO<sub>2</sub> synthesized with different organic amine catalysts at pH = 10.50 (Q3, purple line; Q4, blue line).</p>
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<p>Structural formulas and 3D models of different organic amines (Carbon atom, red; Oxygen atom, yellow; Nitrogen atom, blue; Hydrogen atom, white).</p>
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<p>The adsorption between organic amine molecules and silanol groups: (<b>a</b>) MEA, (<b>b</b>) EDA, and (<b>c</b>) TMAOH.</p>
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<p>Effect of the silicon polishing slurry from the control group and experimental groups on MRR and Ra at pH = 10.50.</p>
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<p>The surface morphology and scratch performance of silicon wafer: (<b>a</b>) control group, (<b>b</b>) MEA, (<b>c</b>) EDA, and (<b>d</b>) TMAOH (the red and green lines characterized the degree of particles aggregation and the depth of scratches).</p>
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<p>The surface morphology and scratch performance of silicon wafer: (<b>a</b>) control group, (<b>b</b>) MEA, (<b>c</b>) EDA, and (<b>d</b>) TMAOH (the red and green lines characterized the degree of particles aggregation and the depth of scratches).</p>
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<p>Potentiodynamic polarization curve of different components in polishing slurries at pH 10.50.</p>
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16 pages, 9972 KiB  
Article
Influence of the Structure of Hydrothermal-Synthesized TiO2 Nanowires Formed by Annealing on the Photocatalytic Reduction of CO2 in H2O Vapor
by Andrey M. Tarasov, Larisa I. Sorokina, Daria A. Dronova, Olga Volovlikova, Alexey Yu. Trifonov, Sergey S. Itskov, Aleksey V. Tregubov, Elena N. Shabaeva, Ekaterina S. Zhurina, Sergey V. Dubkov, Dmitry V. Kozlov and Dmitry Gromov
Nanomaterials 2024, 14(16), 1370; https://doi.org/10.3390/nano14161370 - 21 Aug 2024
Viewed by 611
Abstract
The present study investigates the photocatalytic properties of hydrothermally synthesized TiO2 nanowires (NWs) for CO2 reduction in H2O vapor. It has been demonstrated that TiO2 NWs, thermally treated at 500–700 °C, demonstrate an almost tenfold higher yield of [...] Read more.
The present study investigates the photocatalytic properties of hydrothermally synthesized TiO2 nanowires (NWs) for CO2 reduction in H2O vapor. It has been demonstrated that TiO2 NWs, thermally treated at 500–700 °C, demonstrate an almost tenfold higher yield of products compared to the known commercial powder TiO2 P25. It has been found that the best material is a combination of anatase, TiO2-B and rutile. The product yield increases with increasing heat treatment temperature of TiO2 NWs. This is associated with an increase in the degree of crystallinity of the material. It is shown that the best product yield of the CO2 reduction in H2O vapor is achieved when the TiO2 NW photocatalyst is heated to 100 °C. Full article
(This article belongs to the Section Energy and Catalysis)
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<p>A photograph of nanowire samples on a titanium substrate (<b>a</b>), the reactor appearance (<b>b</b>) and a diagram of the stand for measuring the photocatalytic activity of the samples (<b>c</b>).</p>
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<p>SEM photo of morphology of TiO<sub>2</sub>. (<b>a</b>) Commercial P25, TiO<sub>2</sub> nanowires; (<b>b</b>) original sample; (<b>c</b>) after annealing at 350 °C; (<b>d</b>) after annealing at 500 °C; (<b>e</b>) after annealing at 700 °C; and (<b>f</b>) after annealing at 900 °C.</p>
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<p>XRD patterns of TiO<sub>2</sub> nanowire samples. Phase designation: H—hydrogen titanate, A—anatase, R—rutile, and B—bronze (TiO<sub>2</sub>-B).</p>
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<p>Results of TEM studies of initially synthesized nanowires: (<b>a</b>) TEM image of nanowires; (<b>b</b>) selected area diffraction pattern (SADP); (<b>c</b>) SADP after 10 min of exposure to high-intensity electron beam; and (<b>d</b>,<b>e</b>) high-resolution TEM (HRTEM) images.</p>
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<p>Selected area diffraction patterns (SADPs) of nanowire samples after temperature treatment: (<b>a</b>) 350 °C; (<b>b</b>) 500 °C; (<b>c</b>) 700 °C; and (<b>d</b>) 900 °C.</p>
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<p>TEM images of samples after temperature treatment: (<b>a</b>) 700 °C at 7k× magnification; (<b>b</b>) 700 °C at 20k× magnification; (<b>c</b>) 900 °C at 20k× magnification; and (<b>d</b>) 900 °C at 1M× magnification.</p>
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<p>TEM images of sample fragments annealed at 700 °C in bright-field mode (<b>a</b>) and dark-field mode in electrons scattered by (101) planes of anatase (<b>b</b>) and (110) planes of rutile (<b>c</b>).</p>
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<p>Raman spectra of TiO<sub>2</sub> nanowire samples. Phase designation: H—hydrogen titanate, A—anatase, R—rutile, and B—bronze (TiO<sub>2</sub>-B).</p>
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<p>Nitrogen adsorption–desorption isotherms at 77 K of TiO<sub>2</sub> nanowires without annealing and after annealing at 500 °C.</p>
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<p>Results of Kubelka–Munk theory calculations for TiO<sub>2</sub> nanowires.</p>
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<p>SEM images of a TiO<sub>2</sub> NW-500 layer formed by the drop method: top (<b>a</b>) and side (<b>b</b>) views.</p>
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<p>Average yield of CO<sub>2</sub> photoreduction reaction products for layers of TiO<sub>2</sub> NWs annealed at different temperatures and commercial TiO<sub>2</sub> P25.</p>
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<p>Average product yield in µmol/(g·h) for TiO<sub>2</sub> NW-500.</p>
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11 pages, 2975 KiB  
Article
The Construction of Iodine-Doped Carbon Nitride as a Metal-Free Nanozyme for Antibacterial and Water Treatment
by Xinru Cai, Tongtong Xie, Linshan Luo and Xiting Li
Nanomaterials 2024, 14(16), 1369; https://doi.org/10.3390/nano14161369 - 21 Aug 2024
Viewed by 484
Abstract
Metal-free photocatalysis that produces reactive oxygen species (ROS) shows significant promising applications for environmental remediation. Herein, we constructed iodine-doped carbon nitride (I-CN) for applications in the photocatalytic inactivation of bacteria and the heterogeneous Fenton reaction. Our findings revealed that I-CN demonstrates superior photocatalytic [...] Read more.
Metal-free photocatalysis that produces reactive oxygen species (ROS) shows significant promising applications for environmental remediation. Herein, we constructed iodine-doped carbon nitride (I-CN) for applications in the photocatalytic inactivation of bacteria and the heterogeneous Fenton reaction. Our findings revealed that I-CN demonstrates superior photocatalytic activity compared to pure CN, due to enhanced light adsorption and a narrowed band gap. Antibacterial tests confirmed that I-CN exhibits exceptional antibacterial activity against both Escherichia coli and Staphylococcus aureus. The results showed that I-CN effectively generates superoxide radicals and hydroxyl radicals under light irradiation, resulting in enhanced antibacterial activity. In addition, I-CN can also be applied for a heterogeneous photo-Fenton-like reaction, achieving a high performance for the degradation of sulfamethoxazole (SMX), a typical antibiotic, via the photocatalytic activation of peroxymonosulfate (PMS). These results shed new light on the fabrication of metal-free nanozymes and their applications for disinfection and water decontamination. Full article
(This article belongs to the Special Issue Nanocatalysts for Environmental Remediation)
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<p>(<b>a</b>) SEM image of I-CN; (<b>b</b>) TEM image of I-CN; (<b>c</b>) XRD patterns; (<b>d</b>) Raman spectra of I-CN and CN; (<b>e</b>) high-resolution N 1s XPS spectra; (<b>f</b>) high-resolution XPS I 3d spectra of I-CN.</p>
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<p>(<b>a</b>) Photocurrent response; (<b>b</b>) Nyquist diagram of I-CN and CN; DMPO spin-trapping EPR spectra for (<b>c</b>) O<sub>2</sub><sup>•−</sup> and (<b>d</b>) •OH under irradiation-simulated visible light (• represents DMPO–•OH and ◆ represents DMPO–O<sub>2</sub><sup>•−</sup>).</p>
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<p>(<b>a</b>) UV/Vis DRS spectra, (<b>b</b>) Tauc plots, (<b>c</b>) Mott–Schottky plots, and (<b>d</b>) band structure and photocatalytic mechanism of I-CN.</p>
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<p>Bacterial colony growth in the presence of I-CN for (<b>a</b>) <span class="html-italic">S. aureus</span> and (<b>b</b>) <span class="html-italic">E. coli</span> under different irradiation times; (<b>c</b>,<b>d</b>) show the survival ratio.</p>
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<p>(<b>a</b>) Absorption curves of TMB chromogenic reaction catalyzed by I-CN; (<b>b</b>) degradation of SMX in various systems; influence of (<b>c</b>) catalyst dose, (<b>d</b>) PMS dose, and (<b>e</b>) initial pH on SMX degradation in I-CN/PMS/Vis system; (<b>f</b>) recycling use of I-CN for degradation of SMX via PMS activation over five consecutive cycles. Reaction conditions: [SMX] = 10 mg/L; [catalyst] = 0.6 g/L; [PMS] = 0.3 g/L; initial pH = 5.</p>
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16 pages, 4552 KiB  
Article
In Situ, Nitrogen-Doped Porous Carbon Derived from Mixed Biomass as Ultra-High-Performance Supercapacitor
by Yuqiao Bai, Qizhao Wang, Jieni Wang, Shuqin Zhang, Chenlin Wei, Leichang Cao and Shicheng Zhang
Nanomaterials 2024, 14(16), 1368; https://doi.org/10.3390/nano14161368 - 21 Aug 2024
Viewed by 548
Abstract
How to address the destruction of the porous structure caused by elemental doping in biochar derived from biomass is still challenging. In this work, the in-situ nitrogen-doped porous carbons (ABPCs) were synthesized for supercapacitor electrode applications through pre-carbonization and activation processes using nitrogen-rich [...] Read more.
How to address the destruction of the porous structure caused by elemental doping in biochar derived from biomass is still challenging. In this work, the in-situ nitrogen-doped porous carbons (ABPCs) were synthesized for supercapacitor electrode applications through pre-carbonization and activation processes using nitrogen-rich pigskin and broccoli. Detailed characterization of ABPCs revealed that the best simple ABPC-4 exhibited a super high specific surface area (3030.2–3147.0 m2 g−1) and plentiful nitrogen (1.35–2.38 wt%) and oxygen content (10.08–15.35 wt%), which provided more active sites and improved the conductivity and electrochemical activity of the material. Remarkably, ABPC-4 showed an outstanding specific capacitance of 473.03 F g−1 at 1 A g−1. After 10,000 cycles, its capacitance retention decreased by only 4.92% at a current density of 10 A g−1 in 6 M KOH. The assembled symmetric supercapacitor ABPC-4//ABPC-4 achieved a power density of 161.85 W kg−1 at the maximum energy density of 17.51 Wh kg−1 and maintained an energy density of 6.71 Wh kg−1 when the power density increased to 3221.13 W kg−1. This study provides a mixed doping approach to achieve multi-element doping, offering a promising way to apply supercapacitors using mixed biomass. Full article
(This article belongs to the Special Issue Nanomaterials for Energy Conversion and Storage (2nd Edition))
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<p>SEM images of (<b>a</b>) BC, (<b>b</b>) ABC, (<b>c</b>) BPC-1, (<b>d</b>) ABPC-1, (<b>e</b>) BPC-2, (<b>f</b>) ABPC-2, (<b>g</b>) BPC-4, (<b>h</b>) ABPC-4.</p>
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<p>XRD spectra of (<b>a</b>) pre-carbonization products, (<b>b</b>) high temperature activated porous carbon. Raman patterns of (<b>c</b>) pre-carbonization products, (<b>d</b>) high temperature activated porous carbon.</p>
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<p>(<b>a</b>) N<sub>2</sub> adsorption and desorption isotherms, (<b>b</b>) Pore size distribution diagram.</p>
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<p>(<b>a</b>) XPS measurement spectra of samples ABC, ABPC-1, ABPC-2, and ABPC-4, (<b>b</b>–<b>d</b>) Fine spectra of C 1s, N 1s, and O 1s of sample ABPC-4.</p>
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<p>(<b>a</b>,<b>b</b>) CV curves of pre-carbonization biochar and porous carbon at a scanning rate of 20 mV s<sup>−1</sup>, (<b>c</b>,<b>d</b>) GCD curve of pre-carbonization biochar and porous carbon at current density 1 A g<sup>−1</sup>.</p>
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<p>(<b>a</b>) CV curves of samples ABPC-4 at different scanning rates, (<b>b</b>) GCD curves of sample ABPC-4 at different current densities, (<b>c</b>) Specific capacitance of nitrogen-rich biomass-derived porous carbon, (<b>d</b>) Impedance profile of nitrogen-rich biomass-derived porous carbon.</p>
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<p>(<b>a</b>) CV curves of ABPC-4//ABPC-4 at different voltage windows of 1–1.8 V, (<b>b</b>) CV curves of ABPC-4//ABPC-4 at different scanning rates of 5–200 mV s<sup>−1</sup>, (<b>c</b>) GCD curves at different densities from 0.5 to 30 A g<sup>−1</sup>, (<b>d</b>) Impedance spectra (Nyquist plots).</p>
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<p>(<b>a</b>) The Rogone diagram of ABPC-4; (<b>b</b>) Magnification performance graph of ABPC-4; (<b>c</b>) Cycling stability of sample ABPC-4 in a three-electrode system.</p>
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14 pages, 4527 KiB  
Article
ZIF-8-Based Nitrogen and Monoatomic Metal Co-Doped Pyrolytic Porous Carbon for High-Performance Supercapacitor Applications
by Xiaobo Han, Yihao Geng, Jieni Wang, Shuqin Zhang, Chenlin Wei, Leichang Cao and Shicheng Zhang
Nanomaterials 2024, 14(16), 1367; https://doi.org/10.3390/nano14161367 - 21 Aug 2024
Viewed by 584
Abstract
Metal–organic frameworks (MOFs) receive wide attention owing to their high specific surface area, porosity, and structural designability. In this paper, ZC-Ru and ZC-Cu electrodes loaded with monatomic Ru and Cu doped with nitrogen were prepared by pyrolysis, ion impregnation, and carbonization process using [...] Read more.
Metal–organic frameworks (MOFs) receive wide attention owing to their high specific surface area, porosity, and structural designability. In this paper, ZC-Ru and ZC-Cu electrodes loaded with monatomic Ru and Cu doped with nitrogen were prepared by pyrolysis, ion impregnation, and carbonization process using ZIF-8 synthesized by static precipitation as a precursor. ZC-Cu has a high specific surface area of 859.78 m2 g−1 and abundant heteroatoms O (10.04%) and N (13.9%), showing the specific capacitance of 222.21 F g−1 at 0.1 A g−1 in three-electrode system, and low equivalent series resistance (Rct: 0.13 Ω), indicating excellent energy storage capacity and electrical conductivity. After 10,000 cycles at 1 A g−1 in 6 M KOH electrolyte, it still has an outstanding capacitance retention of 99.42%. Notably, symmetric supercapacitors ZC-Cu//ZC-Cu achieved the maximum power density and energy density of 485.12 W·kg−1 and 1.61 Wh·kg−1, respectively, positioning ZC-Cu among the forefront of previously known MOF-based electrode materials. This work demonstrates the enormous potential of ZC-Cu in the supercapacitor industry and provides a facile approach to the treatment of transition metal. Full article
(This article belongs to the Special Issue Nanomaterials for Energy Conversion and Storage (2nd Edition))
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<p>SEM images of (<b>a</b>) ZC, (<b>b</b>) ZC-Ru, (<b>c</b>) ZC-Cu, (<b>d</b>–<b>f</b>) EDS mapping of ZC-Cu.</p>
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<p>(<b>a</b>) Nitrogen adsorption–desorption isotherms of ZC, ZC-Ru, and ZC-Cu, (<b>b</b>) pore size distributions of ZC, ZC-Ru, and ZC-Cu.</p>
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<p>(<b>a</b>) XRD patterns of ZC, ZC-Ru, and ZC-Cu, (<b>b</b>) Raman spectra of ZC, ZC-Ru, and ZC-Cu.</p>
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<p>(<b>a</b>) XPS full spectrum of ZC, ZC-Ru, and ZC-Cu. (<b>b</b>) XPS high-resolution spectrum of C1s. (<b>c</b>) XPS high-resolution spectrum of N1s. (<b>d</b>) XPS high-resolution spectrum of O1s.</p>
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<p>(<b>a</b>) CV curves of ZC, ZC-Ru, and ZC-Cu. (<b>b</b>) CV curves of ZC-Cu at different scanning rates from 1 to 30 mV s<sup>−1</sup>. (<b>c</b>) GCD curves of ZC, ZC-Ru, and ZC-Cu. (<b>d</b>) GCD curves of ZC-Cu at different densities from 0.1 to 5 A g<sup>−1</sup>. (<b>e</b>) Specific capacitances of the ZC-Cu electrodes (<b>f</b>) Cycling performance of ZC-Cu at 1 A g<sup>−1</sup> for 10,000 cycles.</p>
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<p>(<b>a</b>) Nyquist curves of ZC, ZC-Ru, and ZC-Cu, (<b>b</b>) BODE curves of ZC, ZC-Ru, and ZC-Cu.</p>
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<p>(<b>a</b>–<b>c</b>) The normalized real capacitance (<math display="inline"><semantics> <mrow> <msup> <mrow> <mi>C</mi> </mrow> <mrow> <mo>′</mo> </mrow> </msup> <mo>(</mo> <mi>ω</mi> <mo>)</mo> </mrow> </semantics></math>) and imaginary capacitance (<math display="inline"><semantics> <mrow> <msup> <mrow> <mi>C</mi> </mrow> <mrow> <mo>″</mo> </mrow> </msup> <mo>(</mo> <mi>ω</mi> <mo>)</mo> </mrow> </semantics></math>) of ZC, ZC-Ru, and ZC-Cu, respectively. (<b>d</b>) The normalized ratios of capacitive contribution and diffusion contribution for ZC-Cu. (<b>e</b>) Plots of log (current density) vs. log (scan rate) for ZC-Cu. (<b>f</b>) Area plot of pseudocapacitance contribution of ZC-Cu electrode at a scan rate of 30 mV s<sup>−1</sup>.</p>
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<p>(<b>a</b>) CV of ZC-Cu at different open circuit voltages. (<b>b</b>) CV of ZC-Cu at 1.3 V at open-circuit voltage. (<b>c</b>) GCD of ZC-Cu at different current densities in the voltage window range of 0–1.3 V. (<b>d</b>) Specific capacitance of ZC-Cu at different scan rates in the voltage window range of 0–1.3 V. (<b>e</b>) Relationship between power density and energy density of ZC-Cu.</p>
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13 pages, 25965 KiB  
Article
MIL-Derived Hollow Tubulous-Shaped In2O3/ZnIn2S4 Z-Scheme Heterojunction for Efficient Antibacterial Performance via In Situ Composite
by Jiao Duan, Hui Zhang, Jie Zhang, Mengmeng Sun and Jizhou Duan
Nanomaterials 2024, 14(16), 1366; https://doi.org/10.3390/nano14161366 - 21 Aug 2024
Viewed by 477
Abstract
In this study, a hollow tubulous-shaped In2O3 derived from MIL (MIL-68 (In)) exhibited an enhanced specific surface area compared to MIL. To further sensitize In2O3, ZnIn2S4 was grown in situ on the derived [...] Read more.
In this study, a hollow tubulous-shaped In2O3 derived from MIL (MIL-68 (In)) exhibited an enhanced specific surface area compared to MIL. To further sensitize In2O3, ZnIn2S4 was grown in situ on the derived In2O3. The 40In2O3/ZnIn2S4 composite (1 mmol ZnIn2S4 loaded on 40 mg In2O3) exhibited degradation rates of methyl orange (MO) under visible light (80 mW·cm−2, 150 min) that were 17.9 and 1.4 times higher than those of the pure In2O3 and ZnIn2S4, respectively. Moreover, the 40In2O3/ZnIn2S4 exhibited an obviously improved antibacterial performance against Pseudomonas aeruginosa, with an antibacterial rate of 99.8% after visible light irradiation of 80 mW cm−2 for 420 min. The 40In2O3/ZnIn2S4 composite showed the highest photocurrent density, indicating an enhanced separation of photogenerated charge carriers. Electron spin resonance results indicated that the 40In2O3/ZnIn2S4 composite generated both ·O2 and ·OH radicals under visible light, whereas ·OH radicals were almost not detected in ZnIn2S4 alone, suggesting the presence of a Z-scheme heterojunction between In2O3 and ZnIn2S4, thereby enhancing the degradation and antibacterial capabilities of the composite. This offers fresh perspectives on designing effective photocatalytic materials for use in antibacterial and antifouling applications. Full article
(This article belongs to the Special Issue Heterogeneous Photocatalysts Based on Nanocomposites)
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<p>Synthesis process of the In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub> composites.</p>
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<p>Internal structure of the photochemical reaction apparatus.</p>
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<p>XRD patterns of MIL, In<sub>2</sub>O<sub>3</sub>, ZnIn<sub>2</sub>S<sub>4</sub>, and In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub> composites.</p>
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<p>SEM images of MIL (<b>a</b>), In<sub>2</sub>O<sub>3</sub> (<b>b</b>–<b>d</b>), ZnIn<sub>2</sub>S<sub>4</sub> (<b>e</b>), and 40In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub> (<b>f</b>); TEM images of 40In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub> (<b>f</b>,<b>g</b>); (<b>h</b>) Elemental mapping of 40In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub> composite.</p>
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<p>SEM images of MIL (<b>a</b>), In<sub>2</sub>O<sub>3</sub> (<b>b</b>–<b>d</b>), ZnIn<sub>2</sub>S<sub>4</sub> (<b>e</b>), and 40In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub> (<b>f</b>); TEM images of 40In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub> (<b>f</b>,<b>g</b>); (<b>h</b>) Elemental mapping of 40In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub> composite.</p>
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<p>The full XPS survey spectra of In<sub>2</sub>O<sub>3</sub>, ZnIn<sub>2</sub>S<sub>4</sub>, and 40In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub> (<b>a</b>); high-resolution XPS spectra of In3d (<b>b</b>), O1s (<b>c</b>) Zn2p (<b>d</b>), and S2p (<b>e</b>).</p>
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<p>(<b>a</b>) Photodegradation of MO by MIL, In<sub>2</sub>O<sub>3</sub>, ZnIn<sub>2</sub>S<sub>4</sub>, and In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub> composites; (<b>b</b>) the changes in UV absorbance of methyl orange during the degradation process by 40In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub>; (<b>c</b>) cycling degradation of 40In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub>; (<b>d</b>) XRD patterns of 40In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub> after three cycles under visible light irradiation; (<b>d</b>) the changes in the XRD pattern of 40In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub> after degrading methyl orange.</p>
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<p>(<b>a</b>) Survival rates and (<b>b</b>) antimicrobial rates of MIL, In<sub>2</sub>O<sub>3</sub>, ZnIn<sub>2</sub>S<sub>4</sub>, and In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub> composites against <span class="html-italic">P. aeruginosa</span>.</p>
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<p>(<b>a</b>) UV–Vis diffuse reflection absorbance spectra, (<b>b</b>) Tauc plots, (<b>c</b>) Mott–Schottky curves of MIL, In<sub>2</sub>O<sub>3</sub>, ZnIn<sub>2</sub>S<sub>4</sub>, and 40In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub>, (<b>d</b>) photocurrent response curves of MIL, In<sub>2</sub>O<sub>3,</sub> ZnIn<sub>2</sub>S<sub>4</sub>, and In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub> composites, (<b>e</b>,<b>f</b>) EPR spectra of In<sub>2</sub>O<sub>3</sub>, ZnIn<sub>2</sub>S<sub>4</sub>, and 40In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub>.</p>
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<p>Possible charge transfer mechanism of In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub>.</p>
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14 pages, 5143 KiB  
Article
A Self-Powered, Skin Adhesive, and Flexible Human–Machine Interface Based on Triboelectric Nanogenerator
by Xujie Wu, Ziyi Yang, Yu Dong, Lijing Teng, Dan Li, Hang Han, Simian Zhu, Xiaomin Sun, Zhu Zeng, Xiangyu Zeng and Qiang Zheng
Nanomaterials 2024, 14(16), 1365; https://doi.org/10.3390/nano14161365 - 20 Aug 2024
Viewed by 691
Abstract
Human–machine interactions (HMIs) have penetrated into various academic and industrial fields, such as robotics, virtual reality, and wearable electronics. However, the practical application of most human–machine interfaces faces notable obstacles due to their complex structure and materials, high power consumption, limited effective skin [...] Read more.
Human–machine interactions (HMIs) have penetrated into various academic and industrial fields, such as robotics, virtual reality, and wearable electronics. However, the practical application of most human–machine interfaces faces notable obstacles due to their complex structure and materials, high power consumption, limited effective skin adhesion, and high cost. Herein, we report a self-powered, skin adhesive, and flexible human–machine interface based on a triboelectric nanogenerator (SSFHMI). Characterized by its simple structure and low cost, the SSFHMI can easily convert touch stimuli into a stable electrical signal at the trigger pressure from a finger touch, without requiring an external power supply. A skeleton spacer has been specially designed in order to increase the stability and homogeneity of the output signals of each TENG unit and prevent crosstalk between them. Moreover, we constructed a hydrogel adhesive interface with skin-adhesive properties to adapt to easy wear on complex human body surfaces. By integrating the SSFHMI with a microcontroller, a programmable touch operation platform has been constructed that is capable of multiple interactions. These include medical calling, music media playback, security unlocking, and electronic piano playing. This self-powered, cost-effective SSFHMI holds potential relevance for the next generation of highly integrated and sustainable portable smart electronic products and applications. Full article
(This article belongs to the Special Issue Self-Powered Flexible Sensors Based on Triboelectric Nanogenerators)
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<p>Overview diagram of the proposed SSFHMI. (<b>a</b>) The proposed SSFHMI and its application in intelligence interaction, medical calls, media player control, password unlocking, and electronic keyboard playing. (<b>b</b>) Construction of the SSFHMI. (<b>c</b>) Atomic-scale and macroscopic charge transfer mechanisms during friction between PDMS and PTFE. (<b>i</b>) PDMS and PTFE are in Separated stage. (<b>ii</b>) Compressing stage. (<b>iii</b>) Compressed stage. (<b>iv</b>) Separating stage. (<b>d</b>) The diagram of the mechanism of adhesion effect after contact between the adhesive layer and the human tissue. (<b>e</b>) Photograph of the proposed SSFHMI. (<b>i</b>) MCU connected with SSFHMI. (<b>ii</b>) SSFHMI attached to the back of the hand.</p>
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<p>Preparation, properties of the hydrogel-based adhesive layer. (<b>a</b>) Schematic illustration of the material used to prepare the adhesive layer. (<b>b</b>) Steps and methods for preparing the adhesive layer. (<b>c</b>) The tensile stress-strain curves and dynamic strain amplitude curves of the nanocomposite hydrogel adhesives. (<b>i</b>) Tensile stress-strain curves of LAP nanosheets at different concentrations. (<b>ii</b>) Self-healing characteristic curve. (<b>d</b>) Photograph of the adhesive layer for bonding SSFHMI to biological tissues, and the viscosity curve of the adhesive layer.</p>
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<p>Electrical characterization of the TENG. (<b>a</b>) Illustration of the macro-level working mechanism of a single-electrode TENG. (<b>i</b>) Compressing. (<b>ii</b>) Compressed. (<b>iii</b>) Separating. (<b>iv</b>) Separated. (<b>b</b>–<b>d</b>) Open-circuit voltage, short-circuit current, and short-circuit charge at the working frequency of 3 Hz, respectively. (<b>e</b>) Output voltage, current, and power density under the different external load resistances. (<b>f</b>) Output voltage of the TENG during 18,000 working cycles.</p>
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<p>The output characterization of the TENG array on the proposed SSFHMI. (<b>a</b>) The output waveform of nine TENGs. (<b>b</b>) The output voltage of nine TENGs. (<b>c</b>) Results of the two-sample T-test performed between TENGs. (<b>d</b>) 3D heat map corresponding to the different pressing positions on the TENG array.</p>
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<p>The signal coding of the proposed SSFHMI for intelligent control. (<b>a</b>) Schematic diagram of the human–computer interaction using SSFHMI. (<b>b</b>) Password lock function of the T9 keyboard and its 3D heat map of corresponding operations. (<b>c</b>) Application of the medical call. (<b>i</b>) Practical application demonstration. (<b>ii</b>) Comparison with similar work in Structure Complexity and Anti-interference [<a href="#B45-nanomaterials-14-01365" class="html-bibr">45</a>,<a href="#B46-nanomaterials-14-01365" class="html-bibr">46</a>,<a href="#B47-nanomaterials-14-01365" class="html-bibr">47</a>,<a href="#B48-nanomaterials-14-01365" class="html-bibr">48</a>,<a href="#B49-nanomaterials-14-01365" class="html-bibr">49</a>,<a href="#B50-nanomaterials-14-01365" class="html-bibr">50</a>,<a href="#B51-nanomaterials-14-01365" class="html-bibr">51</a>,<a href="#B52-nanomaterials-14-01365" class="html-bibr">52</a>].</p>
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14 pages, 2462 KiB  
Article
Development of a Gold Nanoparticle-Based Sensor for Authentication of Organic Milk Based on Differential Levels of miRNA
by Karelmar Lopez-Benitez, Patricia Alcazar-Gonzalez, Loubna Abou el qassim, Mª Teresa Fernandez-Argüelles, Fernando Vicente, Luis J. Royo and Mario Menendez-Miranda
Nanomaterials 2024, 14(16), 1364; https://doi.org/10.3390/nano14161364 - 19 Aug 2024
Viewed by 614
Abstract
Dairy production systems significantly impact environmental sustainability, animal welfare, and human health. Intensive farming maximizes output through high-input practices, raising concerns about environmental degradation, animal welfare, and health risks from antibiotic residues. Conversely, organic farming emphasizes sustainable practices, animal welfare, and minimal synthetic [...] Read more.
Dairy production systems significantly impact environmental sustainability, animal welfare, and human health. Intensive farming maximizes output through high-input practices, raising concerns about environmental degradation, animal welfare, and health risks from antibiotic residues. Conversely, organic farming emphasizes sustainable practices, animal welfare, and minimal synthetic inputs, potentially enhancing biodiversity, soil health, and milk quality. MicroRNAs (miRNAs), non-coding RNAs regulating gene expression, are promising biomarkers due to their response to various conditions. In this study, miRNAs bta-miR-103 and bta-miR-155, which are abundant in milk from pasture-fed cows, were selected. Additionally, bta-miR-215, which is abundant in milk fat from intensive systems, was also studied, in order to differentiate dairy production systems. A novel, cost-effective gold nanoparticle (AuNP)-based sensor was developed for miRNA detection, leveraging the unique plasmonic properties of AuNPs for visual detection. The method involves functionalizing AuNPs with complementary RNA probes and detecting miRNA-induced aggregation through colorimetric changes. This rapid, results in 30 min, and sensitive, visual limit of detection of 200 nM, assay requires minimal instrumentation and can be easily interpreted, offering significant advantages for field implementation in characterizing dairy production systems. This study demonstrates the successful application of this sensor in detecting miRNAs in 350 nM miRNA spiked raw milk, highlighting its potential for in situ dairy industry applications. Full article
(This article belongs to the Special Issue Synthesis and Applications of Gold Nanoparticles: 2nd Edition)
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<p>(<b>a</b>) Absorbance spectrum of the synthesized AuNPs; (<b>b</b>) TEM image of AuNPs.</p>
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<p>(<b>a</b>) Scheme of the Head-to-Head (H-H) conformation for the hybridization process. (<b>b</b>) Scheme representation of the Tail-to-Tail (T-T) conformation for the hybridization process.</p>
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<p>Scheme of the detection assay.</p>
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<p>Agarose gel electrophoresis was carried out to optimize the concentration of AggA, AggB, AggC, and AggD for the detection of bta-miR-103. Bioconjugation with different molar ratios of each DNA probe per functionalized AuNP is shown.</p>
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<p>(<b>a</b>) Magnesium chloride optimization for the T-T assay format detection of bta-miR-103; (<b>b</b>) hybridization time optimization for the T-T assay format detection of bta-miR-155; (<b>c</b>) hybridization temperature optimization for the T-T assay format detection of bta-miR-215; − no presence of the analyte; + in presence of the analyte. TLC spots were carried out in triplicate (n = 3).</p>
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<p>Visual limit of detection determination. (<b>a</b>) Visual LOD for bta-miR-103 using H-H (upper row) and T-T (lower row) assay formats. (<b>b</b>) Visual LOD for bta-miR-155 using H-H (upper row) and T-T (lower row) assay formats. (<b>c</b>) Visual LOD for bta-miR-215 using H-H (upper row) and T-T (lower row) assay formats. TLC spots were carried out in triplicate (n = 3).</p>
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<p>(<b>a</b>) Sample analysis using T-T conformations for raw milk (upper row) and spiked sample with 350 nM miR103, miR155, and miR215 (lower row). (<b>b</b>) Sample analysis using H-H conformations for raw milk (upper row) and spiked sample with 350 nM miR103, miR155, and miR215 (lower row). (<b>c</b>) Spiked sample 2 with 350 nM miR103 (upper row); spiked sample 3 with 350 nM miR155 (middle row); and spiked sample 4 with 350 nM miR215 (lower row). TLC spots were carried out in triplicate (n = 3).</p>
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26 pages, 8300 KiB  
Article
Adipocyte-Targeted Nanocomplex with Synergistic Photothermal and Pharmacological Effects for Combating Obesity and Related Metabolic Syndromes
by Yuanyuan Zhang, Xiaojiao Zeng, Fan Wu, Xiaopeng Yang, Tingting Che, Yin Zheng, Jie Li, Yufei Zhang, Xinge Zhang and Zhongming Wu
Nanomaterials 2024, 14(16), 1363; https://doi.org/10.3390/nano14161363 - 19 Aug 2024
Viewed by 924
Abstract
Obesity is a global epidemic which induces a multitude of metabolic disorders. Browning of white adipose tissue (WAT) has emerged as a promising therapeutic strategy for promoting weight loss and improving associated metabolic syndromes in people with obesity. However, current methods of inducing [...] Read more.
Obesity is a global epidemic which induces a multitude of metabolic disorders. Browning of white adipose tissue (WAT) has emerged as a promising therapeutic strategy for promoting weight loss and improving associated metabolic syndromes in people with obesity. However, current methods of inducing white adipose tissue browning have limited applicability. We developed a nanocomplex pTSL@(P+I), which is a temperature-sensitive liposome (TSL) surface-conjugated with an adipocyte-targeting peptide (p) and loaded with both browning-promoting agents (P) and photosensitizing agents (I). This nanocomplex exhibits adipocyte targeting, as well as synergistic pharmacological and photothermal properties to promote browning. pTSL@(P+I) effectively upregulates UCP1 and COX5B expression by activating the transcription axis of PPARγ/PGC1α and HSF1/PGC1α, thereby promoting white adipose tissue browning and reducing obesity. This novel nanocomplex exhibited a uniform spherical shape, with an average diameter of approximately 200 nm. Additionally, the nanocomplexes exhibited remarkable photothermal properties and biocompatibility. Further, when adipocytes were treated with pTSL@(P+I), their triglyceride content decreased remarkably and intracellular mitochondrial activity increased significantly. When applied to diet-induced obesity (DIO) mice, the nanocomplex exhibited significant efficacy, demonstrating a notable 14.4% reduction in body weight from the initial measurement, a decreased fat/lean mass ratio of 20.8%, and no statistically significant disparities (p > 0.05) in associated side effects when compared to the control group. In summary, implementation of the targeted nanocomplex pTSL@(P+I) to enhance energy expenditure by stimulating white adipose tissue browning offers a promising therapeutic approach for the treatment of obesity and related metabolic syndromes. Full article
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<p>(<b>A</b>) <sup>1</sup>H NMR spectra of DSPE-PEG2000-Mal in CDCl<sub>3</sub> and DSPE-PEG2000-Pep in CD<sub>4</sub>O. (<b>B</b>) TEM images of targeted nanocomplex pTSL@(P+I). (<b>C</b>) Histogram of the particle size distribution of pTSL@(P+I) measured by DLS. (<b>D</b>) Potential distribution of the targeted nanocomplex measured by DLS. (<b>E</b>) UV–visible-near infrared (UV–VIS-NIR) spectrum of pTSL@(P+I). (<b>F</b>) Particle size stability of pTSL@(P+I) at 25 °C and 37 °C measured by DLS. Photothermal conversion curves (<b>G</b>) and photothermal images (<b>H</b>) of different concentrations of pTSL@(P+I) after irradiation with 808-nm NIR light (1.0 W/cm<sup>2</sup>) for various durations. (<b>I</b>) Photothermal conversion curves of pTSL@(P+I) at a concentration of 500 μg/mL under varying powers and durations when exposed to 808-nm NIR light. (<b>J</b>) Cumulative release curves of Piog from pTSL@(P+I) at 37 °C and 45 °C, respectively. (<b>K</b>) Hemolysis of different concentrations of pTSL@(P+I). (<b>L</b>) 3T3-L1 cell and differentiated 3T3-L1 cell survival rates measured by CCK-8 method after treatment with different concentrations of pTSL@(P+I) for 48 h.</p>
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<p>(<b>A</b>) After labeling TSL@(P+I) and pTSL@(P+I) with FITC fluorescent probes, CLSM images of differentiated 3T3-L1 cells following co-incubation with TSL@(P+I), pTSL@(P+I), and anti-prohibitin + pTSL@(P+I) for 1 h (left) or 3 h (right), respectively. (the DAPI-stained nucleus as blue fluorescence, the FITC-labeled nanocomplex as green fluorescence) (<b>B</b>) Quantification of the average fluorescence intensity (FI) of FITC in 3T3-L1 cells from each experimental group in (<b>A</b>) using Image J 1.8.0 software. (<b>C</b>) Schematic diagram of cell culture and intervention process. Oil Red O-stained images of 3T3-L1 cells induced differentiation and intervened in each group (<b>D</b>,<b>E</b>) and quantification of lipid droplets after extraction with isopropanol (<b>F</b>). (<b>G</b>) Quantification of the number of lipid droplets per cell following various interventions (<span class="html-italic">n</span> = 5). Concentrations of lipid triglyceride (TAG) (<b>H</b>) and free fatty acid (FFA) (<b>I</b>) in differentiated 3T3-L1 cells subjected to various interventions. Visualization of mitochondrial fluorescence (<b>J</b>) in differentiated 3T3-L1 cells following various interventions and quantification of the average fluorescence intensity (FI) (<b>K</b>) in cells from each experimental group in (<b>J</b>) using Image J 1.8.0 software. (the DAPI-stained nucleus as blue fluorescence, the Mito-Tracker as red fluorescence) * <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01, *** <span class="html-italic">p</span> &lt; 0.001, **** <span class="html-italic">p</span> &lt; 0.0001; ns = not significant. Statistical significance was assessed via two-way ANOVA (<b>B</b>) and one-way ANOVA (<b>F</b>–<b>K</b>).</p>
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<p>(<b>A</b>) Protein expression levels of PGC1α, HSF1, PPARγ, UCP1, and COX5B were assessed via Western blot analysis in each group of 3T3-L1 cells following induction of differentiation and intervention. (<b>B</b>–<b>F</b>) Quantitative analysis of the corresponding protein levels in (<b>A</b>) was conducted using Image J 1.8.0 software. The levels of inflammatory factors IL-1β (<b>G</b>) and TNF-α (<b>H</b>) were measured by ELISA in each group of 3T3-L1 cells following induction of differentiation and intervention. * <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01, *** <span class="html-italic">p</span> &lt; 0.001, **** <span class="html-italic">p</span> &lt; 0.0001; ns = not significant. Statistical significance was assessed via one-way ANOVA.</p>
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<p>(<b>A</b>) A schematic diagram illustrating the in vivo experiments conducted on mice (HI: Latin for hypodermic injection). (<b>B</b>) Representative effect plots depicting the outcomes observed in each group of diet-induced obesity mice following a 4-week treatment. Assessment of daily changes in body weight (<b>C</b>) and dietary food intake (<b>D</b>) of mice (<span class="html-italic">n</span> = 5) in each intervention group. (<b>E</b>) Analysis of the weight ratio of fat/lean at the experiment’s endpoint using a small animal body fat analyzer (<span class="html-italic">n</span> = 5). Typical anatomical drawings (<b>F</b>) and corresponding weights (<b>G</b>) of eWAT, iWAT and BAT of mice (<span class="html-italic">n</span> = 5) in each experimental group at the endpoint. (<b>H</b>) After subcutaneous injection of nanocomplexes into both sides of the iWAT of mice in each group, infrared thermal imaging images of the left inguinal region of mice were irradiated by 808 nm NIR light (0.5 W/cm<sup>2</sup>) at different times. (<b>I</b>) Quantitative analysis of photothermal conversion in the left inguinal area of mice in the PBS, pTSL@I, and pTSL@(P+I) groups at different times with irradiation of 808 nm NIR light (0.5 W/cm<sup>2</sup>) in (H) (<span class="html-italic">n</span> = 3). (<b>J</b>) Quantitative analysis of left and right groin temperature before and after laser irradiation of left groin in pTSL@I and pTSL@(P+I) groups in (H) (<span class="html-italic">n</span> = 3). * <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01, *** <span class="html-italic">p</span> &lt; 0.001, **** <span class="html-italic">p</span> &lt; 0.0001; ns = not significant. Statistical significance was assessed via one-way ANOVA.</p>
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<p>Glucose measurements and area under the curve of glucose tolerance test (GTT) (<b>A</b>,<b>B</b>) and insulin tolerance test (ITT) (<b>C</b>,<b>D</b>) in each group of diet-induced obesity mice after treatment (<span class="html-italic">n</span> = 5). The 24 h mean activity counts (<b>E</b>), mean and time-point O<sub>2</sub> consumption (<b>F</b>,<b>G</b>), mean and time-point CO<sub>2</sub> production (<b>H</b>,<b>I</b>), and mean respiratory quotient (RQ) (<b>J</b>) in mice analyzed by physiological metabolic cages (<span class="html-italic">n</span> = 3). Body temperatures of diet-induced obesity mice (<b>K</b>) and area under the curve (<b>L</b>) in each group during a 4 h cold tolerance test before the end of the experiment (<span class="html-italic">n</span> = 3). * <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01, *** <span class="html-italic">p</span> &lt; 0.001, **** <span class="html-italic">p</span> &lt; 0.0001; ns = not significant. Statistical significance was assessed via one-way ANOVA.</p>
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<p>(<b>A</b>–<b>C</b>) Levels of lipid triglyceride (TAG), TC, and LDL-C in each group of mice (<span class="html-italic">n</span> = 5) at the endpoint of the experiment. Protein expression levels of PGC1α, HSF1, PPARγ, UCP1, and COX5B in iWAT after intervention were detected using Western blotting in each group of mice (<b>D</b>) and quantitative analysis of corresponding protein levels by Image J 1.8.0 software (<b>E</b>–<b>I</b>). * <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01, *** <span class="html-italic">p</span> &lt; 0.001, **** <span class="html-italic">p</span> &lt; 0.0001; ns = not significant. Statistical significance was assessed via one-way ANOVA.</p>
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<p>Levels of iWAT inflammatory cytokines IL-1β (<b>A</b>) and TNF-α (<b>B</b>) in mice measured by ELISA. (<b>C</b>) H&amp;E staining of typical iWAT and eWAT of mice in each group after treatment. (<b>D</b>) Morphometric analysis of adipocyte cell sizes (<span class="html-italic">n</span> = 100 data points) in (<b>C</b>). Uncoupling protein 1 (UCP-1) labeled immunohistochemical staining (<b>E</b>) and quantification of UCP-1 expression (<b>F</b>) in (<b>E</b>) using Image J 1.8.0 software and UCP-1 labeled immunofluorescence images (<b>G</b>) and quantification of UCP-1 expression (<b>H</b>) in (<b>G</b>) using Image J 1.8.0 software of typical iWAT and eWAT of mice in each group after treatment. * <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01, **** <span class="html-italic">p</span> &lt; 0.0001; ns = not significant. Statistical significance was assessed via one-way ANOVA.</p>
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<p>(<b>A</b>) Composition and structure of targeted nanocomplex pTSL@(P+I). (<b>B</b>) NIR light-activated targeted nanocomplex for white adipose tissue browning to enhance anti-obesity effects in mice.</p>
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<p>Anti-obesity mechanisms of pTSL@(P+I)-mediated photothermal and pharmacological synergistic therapy.</p>
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23 pages, 31708 KiB  
Article
Development of In Situ Methods for Preparing La-Mn-Co-Based Compounds over Carbon Xerogel for Oxygen Reduction Reaction in an Alkaline Medium
by Jhony Xavier Flores-Lasluisa, Bryan Carré, Joachim Caucheteux, Philippe Compère, Alexandre F. Léonard and Nathalie Job
Nanomaterials 2024, 14(16), 1362; https://doi.org/10.3390/nano14161362 - 19 Aug 2024
Viewed by 579
Abstract
Metal oxides containing La, Mn, and Co cations can catalyze oxygen reduction reactions (ORRs) in electrochemical processes. However, these materials require carbon support and optimal interactions between both compounds to be active. In this work, two approaches to prepare composites of La-Mn-Co-based compounds [...] Read more.
Metal oxides containing La, Mn, and Co cations can catalyze oxygen reduction reactions (ORRs) in electrochemical processes. However, these materials require carbon support and optimal interactions between both compounds to be active. In this work, two approaches to prepare composites of La-Mn-Co-based compounds over carbon xerogel were developed. Using sol-gel methods, either the metal-based material was deposited on the existing carbon xerogel or vice versa. The metal oxide selected was the LaMn0.7Co0.3O3 perovskite, which has good catalytic behavior and selectivity towards direct ORRs. All the as-prepared composites were tested for ORRs in alkaline liquid electrolytes and characterized by diverse physicochemical techniques such as XRD, XPS, SEM, or N2 adsorption. Although the perovskite structure either decomposed or failed to form using those in situ methods, the materials exhibited great catalytic activity, which can be ascribed to the strengthening of the interactions between oxides and the carbon support via C-O-M covalent bonds and to the formation of new active sites such as the MnO/Co heterointerfaces. Moreover, Co-Nx-C species are formed during the synthesis of the metal compounds over the carbon xerogel. These species possess a strong catalytic activity towards ORR. Therefore, the composites formed by synthesizing metal compounds over the carbon xerogel exhibit the best performance in the ORR, which can be ascribed to the presence of the MnO/Co heterointerfaces and Co-Nx-C species and the strong interactions between both compounds. Moreover, the small nanoparticle size leads to a higher number of active sites available for the reaction. Full article
(This article belongs to the Special Issue Carbon Nanomaterials for Electrocatalytic Application)
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<p>X-ray diffraction patterns for the pristine perovskite (P), carbon xerogel (CX), and composite materials. (<b><span style="color:gray">▬</span></b>) P; (<b><span style="color:green">▬</span></b>) P + CX; (<b>▬</b>) CX; (<b><span style="color:red">▬</span></b>) CX_P_N<sub>2</sub>; (<b><span style="color:#E6AF2D">▬</span></b>) CX_P_O<sub>2</sub>; (<b><span style="color:#292DD7">▬</span></b>) P_CX_5.6; (<b><span style="color:#B4E3FF">▬</span></b>) P_CX_5.3.</p>
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<p>TEM images for the different samples: (<b>a</b>,<b>d</b>) P + CX; (<b>b</b>,<b>e</b>) CX_P_N<sub>2</sub>; and (<b>c</b>,<b>f</b>) P_CX_5.3. Inset (<b>b</b>): magnification of the region indicated by the arrow.</p>
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<p>SEM images for the different samples: (<b>a</b>) pristine perovskite (P); (<b>b</b>) CX; (<b>c</b>) P + CX; (<b>d</b>) CX_P_N<sub>2</sub>; and (<b>e</b>) P_CX_5.3.</p>
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<p>N<sub>2</sub> adsorption isotherms at −196 °C for the pristine CX and P samples and the composites containing both compounds. (<b><span style="color:gray">▬</span></b>) P; (<b>▬</b>) CX; (<b><span style="color:green">▬</span></b>) P + CX; (<b><span style="color:red">▬</span></b>) CX_P_N<sub>2</sub>; (<b><span style="color:#E6AF2D">▬</span></b>) CX_P_O<sub>2</sub>; (<b><span style="color:#292DD7">▬</span></b>) P_CX_5.6; (<b><span style="color:#B4E3FF">▬</span></b>) P_CX_5.3.</p>
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<p>Deconvolution of the Mn 2p (<b>a</b>) and O 1s (<b>b</b>) of the composites.</p>
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<p>Cyclic voltammetry of the composites in 0.1 M KOH medium saturated with either N<sub>2</sub> (<b>a</b>) or O<sub>2</sub> (<b>b</b>). Scan rate: 10 mV s<sup>−1</sup>. (<b>▬</b>) CX; (<b><span style="color:red">▬</span></b>) CX_P_N<sub>2</sub>; (<b><span style="color:#E6AF2D">▬</span></b>) CX_P_O<sub>2</sub>; (<b><span style="color:#292DD7">▬</span></b>) P_CX_5.6; (<b><span style="color:#B4E3FF">▬</span></b>) P_CX_5.3. All current densities are reported by the geometric area of the electrode.</p>
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<p>(<b>a</b>) RDE linear sweep voltammograms for composites in 0.1 M KOH saturated with O<sub>2</sub> at 1600 rpm; (<b>b</b>) number of electrons involved in ORR at increasing potential. (<span style="color:gray">▬</span>) P; (<b>▬</b>) CX; (<b><span style="color:green">▬</span></b>) P + CX; (<b><span style="color:red">▬</span></b>) CX_P_N<sub>2</sub>; (<b><span style="color:#E6AF2D">▬</span></b>) CX_P_O<sub>2</sub>; (<b><span style="color:#292DD7">▬</span></b>) P_CX_5.6; (<b><span style="color:#B4E3FF">▬</span></b>) P_CX_5.3; (▬) 20 wt.% Pt/C. All current densities are reported by the geometric area of the electrode.</p>
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22 pages, 4474 KiB  
Review
Sensors Based on Molecularly Imprinted Polymers in the Field of Cancer Biomarker Detection: A Review
by Camila Quezada, S. Shiva Samhitha, Alexis Salas, Adrián Ges, Luis F. Barraza, María Carmen Blanco-López, Francisco Solís-Pomar, Eduardo Pérez-Tijerina, Carlos Medina and Manuel Meléndrez
Nanomaterials 2024, 14(16), 1361; https://doi.org/10.3390/nano14161361 - 19 Aug 2024
Viewed by 665
Abstract
Biomarkers play a pivotal role in the screening, diagnosis, prevention, and post-treatment follow-up of various malignant tumors. In certain instances, identifying these markers necessitates prior treatment due to the complex nature of the tumor microenvironment. Consequently, advancing techniques that exhibit selectivity, specificity, and [...] Read more.
Biomarkers play a pivotal role in the screening, diagnosis, prevention, and post-treatment follow-up of various malignant tumors. In certain instances, identifying these markers necessitates prior treatment due to the complex nature of the tumor microenvironment. Consequently, advancing techniques that exhibit selectivity, specificity, and enable streamlined analysis hold significant importance. Molecularly imprinted polymers (MIPs) are considered synthetic antibodies because they possess the property of molecular recognition with high selectivity and sensitivity. In recent years, there has been a notable surge in the investigation of these materials, primarily driven by their remarkable adaptability in terms of tailoring them for specific target molecules and integrating them into diverse analytical technologies. This review presents a comprehensive analysis of molecular imprinting techniques, highlighting their application in developing sensors and analytical methods for cancer detection, diagnosis, and monitoring. Therefore, MIPs offer great potential in oncology and show promise for improving the accuracy of cancer screening and diagnosis procedures. Full article
(This article belongs to the Section Biology and Medicines)
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<p>(<b>A</b>) Template molecules. (<b>B</b>) Reagents used in the molecular printing process. (<b>C</b>) General scheme of molecular imprinting polymers, from (<b>a</b>–<b>c</b>), the pre-polymerization, polymerization, and template extraction complex, is presented. (<b>D</b>–<b>H</b>) Scheme of the most common molecular printing methods.</p>
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<p>Solid-phase synthesis template molecule immobilization by different functional groups [<a href="#B68-nanomaterials-14-01361" class="html-bibr">68</a>].</p>
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<p>Sensors made with molecular imprinting polymers for the detection of lung cancer. (<b>A</b>) Proteomic analysis [<a href="#B90-nanomaterials-14-01361" class="html-bibr">90</a>]. (<b>B</b>) Electrochemical sensor for epitope identification [<a href="#B91-nanomaterials-14-01361" class="html-bibr">91</a>]. (<b>C</b>) Electrochemical sensor for the identification of endogenous substances [<a href="#B92-nanomaterials-14-01361" class="html-bibr">92</a>]. (<b>D</b>) Chemoresistive sensor for the determination of hexanal [<a href="#B93-nanomaterials-14-01361" class="html-bibr">93</a>].</p>
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<p>Schematics of sensors designed for the detection of tumor markers for the reproductive system using MIPs as identification material. (<b>A</b>) Sensitive and specific plasmonic biosensor for the detection of PSA [<a href="#B118-nanomaterials-14-01361" class="html-bibr">118</a>]. (<b>B</b>) Electrochemical sensor aimed at the quantitative analysis of PSA [<a href="#B120-nanomaterials-14-01361" class="html-bibr">120</a>]. (<b>C</b>) Electrochemical sensor for the identification of PSA [<a href="#B121-nanomaterials-14-01361" class="html-bibr">121</a>].</p>
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9 pages, 1811 KiB  
Article
Green Phytic Acid-Assisted Synthesis of LiMn1-xFexPO4/C Cathodes for High-Performance Lithium-Ion Batteries
by Yueying Li, Chenlu Hu, Zhidong Hou, Chunguang Wei and Jian-Gan Wang
Nanomaterials 2024, 14(16), 1360; https://doi.org/10.3390/nano14161360 - 19 Aug 2024
Viewed by 707
Abstract
As a promising cathode material, olivine-structured LiMnPO4 holds enormous potential for lithium-ion batteries. Herein, we demonstrate a green biomass-derived phytic-acid-assisted method to synthesize a series of LiMn1−xFexPO4/C composites. The effect of Fe doping on the crystal [...] Read more.
As a promising cathode material, olivine-structured LiMnPO4 holds enormous potential for lithium-ion batteries. Herein, we demonstrate a green biomass-derived phytic-acid-assisted method to synthesize a series of LiMn1−xFexPO4/C composites. The effect of Fe doping on the crystal structure and morphology of LiMnPO4 particles is investigated. It is revealed that the optimal Fe doping amount of x = 0.2 enables a substantial enhancement of interfacial charge transfer ability and Li+ ion diffusion kinetics. Consequently, a large reversible capacity output of 146 mAh g−1 at 0.05 C and a high rate capacity of 77 mAh g−1 at 2 C were acquired by the as-optimized LiMn0.8Fe0.2PO4/C cathode. Moreover, the LiMn0.8Fe0.2PO4/C delivered a specific capacity of 68 mAh g−1 at 2 C after 500 cycles, with a capacity retention of 88.4%. This work will unveil a green synthesis route for advancing phosphate cathode materials toward practical implementation. Full article
(This article belongs to the Topic Advanced Nanomaterials for Lithium-Ion Batteries)
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<p>(<b>a</b>) Schematic illustration for the fabrication of LMFP/C-x. SEM images of (<b>b</b>) LMP/C, (<b>c</b>) LMFP/C-0.1, (<b>d</b>) LMFP/C-0.2, and (<b>e</b>) LMFP/C-0.4. (<b>f</b>) TEM and (<b>g</b>) HRTEM images of LMFP/C-0.2.</p>
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<p>(<b>a</b>) XRD patterns and (<b>b</b>) Raman spectra of LMP/C, LMFP/C-0.1, LMFP/C-0.2, and LMFP/C-0.4 with an enlarged XRD profile of (020) plane (right part). (<b>c</b>) TGA curve of LMFP/C-0.2. (<b>d</b>) N<sub>2</sub> adsorption–desorption isotherms of various samples.</p>
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<p>(<b>a</b>) XPS survey spectrum of LMFP/C-0.2. High-resolution XPS spectra of (<b>b</b>) Mn 2p, (<b>c</b>) Fe 2p, and (<b>d</b>) P 2p of LMFP/C-0.2.</p>
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<p>(<b>a</b>) CV curves at a scan rate of 0.05 mV s<sup>−1</sup>, (<b>b</b>) charge/discharge curves, (<b>c</b>) cycling stabilities at 0.05 C, and (<b>d</b>) rate performances of LMFP/C, LMFP/C-0.1, LMFP/C-0.2, and LMFP/C-0.4. (<b>e</b>) Long-term stability of LMFP/C-0.2 at 2 C (inset: SEM images of the electrode before (<b>left</b>) and after (<b>right</b>) cycling test).</p>
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<p>(<b>a</b>) Nyquist plots and (<b>b</b>) corresponding relationship between Z′ and ω<sup>−1/2</sup> of the electrodes in the low-frequency region.</p>
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12 pages, 3437 KiB  
Article
Analysis of 3D Channel Current Noise in Small Nanoscale MOSFETs Using Monte Carlo Simulation
by Wenpeng Zhang, Qun Wei, Xiaofei Jia and Liang He
Nanomaterials 2024, 14(16), 1359; https://doi.org/10.3390/nano14161359 - 18 Aug 2024
Viewed by 594
Abstract
As field effect transistors are reduced to nanometer dimensions, experimental and theoretical research has shown a gradual change in noise generation mechanisms. There are few studies on noise theory for small nanoscale transistors, and Monte Carlo (MC) simulations mainly focus on 2D devices [...] Read more.
As field effect transistors are reduced to nanometer dimensions, experimental and theoretical research has shown a gradual change in noise generation mechanisms. There are few studies on noise theory for small nanoscale transistors, and Monte Carlo (MC) simulations mainly focus on 2D devices with larger nanoscale dimensions. In this study, we employed MC simulation techniques to establish a 3D device simulation process. By setting device parameters and writing simulation programs, we simulated the raw data of channel current noise for a silicon-based metal–oxide–semiconductor field-effect transistor (MOSFET) with a 10 nm channel length and calculated the drain output current based on these data, thereby achieving static testing of the simulated device. Additionally, this study obtained a 3D potential distribution map of the device channel surface area. Based on the original data from the simulation analysis, this study further calculated the power spectral density of the channel current noise and analyzed how the channel current noise varies with gate voltage, source–drain voltage, temperature, and substrate doping density. The results indicate that under low-temperature conditions, the channel current noise of the 10 nm MOSFET is primarily composed of suppressed shot noise, with the proportion of thermal noise in the total noise slightly increasing as temperature rises. Under normal operating conditions, the channel current noise characteristics of the 10 nm MOSFET device are jointly characterized by suppressed shot noise, thermal noise, and cross-correlated noise. Among these noise components, shot noise is the main source of noise, and its suppression degree decreases as the bias voltage is reduced. These findings are consistent with experimental observations and theoretical analyses found in the existing literature. Full article
(This article belongs to the Special Issue Integrated Circuit Research for Nanoscale Field-Effect Transistors)
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<p>Flowchart of particle−based device simulator.</p>
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<p>The schematic diagram of the simulation structure for a MOSFET.</p>
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<p>Schematic diagram of program structure.</p>
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<p>(<b>a</b>) The potential distribution map of the device along the channel is presented at a gate–source voltage of 0.7 V and a drain–source voltage of 0.3 V; (<b>b</b>) the two-dimensional potential distribution map of the device’s channel region surface direction under different bias voltages.</p>
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<p>Simulation results of output I-V characteristics of 10 nm MOSFET.</p>
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<p>(<b>a</b>) Power dissipation at different gate−source biases; (<b>b</b>) variation in junction temperature with bias voltages.</p>
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<p>Relationship between simulation power spectral density and gate–source bias.</p>
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<p>Relationship between simulation power spectral density and source–drain bias.</p>
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<p>Relationship between simulation power spectral density and temperature.</p>
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<p>Relationship between simulation power spectral density and substrate doping density.</p>
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12 pages, 5082 KiB  
Article
Excellent Hole Mobility and Out–of–Plane Piezoelectricity in X–Penta–Graphene (X = Si or Ge) with Poisson’s Ratio Inversion
by Sitong Liu, Xiao Shang, Xizhe Liu, Xiaochun Wang, Fuchun Liu and Jun Zhang
Nanomaterials 2024, 14(16), 1358; https://doi.org/10.3390/nano14161358 - 17 Aug 2024
Viewed by 405
Abstract
Recently, the application of two–dimensional (2D) piezoelectric materials has been seriously hindered because most of them possess only in–plane piezoelectricity but lack out–of–plane piezoelectricity. In this work, using first–principles calculation, by atomic substitution of penta–graphene (PG) with tiny out–of–plane piezoelectricity, we design and [...] Read more.
Recently, the application of two–dimensional (2D) piezoelectric materials has been seriously hindered because most of them possess only in–plane piezoelectricity but lack out–of–plane piezoelectricity. In this work, using first–principles calculation, by atomic substitution of penta–graphene (PG) with tiny out–of–plane piezoelectricity, we design and predict stable 2D X–PG (X = Si or Ge) semiconductors with excellent in–plane and out–of–plane piezoelectricity and extremely high in–plane hole mobility. Among them, Ge–PG exhibits better performance in all aspects with an in–plane strain piezoelectric coefficient d11 = 8.43 pm/V, an out–of–plane strain piezoelectric coefficient d33 = −3.63 pm/V, and in–plane hole mobility μh = 57.33 × 103 cm2 V−1 s−1. By doping Si and Ge atoms, the negative Poisson’s ratio of PG approaches zero and reaches a positive value, which is due to the gradual weakening of the structure’s mechanical strength. The bandgaps of Si–PG (0.78 eV) and Ge–PG (0.89 eV) are much smaller than that of PG (2.20 eV), by 2.82 and 2.47 times, respectively. This indicates that the substitution of X atoms can regulate the bandgap of PG. Importantly, the physical mechanism of the out–of–plane piezoelectricity of these monolayers is revealed. The super–dipole–moment effect proposed in the previous work is proved to exist in PG and X–PG, i.e., it is proved that their out–of–plane piezoelectric stress coefficient e33 increases with the super–dipole–moment. The e33–induced polarization direction is also consistent with the super–dipole–moment direction. X–PG is predicted to have prominent potential for nanodevices applied as electromechanical coupling systems: wearable, ultra–thin devices; high–speed electronic transmission devices; and so on. Full article
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<p>Top and side views of 2 × 2 supercells of (<b>a</b>) PG, (<b>b</b>) Si–PG, and (<b>c</b>) Ge–PG.</p>
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<p>The phonon spectra with corresponding phonon density of states (PHDOS) of (<b>a</b>) Si–PG and (<b>b</b>) Ge–PG monolayers. (<b>c</b>) Formation energy; (<b>d</b>) Young’s modulus (in units of N/m); (<b>e</b>) Poisson’s ratio of PG and X–PG; (<b>f</b>,<b>g</b>) AIMD simulations of ground states of X–PG.</p>
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<p>Planer–average charge density difference with Bader charge analysis (in red numbers) and electrostatic potentials of (<b>a</b>) PG, (<b>b</b>) Si–PG, and (<b>c</b>) Ge–PG monolayers. Band structures with the corresponding projected density of states (PDOS) of (<b>d</b>) Si–PG and (<b>e</b>) Ge–PG. The unit of PDOS is states/(eV • unit cell). The Fermi level is set to zero.</p>
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<p>(<b>a</b>) The energy shifting and (<b>b</b>) band–edge positions as a function of the uniaxial strain in the <span class="html-italic">x</span> or <span class="html-italic">y</span> transport direction in PG and X–PG monolayers.</p>
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<p>(<b>a</b>) Electron–contributed, ion–contributed, and total values of the out–of–plane piezoelectric stress coefficient <span class="html-italic">e</span><sub>33</sub> of X–PG monolayers. (<b>b</b>) The <span class="html-italic">e</span><sub>33</sub> value of PG and X–PG as a function of the super–dipole–moment inside them. (<b>c</b>) Schematic diagram of the out–of–plane piezoelectric strain coefficient <span class="html-italic">d</span><sub>33</sub> of Ge–PG.</p>
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20 pages, 4735 KiB  
Article
Behavior of Polymer Electrode PEDOT:PSS/Graphene on Flexible Substrate for Wearable Biosensor at Different Loading Modes
by Mariya Aleksandrova, Valentin Mateev and Ivo Iliev
Nanomaterials 2024, 14(16), 1357; https://doi.org/10.3390/nano14161357 - 17 Aug 2024
Viewed by 603
Abstract
In recent years, flexible and wearable biosensor technologies have gained significant attention due to their potential to revolutionize healthcare monitoring. Among the various components involved in these biosensors, the electrode material plays a crucial role in ensuring accurate and reliable detection. In this [...] Read more.
In recent years, flexible and wearable biosensor technologies have gained significant attention due to their potential to revolutionize healthcare monitoring. Among the various components involved in these biosensors, the electrode material plays a crucial role in ensuring accurate and reliable detection. In this regard, polymer electrodes, such as Poly(3,4 ethylenedioxythiophene): poly(styrenesulfonate), combined with graphene (PEDOT:PSS/graphene), have emerged as promising candidates due to their unique mechanical properties and excellent electrical conductivity. Understanding the mechanical behavior of these polymer electrodes on flexible substrates is essential to ensure the stability and durability of wearable biosensors. In this paper, PEDOT:PSS/graphene composite was spray-coated on flexible substrates at different growth conditions to explore the effect of the deposition parameters and mode of mechanical loading (longitudinal or transversal) on the electrical and mechanical behavior of the fabricated samples. It was found that the coating grown at lower temperatures and higher spraying pressure exhibited stable behavior no matter the applied stress type. Full article
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<p>Illustration of the sample subjected to transversal load (<b>left</b>) and longitudinal load (<b>right</b>).</p>
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<p>Sheet resistance variation (<b>a</b>) and sheet resistance degradation rate (<b>b</b>) for PEDOT:PSS/graphene films spray-coated at different conditions and subjected to longitudinal loading (denoted by L below).</p>
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<p>AFM 3D topography of the PEDOT:PSS/graphene coatings sprayed at different conditions and subjected to longitudinal loading for the samples with a thickness of (<b>a</b>) 3.1 µm; (<b>b</b>) 2.5 µm; (<b>c</b>) 1.75 µm; (<b>d</b>) 1.25 µm.</p>
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<p>Admittance and impedance of samples with different thicknesses, subjected to longitude loading: (<b>a</b>) 3.1 µm; (<b>b</b>) 2.5 µm; (<b>c</b>) 1.75 µm; (<b>d</b>) 1.25 µm.</p>
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<p>Sheet resistance variation (<b>a</b>) and sheet resistance degradation rate (<b>b</b>) for PEDOT:PSS/graphene films spray-coated at different conditions and subjected to transversal loading (denoted by T below).</p>
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<p>AFM 3D topography of the PEDOT:PSS/graphene coatings sprayed at different conditions and subjected to transversal loading for the samples with a thickness of (<b>a</b>) 3.1 µm; (<b>b</b>) 1.75 µm; (<b>c</b>) 2.5 µm; (<b>d</b>) 1.25 µm.</p>
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<p>Admittance Y and impedance Z of samples with different thicknesses, subjected to transversal loading: (<b>a</b>) 3.1 µm; (<b>b</b>) 2.5 µm; (<b>c</b>) 1.75 µm; (<b>d</b>) 1.25 µm.</p>
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<p>Optical microscopic images of all loaded samples (L and T denote the type of loading—longitudinal or transversal): (<b>a</b>) 1L; (<b>b</b>) 1T; (<b>c</b>) 3T; (<b>d</b>) 3L; (<b>e</b>) 4T; (<b>f</b>) 4L; (<b>g</b>) 5T; (<b>h</b>) 5L. In the <b>left</b> column, the samples before loading are presented and in the <b>right</b> one, those after the corresponding type of loading (L or T) are presented.</p>
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<p>Optical microscopic images of all loaded samples (L and T denote the type of loading—longitudinal or transversal): (<b>a</b>) 1L; (<b>b</b>) 1T; (<b>c</b>) 3T; (<b>d</b>) 3L; (<b>e</b>) 4T; (<b>f</b>) 4L; (<b>g</b>) 5T; (<b>h</b>) 5L. In the <b>left</b> column, the samples before loading are presented and in the <b>right</b> one, those after the corresponding type of loading (L or T) are presented.</p>
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<p>Optical microscopic images of all loaded samples (L and T denote the type of loading—longitudinal or transversal): (<b>a</b>) 1L; (<b>b</b>) 1T; (<b>c</b>) 3T; (<b>d</b>) 3L; (<b>e</b>) 4T; (<b>f</b>) 4L; (<b>g</b>) 5T; (<b>h</b>) 5L. In the <b>left</b> column, the samples before loading are presented and in the <b>right</b> one, those after the corresponding type of loading (L or T) are presented.</p>
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<p>Sheet resistance variation in the PEDOT:PSS/graphene film prepared at 90 °C and 3.5 bar after multiple bends at 40% and 80% humidity.</p>
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<p>Fabricated sensing device with the proposed electrode coating: (<b>a</b>) closer view of the IDT patterned PEDOT:PSS/graphene electrode, (<b>b</b>) SAW sensor sample image, and (<b>c</b>) sensor response at different MgCl<sub>2</sub> concentrations.</p>
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10 pages, 3795 KiB  
Article
WS2 with Controllable Layer Number Grown Directly on W Film
by Yuxin Zhang, Shiyi Feng, Jin Guo, Rong Tao, Zhixuan Liu, Xiangyi He, Guoxia Wang and Yue Wang
Nanomaterials 2024, 14(16), 1356; https://doi.org/10.3390/nano14161356 - 16 Aug 2024
Viewed by 465
Abstract
As a layered material with single/multi-atom thickness, two-dimensional transition metal sulfide WS2 has attracted extensive attention in the field of science for its excellent physical, chemical, optical, and electrical properties. The photoelectric properties of WS2 are even more promising than graphene. [...] Read more.
As a layered material with single/multi-atom thickness, two-dimensional transition metal sulfide WS2 has attracted extensive attention in the field of science for its excellent physical, chemical, optical, and electrical properties. The photoelectric properties of WS2 are even more promising than graphene. However, there are many existing preparation methods for WS2, but few reports on its direct growth on tungsten films. Therefore, this paper studies its preparation method and proposes an innovative two-dimensional material preparation method to grow large-sized WS2 with higher quality on metal film. In this experiment, it was found that the reaction temperature could regulate the growth direction of WS2. When the temperature was below 950 °C, the film showed horizontal growth, while when the temperature was above 1000 °C, the film showed vertical growth. At the same time, through Raman and band gap measurements, it is found that the different thicknesses of precursor film will lead to a difference in the number of layers of WS2. The number of layers of WS2 can be controlled by adjusting the thickness of the precursor. Full article
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<p>(<b>a</b>) Schematic diagram for the preparation of precursor W films by magnetron sputtering; (<b>b</b>) principle diagram of tungsten disulfide CVD growing equipment; (<b>c</b>) reaction temperature curve.</p>
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<p>(<b>a</b>) XRD diffraction patterns at different reaction temperatures; (<b>b</b>) XRD patterns of 2θ at 10°~20°; (<b>c</b>) Raman spectra of WS<sub>2</sub> grown at different temperatures; (<b>d</b>–<b>f</b>) SEM patterns of WS<sub>2</sub> prepared at different reaction temperatures: (<b>d</b>) 950 °C; (<b>e</b>) 1000 °C; (<b>f</b>) 1050 °C.</p>
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<p>(<b>a</b>) XRD diffraction patterns of WS<sub>2</sub> prepared from different thicknesses of precursor W films; (<b>b</b>) Raman patterns of WS<sub>2</sub> prepared from different thicknesses of precursor W films; (<b>c</b>~<b>f</b>) SEM patterns of WS<sub>2</sub> prepared from different precursor thicknesses: (<b>c</b>) 1 nm; (<b>d</b>) 6 nm; (<b>e</b>) 12 nm; (<b>f</b>) 30 nm.</p>
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<p>(<b>a</b>) Transmission spectra of WS<sub>2</sub> films as a function of W-film thickness; (<b>b</b>) determination of the band gap of WS<sub>2</sub> prepared with different precursor thicknesses using the Tacu method; (<b>c</b>) single-layer WS<sub>2</sub> energy band diagram; (<b>d</b>) multilayer WS<sub>2</sub> energy band diagram.</p>
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11 pages, 3201 KiB  
Article
Substrate Charge Transfer Induced Ferromagnetism in MnSe/SrTiO3 Ultrathin Films
by Chun-Hao Huang, Chandra Shekar Gantepogu, Peng-Jen Chen, Ting-Hsuan Wu, Wei-Rein Liu, Kung-Hsuan Lin, Chi-Liang Chen, Ting-Kuo Lee, Ming-Jye Wang and Maw-Kuen Wu
Nanomaterials 2024, 14(16), 1355; https://doi.org/10.3390/nano14161355 - 16 Aug 2024
Viewed by 559
Abstract
The observation of superconductivity in MnSe at 12 GPa motivated us to investigate whether superconductivity could be induced in MnSe at ambient conditions. A strain-induced structural change in the ultrathin film could be one route to the emergence of superconductivity. In this report, [...] Read more.
The observation of superconductivity in MnSe at 12 GPa motivated us to investigate whether superconductivity could be induced in MnSe at ambient conditions. A strain-induced structural change in the ultrathin film could be one route to the emergence of superconductivity. In this report, we present the physical property of MnSe ultrathin films, which become tetragonal (stretched ab-plane and shortened c-axis) on a (001) SrTiO3 (STO) substrate, prepared by the pulsed laser deposition (PLD) method. The physical properties of the tetragonal MnSe ultrathin films exhibit very different characteristics from those of the thick films and polycrystalline samples. The tetragonal MnSe films show substantial conductivity enhancement, which could be associated with the presence of superparamagnetism. The optical absorption data indicate that the electron transition through the indirect bandgap to the conduction band is significantly enhanced in tetragonal MnSe. Furthermore, the X-ray Mn L-edge absorption results also reveal an increase in unoccupied state valance bands. This theoretical study suggests that charge transfer from the substrate plays an important role in conductivity enhancement and the emergence of a ferromagnetic order that leads to superparamagnetism. Full article
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<p>Cross-sectional TEM image of the three studied MnSe films. The measured thicknesses are (<b>a</b>) 30 nm, (<b>b</b>) 140 nm, and (<b>c</b>) 740 nm. The ink (white layer in each image) is a carbon paste used as a layer on the top of the films to protect from damage during the TEM sample preparation process. The regions (i), (ii), (iii), and (iv) marked in the images are Pt (conduction layer for FIB process), ink (organic protection layer), MnSe film, and STO substrate.</p>
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<p>The temperature dependence of the resistivity of MnSe films. The resistivity decreases dramatically as the thickness of the film becomes thinner, more than one order of magnitude smaller in the 30 nm film than that of the 740 nm film.</p>
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<p>The magnetic susceptibility of (<b>a</b>) polycrystalline MnSe powder and the (<b>b</b>) 740 nm, (<b>c</b>) 140 nm, and (<b>d</b>) 30 nm MnSe films. The polycrystalline MnSe sample was prepared via the solid-state reaction method. Its magnetic characteristics exhibit anomalies at 180 K and 270 K, respectively. The magnetic anomaly at 270 K arises from the antiferromagnetic order of the solitary hexagonal phase, with a partial transformation into the cubic phase [<a href="#B14-nanomaterials-14-01355" class="html-bibr">14</a>]. The magnetic anomaly observed at 180 K is attributed to the antiferromagnetic order of both the collective hexagonal and cubic phases [<a href="#B14-nanomaterials-14-01355" class="html-bibr">14</a>]. The 180 K magnetic anomaly in the polycrystalline sample is only observed in thick (740 nm) films. It is noted that the magnetic susceptibility of the film increases substantially as film thickness decreases.</p>
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<p>An M-H curve of the MnSe films. (<b>a</b>) The M-H curve of films reveals the signatures of superparamagnetism, rapid increase at the low magnetic field region, saturation at the high magnetic region, and no hysteresis (zero coercive field). There is a small hysteresis loop in the low field region, as shown in <a href="#app1-nanomaterials-14-01355" class="html-app">Figure S2</a>. The moment is in the order of 10<sup>−4</sup> emu and higher, which is well beyond the sensitivity of SQUID, ~10<sup>−6</sup> emu. (<b>b</b>) The fitting of the M-H curve of the 20 nm film. The fitting curve (red line) agrees excellently with the experimental data (open circles). The extracted density of the magnetic domain is about 5.74 × 10<sup>18</sup> cm<sup>−3</sup>, and the effective magnetic moment of Mn is about 3.21.</p>
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<p>X-ray diffractions of the MnSe thin films. (<b>a</b>) A radial scan of the MnSe films with thicknesses of 30 nm, 140 nm, and 740 nm on the (001) STO substrate. The films were grown with the c-axis preferred orientation. The * mark (&gt;3 orders of magnitude smaller than the (001) peak) at q near 2.8 Å<sup>−1</sup> and 4.0 Å<sup>−1</sup> are indexed as (112) and (222) peaks of MnSe. (<b>b</b>) A radical scan near the MnSe (002) peak. The peak of the 30 nm film shifts to a higher angle, implying a shorter <span class="html-italic">c</span>-axis lattice constant. (<b>c</b>) ψ-scan profiles with respect to the (022)<sub>STO</sub> and (101)<sub>MnSe</sub> diffraction peaks of the 30 nm film. A 4-fold symmetry in the <span class="html-italic">ab</span>-plane at 45° with respect to the STO <span class="html-italic">a</span>- (<span class="html-italic">b</span>-) axis demonstrates the epitaxial growth of the MnSe film. (<b>d</b>) The (200), (020), and (002) diffraction peaks of the 140 nm film. Their positions have no significant difference. (<b>e</b>) The (200), (020), and (002) diffraction peaks of the 30 nm film. The in-plane diffraction peak is located at a lower angle compared with the (002) peak.</p>
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<p>Mn L-edge X-ray absorption spectra of the studied MnSe films. The XANES (X-ray absorption near edge spectroscopy) spectra of the Mn 2<span class="html-italic">p</span><sub>3/2</sub> to 3<span class="html-italic">d</span> (L<sub>3</sub>) transition. Four peaks are identified, (marked as A, B, C, and D) which originated from different Mn 3<span class="html-italic">d</span>-related final states. The inset shows the full spectrum of L-edge absorption.</p>
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<p>The band structure of tetragonal MnSe. (<b>a</b>) The A-AFM phase. (<b>b</b>) The FM phase. For comparison, an identical unit cell is used for both phases. A rigid shift of 0.7 eV is applied to the conduction bands, as mentioned in the text.</p>
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10 pages, 1994 KiB  
Article
Enhanced Thermal Stability of Conductive Mercury Telluride Colloidal Quantum Dot Thin Films Using Atomic Layer Deposition
by Edward W. Malachosky, Matthew M. Ackerman and Liliana Stan
Nanomaterials 2024, 14(16), 1354; https://doi.org/10.3390/nano14161354 - 16 Aug 2024
Viewed by 572
Abstract
Colloidal quantum dots (CQDs) are valuable for their potential applications in optoelectronic devices. However, they are susceptible to thermal degradation during processing and while in use. Mitigating thermally induced sintering, which leads to absorption spectrum broadening and undesirable changes to thin film electrical [...] Read more.
Colloidal quantum dots (CQDs) are valuable for their potential applications in optoelectronic devices. However, they are susceptible to thermal degradation during processing and while in use. Mitigating thermally induced sintering, which leads to absorption spectrum broadening and undesirable changes to thin film electrical properties, is necessary for the reliable design and manufacture of CQD-based optoelectronics. Here, low-temperature metal–oxide atomic layer deposition (ALD) was investigated as a method for mitigating sintering while preserving the optoelectronic properties of mercury telluride (HgTe) CQD films. ALD-coated films are subjected to temperatures up to 160 °C for up to 5 h and alumina (Al2O3) is found to be most effective at preserving the optical properties, demonstrating the feasibility of metal–oxide in-filling to protect against sintering. HgTe CQD film electrical properties were investigated before and after alumina ALD in-filling, which was found to increase the p-type doping and hole mobility of the films. The magnitude of these effects depended on the conditions used to prepare the HgTe CQDs. With further investigation into the interaction effects of CQD and ALD process factors, these results may be used to guide the design of CQD–ALD materials for their practical integration into useful optoelectronic devices. Full article
(This article belongs to the Section Synthesis, Interfaces and Nanostructures)
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<p>Infrared absorption spectra plotted against the wavelength (nm) of HgTe CQD thin films on sapphire substrates measured as a function of atomic layer deposition cycles and bake conditions. Evolution of the infrared absorption spectrum for HgTe CQD after (<b>a</b>) ZnO, (<b>b</b>) TiO<sub>2</sub>, (<b>c</b>) 4 cycles of alumina, (<b>d</b>) 8 cycles of alumina, and (<b>e</b>) 20 cycles of alumina and being subjected to baking up to 165 °C for up to 5 h.</p>
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<p>Log plots of the current versus voltage for HgTe CQD thin film Au-Au photoconductor devices with a 5-microns electrode gap. The conductance for a control device (black) that was not subjected to atomic layer deposition, a film subjected to 8 cycles of alumina ALD (red), and a film subjected to 20 cycles alumina ALD (green) are plotted for comparison. Conductance of HgTe CQD films measured (<b>a</b>) before and (<b>b</b>) after baking at 130 °C for 2 h under a nitrogen environment are shown.</p>
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<p>Transfer curves for HgTe colloidal quantum dot thin films measured at a 1 V source–drain bias (<b>a</b>) before alumina ALD and (<b>b</b>) after alumina ALD. Black dashed lines indicate the maximum and minimum slopes taken to calculate the carrier mobilities.</p>
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<p>Transfer curves for n-type doped HgTe colloidal quantum dot thin films measured at a 1 V source–drain bias (<b>a</b>) before alumina ALD and (<b>b</b>) after alumina ALD. Black dashed lines indicate the maximum and minimum slopes taken to calculate the carrier mobilities.</p>
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12 pages, 3269 KiB  
Article
The Adsorption Behavior of Gas Molecules on Mn/N- and Mn-Doped Graphene
by Tingyue Xie, Cuifeng Tian, Ping Wang and Guozheng Zhao
Nanomaterials 2024, 14(16), 1353; https://doi.org/10.3390/nano14161353 - 15 Aug 2024
Viewed by 566
Abstract
By using density functional theory (DFT), the adsorption behavior of gas molecules on defective graphene doped with manganese and nitrogen were investigated. The geometric structure, electronic structure, and magnetic properties of two substrates were calculated and the sensing mechanism was also analyzed. The [...] Read more.
By using density functional theory (DFT), the adsorption behavior of gas molecules on defective graphene doped with manganese and nitrogen were investigated. The geometric structure, electronic structure, and magnetic properties of two substrates were calculated and the sensing mechanism was also analyzed. The results indicate that the MnSV-GP and MnN3-GP have stronger structural stability, in which Mn atoms and their coordination atoms will become the adsorption point for five gas molecules (CH2O, CO, N2O, SO2, and NH3), respectively. Moreover, at room temperature (298 K), the recovery time of the MnSV-GP sensor for N2O gas molecules is approximately 1.1 s. Therefore, it can be concluded that the MnSV-GP matrix as a magnetic gas sensor has a promising potential for detecting N2O. These results also provide a new pathway for the potential application of Mn-doped graphene in the field of gas sensors. Full article
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<p>(<b>a</b>,<b>b</b>) The geometric structure, top and side view, obtained from geometry optimization. (<b>c</b>,<b>d</b>) Charge density difference in MnSV-GP and MnN<sub>3</sub>-GP, respectively. Yellow contours indicate electron accumulation, and cyan contours indicate electron depletion. And other colors represent the chemical elements.</p>
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<p>The adsorption energies of five gas molecules adsorbed on two Mn/GN catalysts. Each calculated binding energy is denoted as its absolute value.</p>
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<p>DOS and PDOS distribution: before and after gas molecule adsorption on MnSV-GP (<b>a</b>) CH<sub>2</sub>O, (<b>b</b>) CO, (<b>c</b>) N<sub>2</sub>O, (<b>d</b>) SO<sub>2</sub>, and (<b>e</b>) NH<sub>3</sub>. Fermi energy is set to zero.</p>
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<p>DOS and PDOS distribution: before and after gas molecule adsorption on MnN<sub>3</sub>-GP (<b>a</b>) CH<sub>2</sub>O, (<b>b</b>) CO, (<b>c</b>) N<sub>2</sub>O, (<b>d</b>) SO<sub>2</sub>, and (<b>e</b>) NH<sub>3</sub>.</p>
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<p>The charge density differences in (<b>a</b>–<b>e</b>) CH<sub>2</sub>O, CO, N<sub>2</sub>O, SO<sub>2</sub>, and NH<sub>3</sub> adsorbed on the MnSV-GP and (<b>f</b>–<b>j</b>) CH<sub>2</sub>O, CO, N<sub>2</sub>O, SO<sub>2</sub>, and NH<sub>3</sub> adsorbed on the MnN<sub>3</sub>-GP configuration. Yellow contours indicate electron accumulation, and cyan contours indicate electron depletion. And other colors present chemical elements, such as purple color denotes Mn atom. Isosurface value: 0.002 e/Bohr<sup>3</sup>.</p>
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<p>The spin density for two supports and gas-support chemisorption systems. (<b>a</b>) The spin density of the MnSV-GP before adsorption; (<b>b</b>–<b>f</b>) The spin density of the MnSV-GP after adsorption of CH<sub>2</sub>O, CO, N<sub>2</sub>O, SO<sub>2</sub>, and NH<sub>3</sub>, respectively; (<b>g</b>) The spin density of the MnN<sub>3</sub>-GP before adstorption; (<b>h</b>–<b>l</b>) The spin density of the MnN<sub>3</sub>-GP after adsorption of CH<sub>2</sub>O, CO, N<sub>2</sub>O, SO<sub>2</sub>, and NH<sub>3</sub>, respectively. The yellow and cyan areas indicate the positive and negative spin densities respectively; isosurface value: 0.005 e/Bohr<sup>3</sup>. And other colors present chemical elements, such as red and green color represent oxygen and sulfur atom, respectively.</p>
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13 pages, 8468 KiB  
Article
Construction of Ternary Ce Metal–Organic Framework/Bi/BiOCl Heterojunction towards Optimized Photocatalytic Performance
by Teng Gao, Hongqi Chu, Shijie Wang, Zhenzi Li and Wei Zhou
Nanomaterials 2024, 14(16), 1352; https://doi.org/10.3390/nano14161352 - 15 Aug 2024
Viewed by 617
Abstract
Photocatalysis is the most promising green approach to solve antibiotic pollution in water, but the actual treatment effect is limited by photocatalytic activity. Herein, Bi and BiOCl were loaded onto the surface of Ce-MOF (metal–organic framework) using an electrostatic adsorption method, and a [...] Read more.
Photocatalysis is the most promising green approach to solve antibiotic pollution in water, but the actual treatment effect is limited by photocatalytic activity. Herein, Bi and BiOCl were loaded onto the surface of Ce-MOF (metal–organic framework) using an electrostatic adsorption method, and a special ternary heterojunction of Ce/Bi/BiOCl was successfully prepared as a photocatalyst for the degradation of tetracycline (TC). FTIR demonstrated that the obtained photocatalyst contains functional groups such as -COOH belonging to Ce-MOF and characteristic crystal planes of Bi and BiOCl, indicating the successful construction of a ternary photocatalyst. The results of UV–vis absorption spectra confirm that the band gap of Ce/Bi/BiOCl heterojunction is reduced from 3.35 eV to 2.7 eV, resulting in an enhanced light absorption capability in the visible light region. The special ternary heterojunction constructed by Ce-MOF, Bi, and BiOCl could achieve a narrow band gap and reasonable band structure, thereby enhancing the separation of photogenerated charges. Consequently, the photocatalytic performance of the Ce/Bi/BiOCl ternary heterojunction was significantly enhanced compared to Ce-MOF, Bi, and BiOCl. Therefore, Ce/Bi/BiOCl can achieve a photocatalytic degradation rate of 97.7% within 20 min, which is much better than Bi (14.8%) and BiOCl (67.9%). This work successfully constructed MOF-based ternary photocatalysts and revealed the relationship between ternary heterojunctions and photocatalytic activity. This provides inspiration for constructing other heterogeneous catalysts for use in the field of photocatalysis. Full article
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<p>XRD patterns of Ce-MOF, Bi/BiOCl, BiOCl, and Ce/Bi/BiOCl, respectively.</p>
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<p>TEM images (<b>a</b>,<b>b</b>) and high-resolution TEM images (<b>c</b>,<b>d</b>) of Ce/Bi/BiOCl.</p>
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<p>(<b>a</b>) N<sub>2</sub> adsorption/desorption isotherms of Ce-MOF, Bi/BiOCl, BiOCl, and Ce/Bi/BiOCl. (<b>b</b>) Pore size distribution curves of Ce-MOF, Bi/BiOCl, and Ce/Bi/BiOCl.</p>
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<p>XPS spectra of Ce/Bi/BiOCl: (<b>a</b>) Bi 4f, (<b>b</b>) Cl 2p, (<b>c</b>) Ce 3d, and (<b>d</b>) O 1 s. The XPS characterization was performed on Ce/Bi/BiOCl to probe the chemical states. (<b>e</b>) FTIR spectra of Ce-MOF, Bi/BiOCl, BiOCl, and Ce/Bi/BiOCl, respectively.</p>
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<p>(<b>a</b>) Ultraviolet–visible absorption spectra of Ce-MOF, Bi/BiOCl, BiOCl, and Ce/Bi/BiOCl and (<b>b</b>) the corresponding Kubelka–Munk conversion reflection spectra. (<b>c</b>) Mott–Schottky test. (<b>d</b>) Energy diagram. (<b>e</b>) Transient photocurrent responses. (<b>f</b>) EIS Nyquist plots.</p>
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<p>(<b>a</b>) Photocatalytic activities, (<b>b</b>) kinetic analysis, and (<b>c</b>) pseudo-first-order kinetic constants of Bi/BiOCl, BiOCl, and Ce/Bi/BiOCl, respectively. (<b>d</b>) Mineralization of TC over Bi/BiOCl, BiOCl, and Ce/Bi/BiOCl.</p>
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<p>(<b>a</b>) Trapping experiments of active species for Ce/Bi/BiOCl; (<b>b</b>) EPR signals for ·O<sub>2</sub><sup>−</sup> and (<b>c</b>) ·OH.</p>
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<p>(<b>a</b>) Repeatability experiment of Ce/Bi/BiOCl photocatalytic degradation of TC. XRD (<b>b</b>) and FTIR (<b>c</b>) of Ce/Bi/BiOCl after reusability test.</p>
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31 pages, 4738 KiB  
Article
Synthesized Bis-Triphenyl Phosphonium-Based Nano Vesicles Have Potent and Selective Antibacterial Effects on Several Clinically Relevant Superbugs
by Silvana Alfei, Guendalina Zuccari, Francesca Bacchetti, Carola Torazza, Marco Milanese, Carlo Siciliano, Constantinos M. Athanassopoulos, Gabriella Piatti and Anna Maria Schito
Nanomaterials 2024, 14(16), 1351; https://doi.org/10.3390/nano14161351 - 15 Aug 2024
Viewed by 669
Abstract
The increasing emergence of multidrug-resistant (MDR) pathogens due to antibiotic misuse translates into obstinate infections with high morbidity and high-cost hospitalizations. To oppose these MDR superbugs, new antimicrobial options are necessary. Although both quaternary ammonium salts (QASs) and phosphonium salts (QPSs) possess antimicrobial [...] Read more.
The increasing emergence of multidrug-resistant (MDR) pathogens due to antibiotic misuse translates into obstinate infections with high morbidity and high-cost hospitalizations. To oppose these MDR superbugs, new antimicrobial options are necessary. Although both quaternary ammonium salts (QASs) and phosphonium salts (QPSs) possess antimicrobial effects, QPSs have been studied to a lesser extent. Recently, we successfully reported the bacteriostatic and cytotoxic effects of a triphenyl phosphonium salt against MDR isolates of the Enterococcus and Staphylococcus genera. Here, aiming at finding new antibacterial devices possibly active toward a broader spectrum of clinically relevant bacteria responsible for severe human infections, we synthesized a water-soluble, sterically hindered quaternary phosphonium salt (BPPB). It encompasses two triphenyl phosphonium groups linked by a C12 alkyl chain, thus embodying the characteristics of molecules known as bola-amphiphiles. BPPB was characterized by ATR-FTIR, NMR, and UV spectroscopy, FIA-MS (ESI), elemental analysis, and potentiometric titrations. Optical and DLS analyses evidenced BPPB tendency to self-forming spherical vesicles of 45 nm (DLS) in dilute solution, tending to form larger aggregates in concentrate solution (DLS and optical microscope), having a positive zeta potential (+18 mV). The antibacterial effects of BPPB were, for the first time, assessed against fifty clinical isolates of both Gram-positive and Gram-negative species. Excellent antibacterial effects were observed for all strains tested, involving all the most concerning species included in ESKAPE bacteria. The lowest MICs were 0.250 µg/mL, while the highest ones (32 µg/mL) were observed for MDR Gram-negative metallo-β-lactamase-producing bacteria and/or species resistant also to colistin, carbapenems, cefiderocol, and therefore intractable with currently available antibiotics. Moreover, when administered to HepG2 human hepatic and Cos-7 monkey kidney cell lines, BPPB showed selectivity indices > 10 for all Gram-positive isolates and for clinically relevant Gram-negative superbugs such as those of E. coli species, thus being very promising for clinical development. Full article
(This article belongs to the Section Biology and Medicines)
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<p>Chemical structure of the BPPB.</p>
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<p>Chemical structure of the BPPB with atom numbering for NMR peaks assignation.</p>
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<p>ATR-FTIR spectrum of BPPB.</p>
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<p><sup>1</sup>H NMR spectrum (CDCl<sub>3</sub>, 400 MHz) of BPPB. Signals in squares of the same color indicate the signals present in the original spectrum and their corresponding magnification.</p>
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<p><sup>13</sup>C-NMR spectrum (CDCl<sub>3</sub>, 100 MHz) of BPPB. Signals in squares of the same color indicate the signals present in the original spectrum and their corresponding magnification.</p>
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<p><sup>13</sup>C-NMR DEPT 35 spectrum (CDCl<sub>3</sub>, 100 MHz) of BPPB and its <sup>31</sup>P-NMR spectrum (CDCl<sub>3</sub>, 192 MHz) (red square).</p>
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<p>UV spectrum (water, 190–390 nm) of BPPB. In blue circle the 3 peaks of absorbance reported by Ceccacci et al. [<a href="#B36-nanomaterials-14-01351" class="html-bibr">36</a>] have been evidenced.</p>
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<p>UV spectrum (water, 250–320 nm) of BPPB.</p>
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<p>Potentiometric titration profiles of BPPB (blue line) and the related first derivative curve (FD) (green line).</p>
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<p>Vesicular aggregates of BPPB in water suspension observed with a 40× objective (<b>a</b>), with magnification in the red square. Smaller vesicular aggregates of BPPB visible with the 100× objective (<b>b</b>). Larger aggregates are indicated by the yellow circles.</p>
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<p>Representative images of the particle size distribution (nm) with DPI, including BPPB (<b>a</b>) and of its ζ-p (<b>b</b>).</p>
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<p>Time-killing curves obtained with BPPB (at concentrations equal to 4× MIC) against <span class="html-italic">S. aureus</span> 18 and <span class="html-italic">E. coli</span> 539.</p>
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<p>Growth inhibition and cytotoxic effects of BPPB on Cos-7 and HepG2 cells. Cos-7 and HepG2 cells were seeded on 96-multiwell plates and treated for 24 h with different concentrations (0.5–100 µg/mL) of bis-phosphonium bromide. Growth inhibition was determined by the MTT assay (<b>a</b>,<b>b</b>). The bar graph shows the cell viability (%) of Cos-7 (<b>a</b>) and HepG2 (<b>b</b>) cells untreated (CTRL) and after exposure to increasing concentrations (0.5–100 µg mL<sup>−1</sup>) of BPPB for 24 h. Data are expressed as the mean ± S.E.M. of the survival percentage obtained from 6 to 14 independent experiments run in triplicate. Significance is indicated as ** <span class="html-italic">p</span> &lt; 0.005 and **** <span class="html-italic">p</span> &lt; 0.0001 vs. CTRL (one-way ANOVA followed by Tukey’s multi-comparisons test). Cell cytotoxicity was determined by the LDH assay (<b>c</b>,<b>d</b>). The bar graph shows the quantification of cell damage (expressed as optical density units of absorbance) of Cos-7 (<b>c</b>) and HepG2 (<b>d</b>) cells untreated (CTRL), and after exposure to increasing concentrations (0.5–100 µg mL<sup>−1</sup>) of bis-phosphonium bromide for 24 h. Data are expressed as the mean ± S.E.M. of cell cytotoxicity (OD units recorded, in kinetic mode, after 10 min of LDH reaction), obtained from n = 6–14 independent experiments run in triplicate. Significance is indicated as **** <span class="html-italic">p</span> &lt; 0.0001 vs. CTRL (one-way ANOVA followed by Tukey’s multi-comparisons test). (<b>e</b>,<b>f</b>) Representative phase contrast images of Cos-7 (<b>e</b>) and HepG2 (<b>f</b>) cells acquired in untreated conditions or after exposure to increasing concentrations (0.5–100 µg mL<sup>−1</sup>) of bis-phosphonium bromide for 24 h.</p>
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<p>Synthetic route to achieve BPPB.</p>
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15 pages, 4190 KiB  
Article
Impact of Nanoplastic Particles on Macrophage Inflammation and Intestinal Health in a Mouse Model of Inflammatory Bowel Disease
by Marlene Schwarzfischer, Tano S. Ruoss, Anna Niechcial, Sung Sik Lee, Marcin Wawrzyniak, Andrea Laimbacher, Kirstin Atrott, Roberto Manzini, Marijn Wilmink, Luise Linzmeier, Yasser Morsy, Silvia Lang, Gerhard Rogler, Ralf Kaegi, Michael Scharl and Marianne R. Spalinger
Nanomaterials 2024, 14(16), 1350; https://doi.org/10.3390/nano14161350 - 15 Aug 2024
Viewed by 764
Abstract
Background: The increasing presence of plastics in the human diet is raising public concern about the potential risks posed by nanoplastic (NP) particles, which can emerge from the degradation of plastic debris. NP ingestion poses particular risks to individuals with inflammatory bowel disease [...] Read more.
Background: The increasing presence of plastics in the human diet is raising public concern about the potential risks posed by nanoplastic (NP) particles, which can emerge from the degradation of plastic debris. NP ingestion poses particular risks to individuals with inflammatory bowel disease (IBD), as compromised epithelial barriers may facilitate NP translocation. Methods: In vitro, bone-marrow-derived macrophages (BMDMs) were exposed to 25 nm polymethacrylate (PMMA) or 50 nm polystyrene (PS) particles to assess morphological changes and alterations in pro- and anti-inflammatory gene expression. In vivo, mice received PMMA NP particles for 6 months before acute dextran sodium sulfate (DSS) colitis was induced to investigate NP impacts on intestinal health and inflammation. Results: PMMA and PS NP exposure in BMDMs induced morphological changes indicative of a proinflammatory phenotype characterized by enlarged amoeboid cell shapes. It also triggered an inflammatory response, indicated by increased expression of proinflammatory cytokines such as Tnfa and Il6. Unexpectedly, long-term PMMA NP administration did not affect the intestinal epithelial barrier or exacerbate acute DSS-induced colitis in mice. Colonoscopy and histological analysis revealed no NP-related changes, suggesting adverse effects on intestinal health or inflammation. Conclusion: Our findings from animal models offer some reassurance to IBD patients regarding the effects of NP ingestion. However, variations in lifestyle and dietary habits may lead to significantly higher plastic intake in certain individuals, raising concerns about potential long-term gastrointestinal effects of lifelong plastic consumption. Full article
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<p>NP particles caused phenotypic changes in BMDMs. Bone marrow was isolated from 10-week-old WT mice and cells were differentiated into BMDMs before treatment with 25 nm PMMA or 50 nm PS particles at a concentration of 100, 200, or 400 µg/mL for 2, 4, 8, or 24 h. (<b>A</b>) Schematic overview of experimental procedure. (<b>B</b>) Bright-field images of BMDMs after NP exposure. Original magnification (BF) 40×.</p>
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<p>NP particles were engulfed by BMDMs and resulted in rearrangement of the cytoskeleton and phenotypical changes. Bone marrow was isolated from 10-week-old WT mice and cells were differentiated into BMDMs before treatment with green-fluorescent 25 nm PMMA or 50 nm PS particles at a concentration of 100 µg/mL for 24 h. Confocal microscopy of NP (green)-treated cells stained with DAPI (blue) and Phalloidin (red). White arrows indicate enlarged vacuoles.</p>
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<p>NP administration activated BMDMs and induced proinflammatory cytokine expression. Bone marrow from 10-week-old WT mice was differentiated into BMDMs, then treated with 25 nm PMMA or 50 nm PS particles (100, 200, or 400 µg/mL) for 2, 4, 8, or 24 h. Relative mRNA levels of cytokines (<b>A</b>) <span class="html-italic">Tnfα</span> (<b>B</b>) <span class="html-italic">Il6</span>, (<b>C</b>) <span class="html-italic">Il12b</span>) and costimulatory molecules (<b>D</b>) <span class="html-italic">Cd80</span>, (<b>E</b>) <span class="html-italic">Cd86</span>) following exposure to 25 nm (<b>left</b>) and 50 nm (<b>right</b>) particles are shown. Red asterisks indicate significant differences compared to controls. ∆∆CT method and one-way ANOVA (* = <span class="html-italic">p</span> ≤ 0.05, ** = <span class="html-italic">p</span> ≤ 0.01, *** = <span class="html-italic">p</span> ≤ 0.001, **** = <span class="html-italic">p</span> ≤ 0.0001).</p>
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<p>NPs did not affect intestinal homeostasis. Directly after weaning, female WT mice were supplemented with 25 nm PMMA particles in the drinking water (0.05 mg/mL) for 172 days (6 months). (<b>A</b>) Weight development during pretreatment. (<b>B</b>) Representative colonoscopy images and MEICS scores. (<b>C</b>) H&amp;E staining of distal colon sections with analysis of epithelial damage and infiltration. (<b>D</b>) Colon length and (<b>E</b>) spleen weight. (<b>F</b>) Epithelial barrier integrity assessed by quantifying FITC-dextran levels in serum 5 h after oral administration of 4 kDa FITC-dextran. (<b>A</b>,<b>B</b>) Two-way ANOVA with Tukey’s multiple comparisons. (<b>B</b>,<b>C</b>) Kruskal–Wallis test. (<b>D</b>–<b>F</b>) One-way ANOVA. Original magnification (H&amp;E) ×10.</p>
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<p>Administration of NP particles did not exacerbate acute DSS colitis. Directly after weaning, female WT mice were supplemented with 25 nm PMMA particles in the drinking water (0.05 mg/mL) for 172 days (6 months). Acute colitis was induced by administration of 1.5% DSS in the drinking water for 7 days. (<b>A</b>) Weight development during NP pretreatment and (<b>B</b>) colitis induction. (<b>C</b>) Representative images from colonoscopy and MEICS score. (<b>D</b>) H&amp;E staining of distal colon sections and analysis of epithelial damage and infiltration. (<b>E</b>) Colon length and (<b>F</b>) spleen weight. (<b>A</b>,<b>B</b>) Two-way ANOVA Tukey’s multiple comparison (<b>C</b>,<b>D</b>) Kruskal–Wallis Test. (<b>E</b>,<b>F</b>) One-way ANOVA. Original magnification (H&amp;E) ×10.</p>
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18 pages, 20009 KiB  
Article
Optimization of Cyanide-Free Composite Electrodeposition Based on π-π Interactions Preparation of Silver-Graphene Composite Coatings for Electrical Contact Materials
by Luyi Sun, Xin Chen, Ming Zhou, Jingwei Gao, Chaogui Luo, Xiao Li, Shengli You, Mingyue Wang and Gangqiang Cheng
Nanomaterials 2024, 14(16), 1349; https://doi.org/10.3390/nano14161349 - 15 Aug 2024
Viewed by 571
Abstract
With the rapid development of industrial automation and power electronics, the requirements for electrical contact materials are increasing. However, traditional electrical contact materials encountered significant bottlenecks in terms of performance enhancement and production environmental friendliness. Therefore, this paper proposes a new material design [...] Read more.
With the rapid development of industrial automation and power electronics, the requirements for electrical contact materials are increasing. However, traditional electrical contact materials encountered significant bottlenecks in terms of performance enhancement and production environmental friendliness. Therefore, this paper proposes a new material design idea that utilizes π-π interactions between graphene and compounds with conjugated structures in order to achieve uniform dispersion of graphene in the metal matrix and thus enhance the performance of composites. Based on this design idea, we used nicotinic acid, which has a conjugated structure and is safe, as the complexing agent, and successfully prepared high-quality silver-graphene (Ag-G) composite coatings with graphene uniformly dispersed in the metal matrix on copper substrates by composite electrodeposition technique. Subsequently, the mechanical properties of composite coatings were investigated by hardness test and X-ray diffractometer, and the tribological properties of the composite coatings and the comprehensive performance under the current carrying conditions were systematically evaluated by using friction and wear tester and load key life tester. The results show that the Ag-G composite coatings have significant advantages in mechanical, tribological, and current carrying conditions. This result not only verifies the feasibility of the design idea of the material, but also provides a new direction for the research and development of electrical contact materials. Full article
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<p>Schematic diagram of electrodeposition.</p>
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<p>SEM images and EDS analysis of the coatings: (<b>a</b>) pure Ag coating prepared by niacin silver plating system, (<b>b</b>) Ag-G composite coating prepared by niacin silver plating system, and (<b>c</b>) Ag-G composite coating prepared by thiosulfate silver plating system.</p>
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<p>SEM images and EDS surface scan and line scan results of the coatings in cross-section: (<b>a</b>) pure Ag coating prepared by a niacin silver plating system, (<b>b</b>) Ag-G composite coating prepared by a niacin silver plating system, and (<b>c</b>) Ag-G composite coating prepared by a thiosulfate silver plating system.</p>
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<p>Surface morphology of (<b>a</b>) pure Ag coating and (<b>b</b>) Ag-G composite coating characterized by AFM.</p>
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<p>Raman surface scanning results of the coatings as well as surface morphology (<b>a</b>) Ag-G composite coating prepared by a silver thiosulfate plating system, (<b>b</b>) Ag-G composite coating prepared by a silver nicotinic acid plating system; and (<b>c</b>) schematic diagrams of the electrodeposition process under the condition of graphene agglomeration and (<b>d</b>) under ideal dispersion of graphene.</p>
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<p>(<b>a</b>) Vickers hardness test results of pure Ag coating and Ag-G composite coating, (<b>b</b>) XRD results of pure Ag coating and Ag-G composite coating.</p>
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<p>Coefficient of friction curves; (<b>a</b>) surface wear condition of pure Ag coating and (<b>b</b>) Ag-G composite coating; and (<b>c</b>) cross-section of wear scars.</p>
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<p>On–off experimental resistance curves and contact surface morphology of pure Ag contact and Ag-G composite contact during the on–off cycle.</p>
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<p>Images of surface morphology and distribution of various elements in the localized ablation region of (<b>a</b>) pure Ag contact and (<b>b</b>) Ag-G composite contact after 10,000 times of the on–off experiment.</p>
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<p>(<b>a</b>) Raman spectra of graphene residues at each wear point after different experiments. (<b>b</b>) Raman spectra of the respective ablation zones of pure Ag coatings and Ag-G composite coatings after 10,000 times of the on–off experiment.</p>
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<p>Mechanism of composite electrodeposition under niacin cyanide-free silver plating system.</p>
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12 pages, 8740 KiB  
Article
VO2-Based Spacecraft Smart Radiator with High Emissivity Tunability and Protective Layer
by Qingjie Xu, Haining Ji, Yang Ren, Yangyong Ou, Bin Liu, Yi Wang, Yongxing Chen, Peng Long, Cong Deng and Jingting Wang
Nanomaterials 2024, 14(16), 1348; https://doi.org/10.3390/nano14161348 - 15 Aug 2024
Viewed by 602
Abstract
In the extreme space environment, spacecraft endure dramatic temperature variations that can impair their functionality. A VO2-based smart radiator device (SRD) offers an effective solution by adaptively adjusting its radiative properties. However, current research on VO2-based thermochromic films mainly [...] Read more.
In the extreme space environment, spacecraft endure dramatic temperature variations that can impair their functionality. A VO2-based smart radiator device (SRD) offers an effective solution by adaptively adjusting its radiative properties. However, current research on VO2-based thermochromic films mainly focuses on optimizing the emissivity tunability (Δε) of single-cycle sandwich structures. Although multi-cycle structures have shown increased Δε compared to single-cycle sandwich structures, there have been few systematic studies to find the optimal cycle structure. This paper theoretically discusses the influence of material properties and cyclic structure on SRD performance using Finite-Difference Time-Domain (FDTD) software, which is a rigorous and powerful tool for modeling nano-scale optical devices. An optimal structural model with maximum emissivity tunability is proposed. The BaF2 obtained through optimization is used as the dielectric material to further optimize the cyclic resonator. The results indicate that the tunability of emissivity can reach as high as 0.7917 when the BaF2/VO2 structure is arranged in three periods. Furthermore, to ensure a longer lifespan for SRD under harsh space conditions, the effects of HfO2 and TiO2 protective layers on the optical performance of composite films are investigated. The results show that when TiO2 is used as the protective layer with a thickness of 0.1 µm, the maximum emissivity tunability reaches 0.7932. Finally, electric field analysis is conducted to prove that the physical mechanism of the smart radiator device is the combination of stacked Fabry–Perot resonance and multiple solar reflections. This work not only validates the effectiveness of the proposed structure in enhancing spacecraft thermal control performance but also provides theoretical guidance for the design and optimization of SRDs for space applications. Full article
(This article belongs to the Special Issue Advances in Nanomaterials for Optoelectronics: Second Edition)
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<p>Optimal SRD structure with maximum emissivity tunability.</p>
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<p>The single-cycle sandwich structure and the light propagation when VO<sub>2</sub> is in the metallic state (<b>a</b>) and dielectric state (<b>b</b>), where <span class="html-italic">d<sub>f</sub> </span>and <span class="html-italic">d<sub>s</sub></span> represent the thicknesses of the VO<sub>2</sub> and spacer, respectively.</p>
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<p>Emission tunability (Δ<span class="html-italic">ε</span>) as functions of the thicknesses of VO<sub>2</sub> and three dielectric layer materials, (<b>a</b>) Al<sub>2</sub>O<sub>3</sub>, (<b>b</b>) ZnS, and (<b>c</b>) BaF<sub>2</sub>.</p>
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<p>The IR emittance of high/low temperatures and the emissivity tunability (Δ<span class="html-italic">ε</span>) of the VO<sub>2</sub>-based two-period structure varies with the thickness of the first VO<sub>2</sub> layer (<b>a</b>), the second VO<sub>2</sub> layer (<b>b</b>), the first BaF<sub>2</sub> layer (<b>c</b>) and the second BaF<sub>2</sub> layer (<b>d</b>).</p>
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<p>The IR emittance of high/low temperatures and the emissivity tunability of the VO<sub>2</sub>-based three-period structure varies with the thickness of the VO<sub>2</sub> layer (<b>a</b>–<b>c</b>); the IR emittance of high/low temperatures and the emissivity tunability of the VO<sub>2</sub>-based three-period structure varies with the thickness of the BaF<sub>2</sub> layer (<b>d</b>–<b>f</b>).</p>
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<p>The emissivity tunability of the optimized three-period VO<sub>2</sub>-based structure with protective layers (HfO<sub>2</sub> or TiO<sub>2</sub>), where the red dashed line indicates the maximum Δ<span class="html-italic">ε</span> without a protective layer.</p>
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<p>The IR emittance of a three-period structure with a protective layer varies with wavelength at both metallic and dielectric states.</p>
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<p>The normalized electric field |<span class="html-italic">E</span>/<span class="html-italic">E<sub>0</sub></span>| is shown for metallic (<b>a</b>,<b>b</b>) and dielectric (<b>c</b>,<b>d</b>) states at wavelengths of 2.9527 and 17.67 µm. <span class="html-italic">E<sub>0</sub></span> represents the incident electric field, directed perpendicular to each layer. The white lines represent the boundaries of each layer. In the figures, the air, TiO<sub>2</sub>, and BaF<sub>2</sub> layers are clearly visible, while the VO<sub>2</sub> layer is too thin to be represented.</p>
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18 pages, 2148 KiB  
Article
Nebivolol Polymeric Nanoparticles-Loaded In Situ Gel for Effective Treatment of Glaucoma: Optimization, Physicochemical Characterization, and Pharmacokinetic and Pharmacodynamic Evaluation
by Pradeep Singh Rawat, Punna Rao Ravi, Mohammed Shareef Khan, Radhika Rajiv Mahajan and Łukasz Szeleszczuk
Nanomaterials 2024, 14(16), 1347; https://doi.org/10.3390/nano14161347 - 14 Aug 2024
Viewed by 513
Abstract
Nebivolol hydrochloride (NEB), a 3rd-generation beta-blocker, was recently explored in managing open-angle glaucoma due to its mechanism of action involving nitric oxide release for the vasodilation. To overcome the issue of low ocular bioavailability and the systemic side effects associated with conventional ocular [...] Read more.
Nebivolol hydrochloride (NEB), a 3rd-generation beta-blocker, was recently explored in managing open-angle glaucoma due to its mechanism of action involving nitric oxide release for the vasodilation. To overcome the issue of low ocular bioavailability and the systemic side effects associated with conventional ocular formulation (aqueous suspension), we designed and optimized polycaprolactone polymeric nanoparticles (NEB-PNPs) by applying design of experiments (DoE). The particle size and drug loading of the optimized NEB-PNPs were 270.9 ± 6.3 nm and 28.8 ± 2.4%, respectively. The optimized NEB-PNPs were suspended in a dual-sensitive in situ gel prepared using a mixture of P407 + P188 (as a thermo-sensitive polymer) and κCRG (as an ion-sensitive polymer), reported previously by our group. The NEB-PNPs-loaded in situ gel (NEB-PNPs-ISG) formulation was characterized for its rheological behavior, physical and chemical stability, in vitro drug release, and in vivo efficacy. The NEB-PNPs-loaded in situ gel, in ocular pharmacokinetic studies, achieved higher aqueous humor exposure (AUC0–t = 329.2 ng × h/mL) and for longer duration (mean residence time = 9.7 h) than compared to the aqueous suspension of plain NEB (AUC0–t = 189 ng × h/mL and mean residence time = 6.1 h) reported from our previous work. The pharmacokinetic performance of NEB-PNPs-loaded in situ gel translated into a pharmacodynamic response with 5-fold increase in the overall percent reduction in intraocular pressure by the formulation compared to the aqueous suspension of plain NEB reported from our previous work. Further, the mean response time of NEB-PNPs-loaded in situ gel (12.4 ± 0.6 h) was three times higher than aqueous suspension of plain NEB (4.06 ± 0.3 h). Full article
(This article belongs to the Topic Advances in Controlled Release and Targeting of Drugs)
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<p>Three dimensional plots demonstrating the impact of significant factors on critical responses: (<b>a</b>) PS and (<b>b</b>) DL (%) for optimized NEB-PNPs.</p>
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<p>SEM image of the optimized NEB-PNPs.</p>
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<p>Semi-logarithmic plot of loss tangent versus temperature of the formulations. A—blank ISG; B—NEB-PNPs-ISG; and C—NEB-PNPs-ISG in the presence of STF.</p>
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<p>Drug-release profiles of NEB suspension, NEB-PNPs-Susp, and NEB-PNPs-ISG in the in vitro studies. The mean (±SD) of three replicate formulations (n = 3) is presented at each sampling point. Note: Data of NEB-Susp are from our previous published work [<a href="#B3-nanomaterials-14-01347" class="html-bibr">3</a>].</p>
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<p>Mean concentration of NEB versus time profiles constructed from the ocular administration of NEB-PNPs-Susp, NEB-PNPs-ISG, and NEB-Susp in aqueous humor. Note: Data of NEB-Susp are reproduced from our previous reported work [<a href="#B3-nanomaterials-14-01347" class="html-bibr">3</a>].</p>
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<p>Percent reduction in intra-ocular pressure (ΔIOP (%)) versus time plot of NEB-PNPs-Susp and NEB-PNPs-ISG administered through ocular route in rabbits (n = 6). Note: NEB-Susp profile is reproduced from our previous reported work [<a href="#B3-nanomaterials-14-01347" class="html-bibr">3</a>].</p>
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32 pages, 44965 KiB  
Article
Hybrid Cellulosic Substrates Impregnated with Meta-PBI-Stabilized Carbon Nanotubes/Plant Extract-Synthesized Zinc Oxide—Antibacterial and Photocatalytic Dye Degradation Study
by Hristo Penchev, Katerina Zaharieva, Silvia Dimova, Georgy Grancharov, Petar D. Petrov, Maria Shipochka, Ognian Dimitrov, Irina Lazarkevich, Stephan Engibarov and Rumyana Eneva
Nanomaterials 2024, 14(16), 1346; https://doi.org/10.3390/nano14161346 - 14 Aug 2024
Viewed by 746
Abstract
Novel fibrous cellulosic substrates impregnated with meta-polybenzimidazole (PBI)-stabilized carbon nanotubes/zinc oxide with different weight content of ZnO and with the use of dimethylacetamide as dispersant media. The pristine ZnO nanoparticle powder was prepared by plant extract-mediated synthesis using Vaccinium vitis-idaea L. The green [...] Read more.
Novel fibrous cellulosic substrates impregnated with meta-polybenzimidazole (PBI)-stabilized carbon nanotubes/zinc oxide with different weight content of ZnO and with the use of dimethylacetamide as dispersant media. The pristine ZnO nanoparticle powder was prepared by plant extract-mediated synthesis using Vaccinium vitis-idaea L. The green synthesized ZnO possesses an average crystallite size of 15 nm. The formation of agglomerates from ZnO NPs with size 250 nm–350 nm in the m-PBI@CNTs/ZnO was determined. The prepared materials were investigated by PXRD analysis, XPS, SEM, EDS, AFM, and TEM in order to establish the phase and surface composition, structure, and morphology of the hybrids. The potential of the synthesized hybrid composites to degrade methylene blue (MB) dye as a model contaminant in aqueous solutions under UV illumination was studied. The photocatalytic results show that in the course of the photocatalytic reaction, the m-PBI@CNTs/ZnO 1:3 photocatalyst leads to the highest degree of degradation of the methylene blue dye (67%) in comparison with the other two studied m-PBI@CNTs/ZnO 1:1 and 1:2 composites (48% and 41%). The antibacterial activity of ZnO nanoparticles and the hybrid CNT materials was evaluated by the RMDA and the dynamic contact method, respectively. The profound antibacterial effect of the m-PBI@CNTs/ZnO hybrids was monitored for 120 h of exposition in dark and UV illumination regimes. The photocatalytic property of ZnO nanoparticles significantly shortens the time for bactericidal action of the composites in both regimes. The m-PBI@CNTs/ZnO 1:2 combination achieved complete elimination of 5.105 CFU/mL E. coli cells after 10 min of UV irradiation. Full article
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<p>Schematic representation of m-PBI surface wrapping stabilization of MWCNTs. Pictures of the hybrid dispersions from left to right: pristine ZnO NPs dispersed in DMAc; m-PBI@ZnO; m-PBI@CNTs; m-PBI@CNTs/ZnO 1:1 and m-PBI@CNTs/ZnO 3:1 (<b>A</b>); time stability comparison of the bare plant extract ZnO NPs and m-PBI@ZnO dispersions in DMAc before (<b>left</b>) and after 60 min stay (<b>right</b>) (<b>B</b>).</p>
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<p>Size distribution plot of PBI-modified MWCNTs dispersions in DMAc (<b>A</b>). Size distribution plots of PBI-modified MWCNTs/ZnO dispersions in DMAA at different CNTs/ZnO mass ratios (<b>B</b>).</p>
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<p>Digital pictures of 1 mL free drop spread of m-PBI@CNT and m-PBI@CNTs/ZnO 1:1 suspensions (<b>top</b>) and light microscopy pictures of these two dispersions after 1 mL deposition onto cellulose filter substrate (<b>bottom</b>).</p>
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<p>PXRD patterns of green synthesized ZnO, m-PBI/CNTs, and m-PBI@CNTs/ZnO 1:3.</p>
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<p>Deconvoluted photoelectron spectra of C1s, O1s, and N1s and core level spectra of Zn2p and ZnLMM of m-PBI/ZnO; m-PBI/CNTs; m-PBI@CNTs/ZnO 1:1; and m-PBI@CNTs/ZnO 1:3.</p>
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<p>SEM images of microfibrous cellulose substrates impregnated with (<b>A</b>) m-PBI@CNTs; (<b>B</b>) m-PBI@CNTs/ZnO 1:1; (<b>C</b>) m-PBI@CNTs/ZnO 1:2; and (<b>D</b>) m-PBI@CNTs/ZnO 1:3.</p>
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<p>EDS mapping of cellulose substrate impregnated with m-PBI@CNTs/ZnO 1:1 (<b>A</b>); m-PBI@CNTs/ZnO 1:2 (<b>B</b>); and m-PBI@CNTs/ZnO 1:3 (<b>C</b>).</p>
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<p>EDS mapping of cellulose substrate impregnated with m-PBI@CNTs/ZnO 1:1 (<b>A</b>); m-PBI@CNTs/ZnO 1:2 (<b>B</b>); and m-PBI@CNTs/ZnO 1:3 (<b>C</b>).</p>
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<p>EDS spectra of m-PBI/CNTs, m-PBI@CNTs/ZnO 1:1, PBI@CNTs/ZnO 1:2, and m-PBI@CNTs/ZnO 1:3.</p>
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<p>(<b>A</b>) AFM 2D image of CNTs; (<b>B</b>) AFM 3D image of CNTs; (<b>C</b>) AFM 2D image of green synthesized ZnO nanoparticles; (<b>D</b>) AFM 3D image of green synthesized ZnO nanoparticles; (<b>E</b>) AFM 2D image of m-PBI/ZnO; (<b>F</b>) AFM 3D image of m-PBI/ZnO; (<b>G</b>) AFM 2D image of m-PBI@CNTs/ZnO; (<b>H</b>) AFM 3D image of m-CNTs/ZnO.</p>
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<p>TEM images of (<b>A</b>) green synthesized ZnO nanoparticles; (<b>B</b>) m-PBI/ZnO; (<b>C</b>) m-PBI/CNTs; (<b>D</b>) m-PBI@CNTs/ZnO 1:1; and (<b>E</b>) m-PBI@CNTs/ZnO 1:3.</p>
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<p>HR TEM images of images of green synthesized ZnO nanoparticles (<b>A</b>). m-PBI@CNTs hybrid (<b>B</b>).</p>
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<p>HR TEM images of images of green synthesized ZnO nanoparticles (<b>A</b>). m-PBI@CNTs hybrid (<b>B</b>).</p>
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<p>Digital pictures of preliminary experiment for 15 min UV light illumination of hybrid catalytic m-PBI@CNT/ZnO 1:1 cellulose substrate in contact with diluted MB solution.</p>
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<p>(<b>a</b>) The concentration ratio C/C<sub>0</sub> and (<b>b</b>) degree of degradation of Methylene Blue dye with time of UV illumination using prepared hybrid materials as photocatalysts.</p>
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<p>(<b>a</b>) The concentration ratio C/C<sub>0</sub> and (<b>b</b>) degree of degradation of Methylene Blue dye with time of UV illumination using m-PBI/ZnO and bare green synthesized ZnO as photocatalysts.</p>
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<p>(<b>a</b>) The concentration ratio C/C<sub>0</sub> and (<b>b</b>) degree of degradation of Methylene Blue dye with time of UV illumination using prepared hybrid materials as photocatalysts in the presence of H<sub>2</sub>O<sub>2</sub>.</p>
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<p>Degree of degradation of MB dye after 180 min under UV light using (<b>a</b>) m-PBI@CNTs/ZnO 1:2; (<b>b</b>) m-PBI@CNTs/ZnO 1:1; and (<b>c</b>) m-PBI@CNTs/ZnO 1:3 photocatalysts in three photocatalytic runs.</p>
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<p>RMDA method for evaluation of MIC in 96-well plate. Wells in the rectangles are inoculated with a bacterial culture of 5 × 10<sup>5</sup> CFU/mL. (<b>a</b>) MIC of MWCNTs, lines A, B: a sector from 96-well plate kept in static condition. Lines F–H: a sector from another 96-well plate incubated on a wrist shaker. Legend between B and F lines shows the concentration of MWCNTs in each column of wells. Well G12—positive control. (<b>b</b>) MIC of ZnO nanoparticles, column 6: positive control, column 10: control wells of resazurin dye for each ZnO concentration.</p>
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<p>ASTM Standard Test Method E 2149–10. Data are presented as lg of the CFU/mL. (<b>a</b>,<b>b</b>) Antibacterial effect of the tested hybrid materials, their constituents, and combinations of constituents tested on <span class="html-italic">E. coli</span>. (<b>c</b>) Effect of the combination of cellulose and PBIs, tested on <span class="html-italic">B. subtilis</span>.</p>
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<p>(<b>a</b>). Effect of UV irradiation on standard <span class="html-italic">E. coli</span> suspension with 0.5 mg/mL ZnO NPs. Samples were taken before the 15′ incubation in the dark, at the start of UV irradiation, and at 10′, 20′, and 30′: (1) a beaker irradiated with UV light; (2) a beaker kept in the dark throughout the whole experiment; (<b>b</b>) effect of the tested hybrid materials: left—without irradiation; right—after UV irradiation; K—control, 1—Cell/PBI, 2—Cell/PBI/ZnO, 3—Cell/PBI@CNT, 4—Cell/PBI@CNT/ZnO 1:1, 5—Cell/PBI@CNT/ZnO 1:2, 6—Cell/PBI@CNT/ZnO 1:3. Sample 5 displays bactericidal effect.</p>
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<p>SEM images of the hybrid material Cell/PBI@CNT incubated with <span class="html-italic">E. coli</span> suspension overnight. Putative effusions of cell contents are indicated by arrows. Areas marked in rectangles were observed at higher magnification and shown below: (<b>a</b>) a specimen kept in the dark; (<b>b</b>) a specimen irradiated by UV light.</p>
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15 pages, 3626 KiB  
Article
Optical Fiber Probe with Integrated Micro-Optical Filter for Raman and Surface-Enhanced Raman Scattering Sensing
by Md Abdullah Al Mamun, Tomas Katkus, Anita Mahadevan-Jansen, Saulius Juodkazis and Paul R. Stoddart
Nanomaterials 2024, 14(16), 1345; https://doi.org/10.3390/nano14161345 - 14 Aug 2024
Viewed by 643
Abstract
Optical fiber Raman and surface-enhanced Raman scattering (SERS) probes hold great promise for in vivo biosensing and in situ monitoring of hostile environments. However, the silica Raman scattering background generated within the optical fiber increases in proportion to the length of the fiber, [...] Read more.
Optical fiber Raman and surface-enhanced Raman scattering (SERS) probes hold great promise for in vivo biosensing and in situ monitoring of hostile environments. However, the silica Raman scattering background generated within the optical fiber increases in proportion to the length of the fiber, and it can swamp the signal from the target analyte. While filtering can be applied at the distal end of the fiber, the use of bulk optical elements has limited probe miniaturization to a diameter of 600 µm, which in turn limits the potential applications. To overcome this limitation, femtosecond laser micromachining was used to fabricate a prototype micro-optical filter, which was directly integrated on the tip of a 125 µm diameter double-clad fiber (DCF) probe. The outer surface of the microfilter was further modified with a nanostructured, SERS-active, plasmonic film that was used to demonstrate proof-of-concept performance with thiophenol as a test analyte. With further optimization of the associated spectroscopic system, this ultra-compact microprobe shows great promise for Raman and SERS optical fiber sensing. Full article
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Figure 1

Figure 1
<p>Schematic of the microfilter assembly on the DCF tip. Filter coatings are deposited onto both sides of a UV-grade fused silica substrate. A ring of the short-pass coating is ablated out to the diameter of the inner cladding, leaving an island at the center that blocks Raman-scattered light from the single/few-mode core. The LPF on the second side of the glass substrate has a hole drilled into the axis of the core to pass the clean laser excitation and reduce the intensity of Rayleigh-scattered light from the sample that returns to the inner cladding. Depending on the transmission characteristics of the sample, a second glass plate can be used to allow the Raman-scattered light from the sample to completely fill the aperture of the inner cladding. The SERS substrate is deposited onto the spacer plate as required.</p>
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<p>Schematic illustration of the sequence of fabrication steps used to form the double-sided microfilter assembly for use on a DCF fiber tip (figure not to scale). (<b>a</b>) A commercially available LPF was used as the starting point (see text for details). (<b>b</b>) The glass substrate was ground down and polished to reduce the thickness of the substrate to approximately 0.7 mm. (<b>c</b>) The SPF was deposited onto the opposing surface to the long-pass coating. (<b>d</b>) A ring of SPF was removed through femtosecond laser drilling, after which (<b>e</b>) the hole in the LPF was drilled as described in the text. (<b>f</b>) Finally, a further glass spacer was bonded to the LPF surface to provide a substrate for the SERS sensing surface. (<b>g</b>) Perspective view of the filter patterns. (<b>h</b>) Scanning electron microscope image of SERS-active, photochemically deposited silver nanoparticles on the surface of the outer glass substrate.</p>
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<p>Tool paths programmed for ablating (<b>a</b>) the short-pass coating and (<b>b</b>) the long-pass coating. For the SERS testing presented below, <span class="html-italic">R</span><sub>1</sub> = 5 µm and <span class="html-italic">R</span><sub>2</sub> = 55 µm were used. The spacing and number of paths in each case were determined by the laser spot size (4.5 μm), the track overlap (1.5 μm), and the depth to be ablated.</p>
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<p>Translation stages and UV curing system used for aligning and attaching the microfilter assembly to the DCF tip.</p>
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<p>The double-sided filter combines the transmission characteristics of both the long- and short-pass filters. The SPF (black line) passes the laser line (shown in green) while blocking the silica Raman-scattered signal in the Raman spectral range. To enter the inner cladding of the DCF, Raman-scattered light from the sample passes through the LPF (red line) and through the ablated region of the short-pass coating, while Rayleigh scattering from the sample is blocked.</p>
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<p>(<b>a</b>) Optical profilometer measurement of a typical short-pass island (<span class="html-italic">R</span><sub>1</sub> = 8 µm) and ablated ring after cleaning. (<b>b</b>) Magnified view of the short-pass island region from (<b>a</b>). (<b>c</b>) Microscopic image of another example with <span class="html-italic">R</span><sub>1</sub> = 5 µm, taken under white light epi-illumination (20× objective). Wavelengths above 520 nm are transmitted by the LPF on the far side of the plate, while the shorter, mainly blue wavelengths are reflected, resulting in the observed blue color of the ablated region. (<b>d</b>) SEM image of the short-pass island from (<b>c</b>), with the edges of the island showing some evidence of the discrete layers deposited to form the SPF. The ablated region is accurate to the design dimensions, and the boundaries between the ablated region and the remaining SPF are relatively narrow. While the circumferential tool path from <a href="#nanomaterials-14-01345-f003" class="html-fig">Figure 3</a>a can be discerned here in (<b>c</b>), and individual ablation sites can be seen on the glass surface in (<b>d</b>), there is no sign of any significant residual filter coating material on the ablated surface.</p>
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<p>(<b>a</b>) Spectrum acquired through a 25 cm DCF segment with integrated microfilter assembly. (<b>b</b>) The characteristic SERS peaks of thiophenol are clearly visible after subtracting the fiber Raman background, which is generated primarily by the transmitted laser excitation in this simplified setup. The thiophenol spectrum could not be detected in any of the DCF probes without filtering assembly. (<b>c</b>) As expected, the intensity of the fiber Raman background scales approximately proportionally with the probe length, whereas the SERS peak intensity is reasonably constant with relatively minor losses for longer probe lengths. Peak intensities have been normalized against the 12 cm DCF probe in each case.</p>
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