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13 pages, 3406 KiB  
Article
Coral Reef-like CdS/g-C3N5 Heterojunction with Enhanced CO2 Adsorption for Efficient Photocatalytic CO2 Reduction
by Fuhai Zhang, Jing Xiong, Xiaoxiao Yu, Lei Wang, Tongyu Wu, Zhendong Yu, Minmeng Tang, Haiyan Liu, Yanhong Chao and Wenshuai Zhu
Catalysts 2025, 15(1), 94; https://doi.org/10.3390/catal15010094 (registering DOI) - 20 Jan 2025
Viewed by 141
Abstract
As a promising member of the carbon nitride family, nitrogen-rich g-C3N5 has attracted significant attention because of its excellent light absorption performance. Nevertheless, its practical application in photocatalytic CO2 reduction is hindered by severe photogenerated charge recombination and limited [...] Read more.
As a promising member of the carbon nitride family, nitrogen-rich g-C3N5 has attracted significant attention because of its excellent light absorption performance. Nevertheless, its practical application in photocatalytic CO2 reduction is hindered by severe photogenerated charge recombination and limited CO2 adsorption capacity. Constructing a heterojunction has emerged as an effective strategy to mitigate charge recombination, thereby enhancing the photocatalytic performance of the catalyst. Herein, a series of CdS/g-C3N5-X heterojunction catalysts were prepared via an in situ hydrothermal approach. The obtained heterojunction catalysts exhibited a novel coral reef-like morphology which facilitated the exposure of additional active sites, thereby enhancing the adsorption and activation of CO2. Moreover, studies have shown that CdS can be anchored to the surface of g-C3N5 through C-S bonds, forming a built-in electric field at the interface, which accelerated the separation and transfer of photogenerated charges. Consequently, the resulting heterojunction materials demonstrated high efficiency in photocatalytic CO2 reduction with H2O as a sacrificial agent. In particular, CdS/g-C3N5-0.2 exhibited the maximum photocatalytic performance up to 22.9 μmol·g−1·h−1, which was 6 times and 3 times that of unmodified g-C3N5 and CdS, respectively. The results indicated that the increased active sites and enhanced charge separation of the Cd/g-C3N5-0.2 catalyst were the primary reasons for its improved photocatalytic CO2 reduction performance. This work provides a novel heterojunction-based photocatalyst for efficient CO2 photocatalytic reduction, offering insights into the preparation of high-performance photocatalysts for sustainable energy applications. Full article
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<p>(<b>a</b>) XRD patterns of g-C<sub>3</sub>N<sub>5</sub>, CdS, and CdS/g-C<sub>3</sub>N<sub>5</sub>, (<b>b</b>) SEM, (<b>c</b>) TEM, (<b>d</b>,<b>e</b>) HRTEM, and (<b>f</b>–<b>i</b>) element mapping images of CdS/g-C<sub>3</sub>N<sub>5</sub>.</p>
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<p>(<b>a</b>) N<sub>2</sub> adsorption–desorption isotherms and (<b>b</b>) CO<sub>2</sub> adsorption isotherms of the as-prepared samples.</p>
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<p>High-resolution XPS spectra of (<b>a</b>) C 1s, (<b>b</b>) N 1s, (<b>c</b>) S 2p, and (<b>d</b>) Cd 3d for the as-prepared specimens.</p>
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<p>(<b>a</b>) UV–Vis DRS and (<b>b</b>) band structures of g-C<sub>3</sub>N<sub>5</sub>, CdS, and CdS/g-C<sub>3</sub>N<sub>5</sub>, (<b>c</b>) PL spectra, (<b>d</b>) tr-PL spectra, and (<b>e</b>) TPC responses of g-C<sub>3</sub>N<sub>5</sub> and CdS/g-C<sub>3</sub>N<sub>5</sub>, (<b>f</b>) EIS plots of g-C<sub>3</sub>N<sub>5</sub>, CdS, and CdS/g-C<sub>3</sub>N<sub>5</sub>.</p>
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<p>(<b>a</b>) Average productivity of CO and CH<sub>4</sub> over the as-prepared samples, (<b>b</b>) recyclability test of CdS/g-C<sub>3</sub>N<sub>5</sub>-0.2.</p>
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<p>Synthesis routes of CdS/g-C<sub>3</sub>N<sub>5</sub>-X.</p>
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15 pages, 5281 KiB  
Article
Fabrication and Compression Properties of Two-Layered Porous Structure of Different Materials by Direct Printing of Resin Porous Structure on Aluminum Foam Using a 3D Printer
by Yoshihiko Hangai, Reiji Yamazaki and Takaaki Suzuki
Materials 2025, 18(2), 433; https://doi.org/10.3390/ma18020433 - 17 Jan 2025
Viewed by 331
Abstract
The porous structure, in which many pores are intentionally placed inside the material, has excellent impact energy absorption properties. Recent studies have attempted to fabricate multi-layered porous structures with different mechanical properties within a single porous structure sample, and the mechanical properties of [...] Read more.
The porous structure, in which many pores are intentionally placed inside the material, has excellent impact energy absorption properties. Recent studies have attempted to fabricate multi-layered porous structures with different mechanical properties within a single porous structure sample, and the mechanical properties of these structures are being elucidated. However, these studies mainly attempted to vary the densities, pore structures, and alloy compositions within a single material, such as aluminum, for the entire sample. Since multi-materials are now being promoted to utilize the most suitable material type in the right place, porous structures made of different materials, such as a combination of aluminum and resin, are expected to be required in the future. In this study, we attempted to fabricate two-layered porous structure samples of different materials by printing a resin porous structure using a 3D printer on an aluminum foam fabricated by a precursor foaming process. Static compression tests were performed on the resulting two-layered porous structure samples to investigate their mechanical properties. The resin porous structure printed by the 3D printer and the aluminum foam were both designed to expose the porous structure on the surface of the specimen so that the deformation behavior can be easily observed. The density of the resin porous structure was varied by systematically varying the filling rate of the resin porous structure to be printed, and the effect on the compression properties was investigated. The fabricated two-layered porous structure was effectively bonded between the two layers by the anchor effect, which is a mechanical bonding caused by the resin penetrating into the pores. The layers exhibited robust bonding with no evidence of separation. It was possible to fabricate a two-layered porous structure that exhibited both properties of aluminum foam and those of resin porous structure. It was found that the plateau stress in the resin porous structure layer can be controlled between about 0.5 MPa and 40 MPa, and the deformation behavior and energy absorption properties of the two-layered porous structure can be controlled by varying the resin filling rate of the resin porous structure layer. That is, it was indicated that multi-layered porous structures with various densities and consisting of various types of materials allow for the optimal design of porous structures used in structural materials. Full article
(This article belongs to the Special Issue Advances in Materials Processing (3rd Edition))
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<p>Schematic illustration of precursor fabrication. (<b>a</b>) A laminate plate was made by placing a foaming agent powder and a pore structures stabilizer powder between two aluminum alloy plates. (<b>b</b>) The FSW tool was traversed over the laminate plate.</p>
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<p>Obtained sample. (<b>a</b>) Precursor. (<b>b</b>) Foamed sample. (<b>c</b>) Aluminum foam specimen.</p>
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<p>Resin porous structure was printed on the aluminum foam sample using a 3D printer.</p>
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<p>Cross-section of the printing data input to the 3D printer for the resin filling rate <span class="html-italic">φ</span> = 10%, 40%, and 70% to print a resin porous structure.</p>
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<p>Obtained two-layered porous structure compression specimens with filling rates of (<b>a</b>) <span class="html-italic">φ</span> = 10%, (<b>b</b>) <span class="html-italic">φ</span> = 40%, and (<b>c</b>) <span class="html-italic">φ</span> = 70%, for the resin porous structure layer.</p>
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<p>Results of compression test of uniform resin porous structures. (<b>a</b>) Compression deformation behaviors. (<b>b</b>) Stress <span class="html-italic">σ</span>–strain <span class="html-italic">ε</span> curves. (<b>c</b>) Relationship between stress and absorbed energy. (<b>d</b>) Specimens after compression tests.</p>
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<p>Results of compression test of a two-layered porous structure compression specimen with a filling rate of <span class="html-italic">φ</span> = 10% in the resin porous structure layer. (<b>a</b>) Compression deformation behavior. (<b>b</b>) Stress <span class="html-italic">σ</span>–strain <span class="html-italic">ε</span> curve. (<b>c</b>) Specimen of aluminum foam layer side after compression test. (<b>d</b>) Specimen of resin porous structure layer side after compression test. (<b>e</b>) X-ray CT image of specimen before compression test. The white arrows indicate where PLA penetration can be observed in the pores.</p>
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<p>Results of compression test of a two-layered porous structure compression specimen with a filling rate of <span class="html-italic">φ</span> = 70% in the resin porous structure layer. (<b>a</b>) Compression deformation behavior. (<b>b</b>) Stress <span class="html-italic">σ</span>–strain <span class="html-italic">ε</span> curve.</p>
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<p>Results of compression test of a two-layered porous structure compression specimen with a filling rate of <span class="html-italic">φ</span> = 40% in the resin porous structure layer. (<b>a</b>) Compression deformation behavior. (<b>b</b>) Stress <span class="html-italic">σ</span>–strain <span class="html-italic">ε</span> curve.</p>
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<p>Plateau stresses of the resin porous structure in the two-layered porous structures and the uniform resin porous structures for each filling rate <span class="html-italic">φ</span>.</p>
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<p>Relationship between stress and absorbed energy estimated from the <span class="html-italic">σ</span>–<span class="html-italic">ε</span> curves of the obtained two-layered porous structures.</p>
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11 pages, 686 KiB  
Review
Immobilization of Enzymes in Polymeric Materials Based on Polyamide: A Review
by Carolina E. Demaman Oro, Bruna M. Saorin Puton, Luciana D. Venquiaruto, Rogério Marcos Dallago and Marcus V. Tres
Processes 2025, 13(1), 200; https://doi.org/10.3390/pr13010200 - 13 Jan 2025
Viewed by 648
Abstract
The immobilization of enzymes in polyamide-based polymeric materials through covalent bonding is an established technique to stabilize and reuse biocatalysts in industrial processes. Traditionally, enzymes are immobilized using crosslinking agents that activate functional groups on both the support and the enzyme, creating strong [...] Read more.
The immobilization of enzymes in polyamide-based polymeric materials through covalent bonding is an established technique to stabilize and reuse biocatalysts in industrial processes. Traditionally, enzymes are immobilized using crosslinking agents that activate functional groups on both the support and the enzyme, creating strong bonds that securely anchor the enzyme to the surface. While effective for maintaining enzyme activity over multiple cycles, this method can reduce catalytic efficiency due to rigid binding and involves complex activation steps. Recently, in situ immobilization approaches have emerged as promising alternatives. In this method, enzymes are directly entrapped within the polymer matrix during the synthesis of the polyamide support, such as nylon, simplifying the process and offering enhanced control over enzyme distribution. For instance, studies have demonstrated that in situ immobilization can improve enzyme stability by protecting it within the polymeric network, while reducing production costs and waste. This review explores the ability of polyamide as a support material for immobilization of enzymes, analyzing key techniques, performance across applications, and future strategies to optimize polymer-enzyme interactions for industrial use. Full article
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<p>Classification of enzyme immobilization methods.</p>
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<p>Nylon structural unit.</p>
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17 pages, 4305 KiB  
Article
Resistance Spot Welding Defect Detection Based on Visual Inspection: Improved Faster R-CNN Model
by Weijie Liu, Jie Hu and Jin Qi
Machines 2025, 13(1), 33; https://doi.org/10.3390/machines13010033 - 7 Jan 2025
Viewed by 369
Abstract
This paper presents an enhanced Faster R-CNN model for detecting surface defects in resistance welding spots, improving both efficiency and accuracy for body-in-white quality monitoring. Key innovations include using high-confidence anchor boxes from the RPN network to locate welding spots, using the SmoothL1 [...] Read more.
This paper presents an enhanced Faster R-CNN model for detecting surface defects in resistance welding spots, improving both efficiency and accuracy for body-in-white quality monitoring. Key innovations include using high-confidence anchor boxes from the RPN network to locate welding spots, using the SmoothL1 loss function, and applying Fast R-CNN to classify detected defects. Additionally, a new pruning model is introduced, reducing unnecessary layers and parameters in the neural network, leading to faster processing times without sacrificing accuracy. Tests show that the model achieves over 90% accuracy and recall, processing each image in about 15 ms, meeting industrial requirements for welding spot inspection. Full article
(This article belongs to the Section Industrial Systems)
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<p>Overall structure of the Faster R-CNN detection algorithm.</p>
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<p>Improved training network structure diagram. The RPN_forward structure (<b>left</b>), the Fast R-CNN structure (<b>right</b>).</p>
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<p>RPN structure (<b>left</b>); anchor box setting diagram (<b>right</b>).</p>
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<p>Comparison of <math display="inline"><semantics> <mrow> <msub> <mi>L</mi> <mn>1</mn> </msub> </mrow> </semantics></math>, <math display="inline"><semantics> <mrow> <msub> <mi>L</mi> <mn>2</mn> </msub> </mrow> </semantics></math>, and Smooth <math display="inline"><semantics> <mrow> <msub> <mi>L</mi> <mn>1</mn> </msub> </mrow> </semantics></math> losses.</p>
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<p>Image samples of body-in-white welding spots and labels.</p>
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<p>The procedure diagram of the welding spot quality inspection process.</p>
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<p>The comparison of recall rates of different models.</p>
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<p>The results of several samples to show the performance of different models. SSD model (<b>a</b>), CNN-Lenet5 (<b>b</b>), Faster RCNN (<b>c</b>), and the proposed model (<b>d</b>).</p>
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<p>Additional examples of detected defects on the testing data.</p>
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14 pages, 2602 KiB  
Article
Roles of Mature Domain Targeting Signals (MTSs) for Protein Translocation and Secretion in Lactococcus lactis
by Mai Ngoc Hoang and Clemens Peterbauer
Int. J. Mol. Sci. 2025, 26(1), 219; https://doi.org/10.3390/ijms26010219 - 30 Dec 2024
Viewed by 491
Abstract
Lactococcus lactis is a potential bacterial cell factory to develop delivery systems for vaccines and therapeutic proteins. Much progress has been made in applications using engineered L. lactis against, e.g., inflammatory bowel disease and cervical cancer, but the improvement of secretion and cell [...] Read more.
Lactococcus lactis is a potential bacterial cell factory to develop delivery systems for vaccines and therapeutic proteins. Much progress has been made in applications using engineered L. lactis against, e.g., inflammatory bowel disease and cervical cancer, but the improvement of secretion and cell anchoring efficacy is still desirable. A double-labeling method based on biarsenical hairpin binding and nickel–polyhistidine affinity was used for visualization of protein trafficking and the quantification of targeted proteins on the cell surface and in the cytoplasm. To investigate the importance of mature domain targeting signals (MTSs), we generated truncated constructs encoding 126, 66, and 26 amino acid residues from the N-terminus of the basic membrane protein A (BmpA) and fused those with the gene for the human papillomavirus serotype 16 (HPV16) E7 oncoprotein. Overexpression of fusion proteins was observed to come at the cost of cell proliferation. L. lactis cells produced and displayed the shortest fusion protein only with difficulty, suggesting that the entire absence of a homologous sequence containing MTSs significantly impedes the export and surface anchoring of fusion proteins. With 40 amino acids following the signal peptide and containing one MTS, effective translocation was possible. Mutations of MTSs towards increased hydrophobicity resulted in increased secreted and surface-displayed fusion protein, suggesting the potential to design rationally improved constructs. Full article
(This article belongs to the Section Molecular Microbiology)
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<p>Growth profile of <span class="html-italic">L. lactis</span> carrying homologous proteins and fusion proteins. Optical density (OD) at 600 nm wavelength was measured after 3-, 9- and 24-h post-induction.</p>
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<p>Quantitative comparison on surface and intracellular fluorescence expression of <span class="html-italic">L. lactis</span> carrying homologous and fusion proteins over three time points (3, 9, 24 h post induction). Color of columns: blue—3 h, orange—9 h, gray—24 h. (<b>a</b>) Surface fluorescence, y-axis: corrected fluorescence intensity of Ni-NTA-Atto 488 (His-tag); (<b>b</b>) intracellular fluorescence, y-axis: corrected average cell fluorescence of ReAsH (Tetra-cysteine tag).</p>
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<p>Hydropathy plot of BmpA and fusion proteins. (<b>a</b>) BmpA conjugated C-terminally with hexa-histidine and tetra-cysteine tags, 366 amino acids in length. (<b>b</b>) BE1, BE2, and BE3 (126, 66, and 26 amino acids at the N-terminus of BmpA fused with HPV16 E7 and C-terminally tagged with hexa-histidine and tetra-cysteine), window size = 5. Red line: threshold +1.6. Graph was created by ProtScale Expasy.</p>
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<p>Site-directed designation for mutations. (<b>a</b>) Sequence map of BE1 fusion construct. Hydrophobic patches (signal peptide—H1, H2, H3, H4) were identified by Kyte–Doolittle hydropathy evaluation and annotated accordingly. (<b>b</b>) List of mutations created using site-directed mutagenesis.</p>
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<p>Quantitative comparison on surface and intracellular fluorescence protein expression of alanine variants at 3, 9, and 24 h are included. (<b>a</b>) Quantitative comparison of surface expression and (<b>b</b>) quantitative comparison of intracellular expression: blue bar—three hours; orange bar—nine hours; light gray bar—24 h.</p>
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<p>Maps of plasmid constructs. (<b>a</b>) pNZ8150 with the gene for the membrane-anchored protein BmpA. (<b>b</b>) pNZ8150 with the sequence encoding the first 126 N-terminal amino acids of BmpA fused with the gene for the heterologous oncoprotein E7 from HPV-16. (<b>c</b>, <b>d</b>) Truncated constructs of the insert from the plasmid in b, containing the first 66 N-terminal amino acids of BmpA, or only the first 26 amino acids (the signal peptide) of BmpA, and E7.</p>
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11 pages, 1603 KiB  
Article
Photoinduced Interactions in Thin Films of Azo Dyes and Planar-Aligned Nematic Liquid Crystal
by Aleksey Kudreyko, Vladimir Chigrinov and Arina Perestoronina
Crystals 2025, 15(1), 22; https://doi.org/10.3390/cryst15010022 - 28 Dec 2024
Viewed by 483
Abstract
Properties of surface anchoring depend on the absorbed exposure energy and various potential interactions associated with liquid crystal and azo dye layers. In this study, we investigate a model of dispersion, steric and photoinduced interactions with the goal of providing a qualitative and [...] Read more.
Properties of surface anchoring depend on the absorbed exposure energy and various potential interactions associated with liquid crystal and azo dye layers. In this study, we investigate a model of dispersion, steric and photoinduced interactions with the goal of providing a qualitative and quantitative description of orientationally ordered hard uniaxial liquid crystals and azo dye molecules. By using the Onsager theory, we estimated the effect of excluded volume. Typical repulsive potentials between liquid crystal and azo dye molecules are displayed graphically. The presence of statistical dispersion in molecular alignment of liquid crystals leads to potential wells in dipole–dipole interactions. Our mean field theory investigation of dipole–dipole interactions shows that the anchoring free energy is governed by the net interaction energy associated with the averaged dipole moments of liquid crystal and azo dye molecules, photoaligned surface dipole moments, and local charge densities. We also use the Fokker–Planck equation to show that rotational diffusion is described by the effective mean field potential, which includes photoinduced and van der Waals interactions. Our findings underscore the potential of mean field theory for intermolecular couplings in photoaligned surfaces, opening up new pathways of molecular design for a broad range of parameters. Full article
(This article belongs to the Collection Liquid Crystals and Their Applications)
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<p>(<b>a</b>) Various configurations of dipole moments, providing repulsive and attractive interactions; (<b>b</b>) potential energy of pairwise dipole–dipole coupling versus <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="sans-serif">φ</mi> </mrow> <mrow> <mi mathvariant="normal">L</mi> <mi mathvariant="normal">C</mi> </mrow> </msub> </mrow> </semantics></math> for normally distributed LC alignment (solid curve) and perfect alignment of LC molecules (dashed curve).</p>
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<p>(<b>a</b>) Excluded volume versus principal axes, defining long molecular axes; illustration of the excluded volume effects for uniaxial molecules of LC and AD: (<b>b</b>) perpendicular and (<b>c</b>) parallel alignment. Chemical formulas in cylinder-shaped molecules represent azo dyes SD1m and SD1, respectively. Half-transparent cylinders denote the excluded volume.</p>
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<p>Simulation of 5CB (blue molecules) alignment along long molecular axis of SD1 (green molecules) on the substrate plane; surface size: 150 Å <math display="inline"><semantics> <mrow> <mo>×</mo> </mrow> </semantics></math> 150 Å.</p>
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<p>Repulsive effect of steric interaction for various distances between molecular centers of AD and LC for (<b>a</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>X</mi> </mrow> <mrow> <mn>0</mn> </mrow> </msub> <mo>=</mo> <mn>4</mn> </mrow> </semantics></math> and (<b>b</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>X</mi> </mrow> <mrow> <mn>0</mn> </mrow> </msub> <mo>=</mo> <mn>6</mn> </mrow> </semantics></math>; (<b>c</b>) Gay−Berne potential versus separation distance between molecular centers of azo dye and LC for various angles <math display="inline"><semantics> <mrow> <mi mathvariant="sans-serif">θ</mi> </mrow> </semantics></math>.</p>
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15 pages, 7050 KiB  
Article
Formation and Surface Structures of Long-Range Ordered Self-Assembled Monolayers of 2-Mercaptopyrazine on Au(111)
by Dongjin Seo, Jin Wook Han, Hongki Kim, Yeon O Kim, Hyun Sun Sung, Riko Kaizu, Glenn Villena Latag, Tomohiro Hayashi, Nam-Suk Lee and Jaegeun Noh
Int. J. Mol. Sci. 2025, 26(1), 160; https://doi.org/10.3390/ijms26010160 - 27 Dec 2024
Viewed by 438
Abstract
The effect of solution pH on the formation and surface structure of 2-pyrazinethiolate (2-PyzS) self-assembled monolayers (SAMs) formed by the adsorption of 2-mercaptopyrazine (2-PyzSH) on Au(111) was investigated using scanning tunneling microscopy (STM) and X-ray photoelectron microscopy (XPS). Molecular-scale STM observations clearly revealed [...] Read more.
The effect of solution pH on the formation and surface structure of 2-pyrazinethiolate (2-PyzS) self-assembled monolayers (SAMs) formed by the adsorption of 2-mercaptopyrazine (2-PyzSH) on Au(111) was investigated using scanning tunneling microscopy (STM) and X-ray photoelectron microscopy (XPS). Molecular-scale STM observations clearly revealed that 2-PyzS SAMs at pH 2 had a short-range ordered phase of (2√3 × √21)R30° structure with a standing-up adsorption structure. However, 2-PyzS SAMs at pH 8 had a very unique long-range ordered phase, showing a “ladder-like molecular arrangement” with bright repeating rows. This ordered phase was assigned to the (3 × √37)R43° structure, consisting of two different adsorption structures: standing-up and tilted adsorption structures. The average arial density of 2-PyzS SAMs on Au(111) at pH 8 was calculated to be 49.47 Å2/molecule, which is 1.52 times more loosely packed compared to the SAMs at pH 2 with 32.55 Å2/molecule. XPS measurements showed that 2-PyzS SAMs at pH 2 and pH 8 were mainly formed through chemical interactions between the sulfur anchoring group and the Au(111) substrates. The proposed structural models of packing structures for 2-PyzS SAMs on Au(111) at different pHs are well supported by the XPS results. The results of this study will provide new insights into the formation, surface structure, and molecular orientation of SAMs by N-heteroaromatic thiols with pyrazine molecular backbone on Au(111) at the molecular level. Full article
(This article belongs to the Section Biochemistry)
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Graphical abstract
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<p>A chemical structure of 2-PyzSH and the formation of 2-PyzS SAMs on Au(111) by the spontaneous adsorption of 2-PyzSH molecules.</p>
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<p>(<b>a</b>,<b>c</b>,<b>d</b>) STM images of 2-PyzS SAMs on Au(111) in 0.01 mM ethanol solution of 2-PyzSH at pH 2 for 1 h at RT. (<b>b</b>) Height profile of a blue line drawn along on the bright island protruding from the surface. The scan sizes of the STM images are (<b>a</b>) 90 nm × 90 nm, (<b>b</b>) 60 nm × 60 nm, and (<b>d</b>) 10 nm × 10 nm. The disordered phase, ordered phase, and small bright islands in (<b>c</b>) are marked with A, B, and blue circle, respectively.</p>
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<p>(<b>a</b>) High-resolution STM image (5 nm × 5 nm) of 2-PyzS SAMs on Au(111) in 0.01 mM ethanol solution of 2-PyzSH at pH 2 for 1 h at RT. (<b>b</b>) Proposed structural model of the SAMs on Au(111). (<b>c</b>) Top and side views of 2-PyzS molecules adsorbed on Au(111). In the structural model, white, blue, and red spheres represent the carbon, nitrogen, and sulfur atoms. Note that a and b in (<b>b</b>) correspond to the unit cell vectors of lattice, and δ corresponds to rotation angle of the unit cell.</p>
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<p>(<b>a</b>,<b>b</b>) STM images of 2-PyzS SAMs on Au(111) in 0.01 mM ethanol solution of 2-PyzSH at pH 8 for 1 h at RT. The scan sizes of the STM images are (<b>a</b>) 90 nm × 90 nm and (<b>b</b>) 30 nm × 30 nm. The disordered phase, ordered phase, and small bright islands in (<b>a</b>) are marked with A, B, and blue circle, respectively. Structural defects in (<b>b</b>) are indicated by the white arrows.</p>
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<p>(<b>a</b>) High-resolution STM image and (<b>b</b>) low-pass-filtered STM image of 2-PyzS SAMs on Au(111) in 0.01 mM ethanol solution of 2-PyzSH at pH 8 for 1 h at RT. (<b>c</b>) Proposed structural model of the SAMs on Au(111). (<b>d</b>) Top and side views of 2-PyzS molecules adsorbed on Au(111). In the structural model, white, blue, and red spheres represent the carbon, nitrogen, and sulfur atoms. The scan sizes of the STM images are (<b>a</b>) 10 nm × 10 nm and (<b>b</b>) 5 nm × 5 nm. The one and paired molecular spots in (<b>b</b>) are marked with open white and oval blue circles, respectively. Note that a and b in (<b>b</b>,<b>c</b>) correspond to the unit cell vectors of lattice, and δ in (<b>c</b>) corresponds to rotation angle of the unit cell.</p>
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<p>S 2p XPS spectra of 2-PyzS SAMs on Au(111) in 0.01 mM ethanol solution of 2-PyzSH at (<b>a</b>) pH 2 and (<b>b</b>) pH 8 for 1 h at RT.</p>
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<p>N 1s XPS spectra of 2-PyzS SAMs on Au(111) in 0.01 mM ethanol solution of 2-PyzSH at (<b>a</b>) pH 2 and (<b>b</b>) pH 8 for 1 h at RT.</p>
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12 pages, 2430 KiB  
Article
Buried Interface Modification Using Diammonium Ligand Enhances Mechanical Durability of Flexible Perovskite Solar Cells
by Xuan Ji, Xin Chen, Wanlei Dai, Yongshuai Gong, Zheng Zhang, Lei Zhang, Cheng Ma, Tinghuan Yang, Yixin Dong, Buyi Yan, Dongxue Liu and Tianqi Niu
Coatings 2025, 15(1), 15; https://doi.org/10.3390/coatings15010015 - 27 Dec 2024
Viewed by 495
Abstract
Flexible perovskite solar cells (F-PSCs) hold great potential for lightweight photovoltaic applications due to their flexibility, bending compatibility, and low manufacturing cost. However, tin oxide (SnO2), as a common electron transport layer (ETL) used in F-PSCs, typically suffers from high-density surface [...] Read more.
Flexible perovskite solar cells (F-PSCs) hold great potential for lightweight photovoltaic applications due to their flexibility, bending compatibility, and low manufacturing cost. However, tin oxide (SnO2), as a common electron transport layer (ETL) used in F-PSCs, typically suffers from high-density surface defects that hinder the charge extraction efficiency and deteriorate the crystallization quality of the upper perovskite film. Additionally, the poor buried interface quality intensifies lattice extrusion and strain residue across the perovskite films, further aggravating the mechanical brittleness in devices. To address the issues, we developed a molecular bridging strategy by introducing the 2,2′-oxybis(ethylenediamine) dihydrochloride (DO) at the perovskite/SnO2 interface. The diammonium groups of spacer ligands can achieve the bidentate anchoring on the SnO2 and perovskite films, cooperating with the oxygen atom on the alkyl chain to passivate the charged defects at the buried interface. The tailored interface properties also endow the optimized crystallization quality of perovskite films and significantly alleviate tensile strain to strengthen the perovskite’s pliability. As a result, the F-PSCs achieved a champion efficiency of 23.50%, outperforming the value of 21.87% for the control device. Furthermore, the devices exhibited excellent mechanical robustness, maintaining 90% of the initial PCE after 6000 bending cycles at a radius of 4 mm. This work presents a reliable strategy for the synergistic optimization of the buried contact at the electron extraction interface, contributing to the further development of efficient and stable F-PSCs. Full article
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<p>(<b>a</b>) Schematic illumination of the buried interface modification using DO ligands. High-resolution XPS spectra of (<b>b</b>) Pb 4f and (<b>c</b>) N 1s signals for the perovskite films deposited on SnO<sub>2</sub> with and without DO modification. Plane-view SEM images of the top interface (<b>d</b>) and buried interface (<b>e</b>) for the different perovskite films (red circles represent the pinholes at perovskite surface); (<b>f</b>) cross-sectional images for the different perovskite films (red circles represent the voids at contact interface); (<b>g</b>) 2D GIWAXS patterns of perovskite films; (<b>h</b>) line-cut profiles from GIWAXS patterns.</p>
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<p>(<b>a</b>,<b>b</b>) PFQNM images of the perovskite films deposited on SnO<sub>2</sub> with and without DO decoration. (<b>c</b>,<b>d</b>) Depth-dependent GIXRD patterns of perovskite films. (<b>e</b>) Linear fit of sin<sup>2</sup> Ψ and 2θ curves of perovskite films. (<b>f</b>) Statistics of residual stress within perovskite films.</p>
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<p>(<b>a</b>) UV-vis absorption spectra. (<b>b</b>) Tauc plots extracted from UV-vis absorption spectra. (<b>c</b>) Dark <span class="html-italic">I</span>–<span class="html-italic">V</span> curves of the electron-only devices. (<b>d</b>) <span class="html-italic">I</span>–<span class="html-italic">V</span> curves determining the conductivity of perovskite films. (<b>e</b>,<b>f</b>) Steady-state PL and TRPL spectra of perovskite films deposited on ITO substrates.</p>
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<p>(<b>a</b>) Device configuration of the n-i-p-structured F-PSCs. (<b>b</b>) <span class="html-italic">J</span>–<span class="html-italic">V</span> curves of champion F-PSCs using SnO<sub>2</sub> with and without DO decoration. (<b>c</b>) EQE curves and the corresponding integrated current density of F-PSCs. (<b>d</b>–<b>f</b>) Nyquist plots, dark <span class="html-italic">I</span>–<span class="html-italic">V</span> curves, and Mott–Schottky plots for different devices. (<b>g</b>) Humidity stability test of F-PSCs in ambient air at ca. 40% humidity condition. (<b>h</b>) Bending stability test of F-PSCs with a bending radius of 4 mm.</p>
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16 pages, 9041 KiB  
Article
Carbon Nanofiber-Reinforced Carbon Black Support for Enhancing the Durability of Catalysts Used in Proton Exchange Membrane Fuel Cells Against Carbon Corrosion
by Minki Sung, Hyeonseok Yi, Jimin Han, Jong Beom Lee, Seong-Ho Yoon and Joo-Il Park
Membranes 2025, 15(1), 3; https://doi.org/10.3390/membranes15010003 - 26 Dec 2024
Viewed by 532
Abstract
This study addresses the critical challenge of carbon corrosion in proton exchange membrane fuel cells (PEMFCs) by developing hybrid supports that combine the high surface area of carbon black (CB) with the superior crystallinity and graphitic structure of carbon nanofibers (CNFs). Two commercially [...] Read more.
This study addresses the critical challenge of carbon corrosion in proton exchange membrane fuel cells (PEMFCs) by developing hybrid supports that combine the high surface area of carbon black (CB) with the superior crystallinity and graphitic structure of carbon nanofibers (CNFs). Two commercially available CB samples were physically activated and composited with two types of CNFs synthesized via chemical vapor deposition using different carbon sources. The structure, morphology, and crystallinity of the resulting CNF–CB hybrid supports were characterized, and the performances of these hybrid supports in mitigating carbon corrosion and enhancing the PEMFC performance was evaluated through full-cell testing in collaboration with a membrane electrode assembly (MEA) manufacturer (VinaTech, Seoul, Republic, of Korea), adhering to industry-standard fabrication and evaluation procedures. Accelerated stress tests following the US Department of Energy protocols revealed that incorporating CNFs enhanced the durability of the CB-based hybrid supports without compromising their performance. The improved performance of the MEAs with the hybrid carbon support is attributed to the ability of the CNF to act as a structural backbone, facilitate water removal, and provide abundant edge plane sites for anchoring the platinum catalyst, which promoted the oxygen reduction reaction and improved catalyst utilization. The findings of this study highlight the potential of CNF-reinforced CB supports for enhancing the durability and performance of PEMFCs. Full article
(This article belongs to the Special Issue New Challenges in Proton Exchange Membrane Fuel Cells)
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<p>Transmission electron microscopy images and schematic illustration of the carbon structures in (<b>a</b>) platelet-type and (<b>b</b>) herringbone-type carbon nanofibers.</p>
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<p>X-ray diffraction spectra of carbon peaks. (<b>a</b>) Platelet-types and (<b>b</b>) herringbone-types.</p>
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<p>Scanning electron microscopy images of the carbon nanofibers (CNFs) synthesized at different temperatures using different carbon sources: (<b>a</b>–<b>c</b>) platelet-type and (<b>d</b>–<b>f</b>) herringbone-type CNFs.</p>
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<p>N<sub>2</sub> adsorption–desorption isotherms recorded at 77K for CNF-CB hybrid supports: (<b>a</b>) CBAa series and (<b>c</b>) CBBa series. QSDFT pore size distributions: (<b>b</b>) CBAa series and (<b>d</b>) CBBa series.</p>
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<p>Scanning electron microscopy images of the CNF-CB hybrid supports: (<b>a</b>) CBAa_5, (<b>b</b>) CBAa_10, (<b>c</b>) CBBa_5, and (<b>d</b>) CBBa_10.</p>
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<p>Transmission electron microscopy images of the CNF-CB hybrid supports: (<b>a</b>) CBAa_5, (<b>b</b>) CBAa_10, (<b>c</b>) CBBa_5, and (<b>d</b>) CBBa_10.</p>
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<p>Initial performance evaluation and electrochemically active surface areas of MEAs with CNF-CB hybrid supports and reference samples. (<b>a</b>,<b>c</b>) CBAa series and (<b>b</b>,<b>d</b>) CBBa series.</p>
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<p>AST polarization curves and power density curves for full-cell MEAs: (<b>a</b>) CBAa, (<b>b</b>) CBAa_5, (<b>c</b>) CBAa_10, (<b>d</b>) CBBa, (<b>e</b>) CBBa_5, and (<b>f</b>) CBBa_10.</p>
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16 pages, 6568 KiB  
Article
A Pool of Bacterium-like Particles Displaying African Swine Fever Virus Antigens Induces Both Humoral and Cellular Immune Responses in Pigs
by Jingshan Huang, Hongxia Wu, Tianqi Gao, Huanjie Zhai, Assad Moon, Xin Song, Shuwen Li, Zhanhao Lu, Jing Lan, Dailang Zhong, Xinyu Zhang, Hua-Ji Qiu, Yongfeng Li and Yuan Sun
Vaccines 2025, 13(1), 5; https://doi.org/10.3390/vaccines13010005 - 24 Dec 2024
Viewed by 525
Abstract
Background/Objectives: African swine fever (ASF), caused by African swine fever virus (ASFV), poses a significant threat to the global swine industry. This underscores the urgent need for safe and effective ASF vaccines. Methods: Here, we constructed five bacterium-like particles (BLPs) that each display [...] Read more.
Background/Objectives: African swine fever (ASF), caused by African swine fever virus (ASFV), poses a significant threat to the global swine industry. This underscores the urgent need for safe and effective ASF vaccines. Methods: Here, we constructed five bacterium-like particles (BLPs) that each display one of the five ASFV antigens (F317L, H171R, D117L, B602L, and p54) based on the Gram-positive enhancer matrix-protein anchor (GEM-PA) system. GEM is a bacterial particle that contains only peptidoglycan, while PA is composed of three lysin motifs (Lysm) derived from the C-terminus of the AcmA protein, capable of non-covalently binding to GEM. By fusing the ASFV antigens with PA, the ASFV antigens can be firmly attached to the surface of GEM. Subsequently, the piglets were immunized via intramuscular injection with a mixture of BLPs-F317L, BLPs-H171R, BLPs-D117L, BLPs-B602L, and BLPs-p54. Results: The results showed that the piglets developed detectable serum IgG antibodies 2 weeks after the first immunization, and these high antibody levels were maintained 4 weeks after the booster immunization. Moreover, these piglets produced more IFN-γ-producing lymphocytes than the control piglets. Conclusions: The data indicate that the generated BLPs mixture can stimulate both humoral and cellular immune responses in piglets, these five ASFV proteins are promising antigens, and the BLPs generated represent candidate ASF vaccines. Full article
(This article belongs to the Special Issue Vaccine Development for Swine Viral Pathogens)
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<p>Construction of the prokaryotic expression plasmids and identification of soluble expression of the fusion proteins. (<b>a</b>) Schematic diagram of the recombinant plasmids expressing the fusion proteins. The plasmid pGEX-6P-1-PA was digested with <span class="html-italic">Eco</span>RI and <span class="html-italic">Bam</span>HI, and then the five ASFV genes (<span class="html-italic">F317L</span>, <span class="html-italic">H171R</span>, <span class="html-italic">D117L</span>, <span class="html-italic">B602L</span>, and <span class="html-italic">E183L</span>) were individually cloned in the pGEX-6P-1-PA vector to construct the corresponding recombinant plasmid. The ASFV proteins and the anchor protein PA were fused by a flexible linker (4GS). (<b>b</b>–<b>f</b>) Identification of the soluble expression of F317L-PA (<b>b</b>), H171R-PA (<b>c</b>), D117L-PA (<b>d</b>), B602L-PA (<b>e</b>), and p54-PA (<b>f</b>) by Western blotting. M represents the protein marker, and the red arrows represent the ASFV fusion proteins or the GST protein.</p>
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<p>Identification of the surface display of the five ASFV antigens on BLPs and observation of the structure of BLPs. (<b>a</b>) Identification of the surface display of the five ASFV antigens on BLPs by IFA. Here, reference anti-ASFV sera were used as the primary antibody, and anti-pig IgG (whole molecule) FITC antibody was used as the secondary antibody. Subsequently, the samples were observed by a laser scanning confocal microscope. (<b>b</b>) TEM observation of <span class="html-italic">L. lactis</span> NZ3900, GEM, and BLPs-p54. The scale bars represent 200 nm.</p>
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<p>Quantification of the maximum loading capacity of the GEM. Determine the maximum loading capacity of F317L-PA (<b>a</b>), H171R-PA (<b>b</b>), D117L-PA (<b>c</b>), B602L-PA (<b>d</b>), and p54-PA (<b>e</b>) proteins for 1 U of the GEM by SDS-PAGE. Using different concentrations of BSA as a control, a standard curve was established to quantify the protein concentration of the sample. M represents the protein marker, and lanes 3 to 10 represent 0, 0.05, 0.1, 0.15, 0.2, 0.3, 0.4, and 0.5 mg/mL BSA standard protein, respectively.</p>
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<p>The serum ASFV antigen-specific IgG antibodies were produced in the immunized piglets. (<b>a</b>) Immunization schedule of piglets. (<b>b</b>–<b>f</b>) The level of serum ASFV antigen-specific IgG antibodies against F317L (<b>b</b>), H171R (<b>c</b>), D117L (<b>d</b>), B602L (<b>e</b>), and p54 (<b>f</b>) in the sera of the immunized piglets. Each ASFV antigen was used to coat 96-well ELISA plates, and the serum ASFV antigen-specific IgG antibodies against the different antigens were examined by ELISA. Statistical analysis was conducted using a one-way analysis of variance. Statistical significance was defined as the following: ns, <span class="html-italic">p</span> ≥ 0.05; *, <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.</p>
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<p>Quantification of antigen-specific IFN-<span class="html-italic">γ</span>-producing T cells per million PBMCs in the immunized piglets by ELIspot assay. The isolated PBMCs were stimulated with 100 µL of the ASFV HLJ/18 strain (10<sup>6</sup> TCID<sub>50</sub>) per well. The results were read using the AID iSpot FluoroSpot reader system, and the IFN-<span class="html-italic">γ</span>-producing T cells per million PBMCs were calculated. The differences in the results were analyzed by a one-way analysis of variance. Statistical significance was defined as follows: ns, <span class="html-italic">p</span> ≥ 0.05; **, <span class="html-italic">p</span> &lt; 0.01.</p>
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22 pages, 8365 KiB  
Article
FP-YOLOv8: Surface Defect Detection Algorithm for Brake Pipe Ends Based on Improved YOLOv8n
by Ke Rao, Fengxia Zhao and Tianyu Shi
Sensors 2024, 24(24), 8220; https://doi.org/10.3390/s24248220 - 23 Dec 2024
Viewed by 503
Abstract
To address the limitations of existing deep learning-based algorithms in detecting surface defects on brake pipe ends, a novel lightweight detection algorithm, FP-YOLOv8, is proposed. This algorithm is developed based on the YOLOv8n framework with the aim of improving accuracy and model lightweight [...] Read more.
To address the limitations of existing deep learning-based algorithms in detecting surface defects on brake pipe ends, a novel lightweight detection algorithm, FP-YOLOv8, is proposed. This algorithm is developed based on the YOLOv8n framework with the aim of improving accuracy and model lightweight design. First, the C2f_GhostV2 module has been designed to replace the original C2f module. It reduces the model’s parameter count through its unique design. It achieves improved feature representation by adopting specific technique within its structure. Additionally, it incorporates the decoupled fully connected (DFC) attention mechanism, which minimizes information loss during long-range feature transmission by separately capturing pixel information along horizontal and vertical axes via convolution. Second, the Dynamic ATSS label allocation strategy is applied, which dynamically adjusts label assignments by integrating Anchor IoUs and predicted IoUs, effectively reducing the misclassification of high-quality prediction samples as negative samples. Thus, it improves the detection accuracy of the model. Lastly, an asymmetric small-target detection head, FADH, is proposed to utilize depth-separable convolution to accomplish classification and regression tasks, enabling more precise capture of detailed information across scales and improving the detection of small-target defects. The experimental results show that FP-YOLOv8 achieves a mAP50 of 89.5% and an F1-score of 87% on the ends surface defects dataset, representing improvements of 3.3% and 6.0%, respectively, over the YOLOv8n algorithm, Meanwhile, it reduces model parameters and computational costs by 14.3% and 21.0%. Additionally, compared to the baseline model, the AP50 values for cracks, scratches, and flash defects rise by 5.5%, 5.6%, and 2.3%, respectively. These results validate the efficacy of FP-YOLOv8 in enhancing defect detection accuracy, reducing missed detection rates, and decreasing model parameter counts and computational demands, thus meeting the requirements of online defect detection for brake pipe ends surfaces. Full article
(This article belongs to the Section Fault Diagnosis & Sensors)
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<p>The structure of FP-YOLOv8.</p>
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<p>The structure of the Ghostblockv2.</p>
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<p>The principles of the cheap operations. Cheap operations use point convolution and depth convolution to obtain more feature maps with less computational cost.</p>
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<p>The principles of the DFC attention mechanism. The horizontal and vertical Fully Connected layers capture the long-range information along the two directions, respectively.</p>
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<p>Dynamic ATSS network architecture diagram. Dynamic ATSS uses the predicted boxes decoded from the regression branch. The predicted IoUs and anchor IoUs are calculated by comparing the predicted and anchor boxes with the GTs. The Combined IoUs (CIoUs) are obtained by summing the predicted and anchor IoUs. The combined mean and std are calculated similarly. The IoU threshold is the sum of the combined mean and std, and positive candidates are defined as samples with Combined IoUs greater than or equal to the threshold, restricted within the ground truth bounding boxes as final positive samples.</p>
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<p>The structure of the YOLOv8 detection head and FADH detection head.</p>
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<p>Brake pipes.</p>
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<p>Types of surface defects in brake pipe ends.</p>
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<p>Confusion matrix.</p>
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<p>Comparison of heatmaps for different algorithms across four types of defects.</p>
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<p>Score values of each model; (<b>a</b>) mAP50; (<b>b</b>) F1-score.</p>
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<p>Comparison of each parameter of each model.</p>
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<p>Illustration of six types of defects in the NEU-DET dataset.</p>
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<p>Experiments on sensitivity analysis of learning rate and batch size hyperparameters.</p>
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<p>In-line visual inspection device for brake pipe ends.</p>
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<p>Actual production environment application. (<b>a</b>) shows the light source and clamp in actual manufacturing, (<b>b</b>) shows the automotive brake pipe being transferred from the clamp to the vision inspection system for defect detection.</p>
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<p>Brake pipe ends measurement result display interface. The yellow circle represents the outer circle of the brake pipe end and the red circle represents the inner circle of the brake pipe end.</p>
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18 pages, 6538 KiB  
Article
Yeast Glucan Remodeling Protein Bgl2p: Amyloid Properties and the Mode of Attachment in Cell Wall
by Nikita A. Motorin, Gennady I. Makarov, Valentina V. Rekstina, Evgeniy G. Evtushenko, Fanis A. Sabirzyanov, Rustam H. Ziganshin, Alexey K. Shaytan and Tatyana S. Kalebina
Int. J. Mol. Sci. 2024, 25(24), 13703; https://doi.org/10.3390/ijms252413703 - 22 Dec 2024
Viewed by 482
Abstract
Bgl2p is a major, conservative, constitutive glucanosyltransglycosylase of the yeast cell wall (CW) with amyloid amino acid sequences, strongly non-covalently anchored in CW, but is able to leave it. In the environment, Bgl2p can form fibrils and/or participate in biofilm formation. Despite a [...] Read more.
Bgl2p is a major, conservative, constitutive glucanosyltransglycosylase of the yeast cell wall (CW) with amyloid amino acid sequences, strongly non-covalently anchored in CW, but is able to leave it. In the environment, Bgl2p can form fibrils and/or participate in biofilm formation. Despite a long study, the question of how Bgl2p is anchored in CW remains unclear. Earlier, it was demonstrated that Bgl2p lost the ability to attach in CW and to fibrillate after the deletion of nine amino acids in its C-terminal region (CTR). Here, we demonstrated that a Bgl2p anchoring is weakened by substitution Glu-233/Ala in the active center. Using AlphaFold and molecular modeling approach, we demonstrated the role of CTR on Bgl2p attachment and supposed the conformational possibilities determined by the presence or absence of an intramolecular disulfide bond, forming by Cys-310, leading to accessibility of amyloid sequence and β-turns localized in CTR of Bgl2p for protein interactions. We hypothesized the mode of Bgl2p attachment in CW. Using atomic force microscopy, we investigated fibrillar structures formed by peptide V187MANAFSYWQ196 and suggested that it can serve as a factor leading to the induction of amyloid formation during interaction of Bgl2p with other proteins and is of medical interest being located close to the surface of the molecule. Full article
(This article belongs to the Special Issue 25th Anniversary of IJMS: Advances in Biochemistry)
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<p>Potential energies of globules and entropies of its torsion angles for models of Bgl2p from <span class="html-italic">Saccharomyces cerevisiae</span> (red) and homologous glycosidases from the GH17 family (blue). Points show average values and error bars show root mean square deviations. Labels represent instruments applied to the generation of the Bgl2 model or PDB ID for structures of homologous glycosidases.</p>
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<p>The structure of Bgl2p and position of strong amyloidogenic sites F<sub>83</sub>TIFVGV<sub>89</sub> (Site I) are highlighted in coral, N<sub>190</sub>AFS<sub>193</sub> (Site II)—in purple and G<sub>268</sub>VNVIVFEA<sub>276</sub> (Site III)—in olive. Primary structure of Bgl2p with designations of the secondary structure elements (<b>A</b>): α-helices underlined as helices, β-strands underlined as arrows. Tertiary Bgl2p structure (<b>B</b>) and the part of a molecule with sites I, II and III (<b>C</b>). The black dashed lines show hydrogen bonds between amyloidogenic sites and the rest of the Bgl2p globule, shown by green tubes and ribbons. Oxygen, nitrogen and hydrogen atoms are shown as red, blue and grey sticks, correspondingly.</p>
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<p>Representative AFM images of V<sub>187</sub>MANAFSYWQ<sub>196</sub> peptide on Ultraflat polystyrene support. (<b>A</b>) Sample from the bulk liquid. (<b>B</b>,<b>C</b>) The sample was prepared by Langmuir–Schaefer and transferred from the liquid-air interface. Panel B illustrates the complete monolayer of short fibrils present on the liquid-air interface with rare fibrils on top (white). The inset contains 2× enlarged fragment of short fibrils monolayer for visual clarity. Panel C hows bundles of longer fibrils of various morphology on top of this monolayer. (<b>D</b>) The scheme of prepared samples revealed the localization of fibrils.</p>
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<p>Conformation of the C-terminal region of the Bgl2p structure model. The L<sub>308</sub>DCD<sub>311</sub> residues of the C-terminal region, forming unstable β-turn, are shown by a yellow tube. Phe-298 and Leu-304 residues, forming a stable β-bridge, are shown by violet rods, while Asp-302, Lys-305 and Tyr-306, forming stable β-turn, are shown by deepteal rods. The black dashed lines show hydrogen bonds. The laying of the rest of the globule is shown by green tubes and ribbons. Oxygen, nitrogen and hydrogen atoms are shown as red, blue and grey sticks, correspondingly.</p>
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<p>The impact of deletion of nine amino acid residues of Bgl2p from the C-terminus on the conformational stability of certain regions of the Bgl2p molecule. RMSF profiles in the C-terminal region along the sequence for Bgl2p and Bgl2pΔC<sub>305–313</sub> are shown with designations of the secondary structure elements: α-helices underlined as helices, β-strands underlined as arrows. Three curves for each system correspond to three independent calculations. The protein sites with mobility changes reproducibly are highlighted in color: region 192–211—orange, region 238–248—blue, region 255–260—purple, region 299–304—yellow.</p>
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<p>An illustration of the conformational mobility obtained during the MD calculations of (<b>A</b>) Bgl2p and (<b>B</b>) Bgl2pΔC<sub>305–313</sub>. The color scheme of the sites, the mobility of which changes with the deletion of the C-terminal region, corresponds to <a href="#ijms-25-13703-f005" class="html-fig">Figure 5</a>; the amino acid residues of the active center are marked in green (Glu-233—light green, Glu-124—dark green). An overlay of several frames from the MD trajectory is presented to illustrate conformational mobility/variability.</p>
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<p>The conformations of the loop forming by aa 238–248 affect the geometry of the Bgl2p catalytic gap. (<b>A</b>) Bgl2p structure. (<b>B</b>) Bgl2pΔC<sub>305–313</sub> structure. Loop 238–248 are depicted in cyan. Active site: Glu-233—light green, Glu-124—dark green. The dotted line indicates the catalytic gap. The red circle indicates the overlapping zone of the catalytic gap.</p>
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<p>Western blot stained with antibodies to Bgl2 of samples obtained from <span class="html-italic">Saccharomyces cerevisiae</span> cell walls of E233 control and E233A mutant strains, untreated (-) or pretreated (+) with 1% SDS, and then incubated with 0.1 M Tris. The remaining protein was extracted from CW into a Laemmli buffer with β-mercaptoethanol after Tris incubation (lanes 1). Proteins extracted in Tris (lanes 2). All extracts were equalized by the optical density of untreated CW.</p>
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<p>The conformational mobility of the C-terminus (marked in green) of Bgl2p structures, non-mutated (gray) and with C310A substitution (coral). RMSF profiles of three trajectories for both structures.</p>
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14 pages, 4492 KiB  
Article
Conjugated Human Serum Albumin/Gold-Silica Nanoparticles as Multifunctional Carrier of a Chemotherapeutic Drug
by Elena Morrone, Lucie Sancey, Fabien Dalonneau, Loredana Ricciardi and Massimo La Deda
Int. J. Mol. Sci. 2024, 25(24), 13701; https://doi.org/10.3390/ijms252413701 - 21 Dec 2024
Viewed by 720
Abstract
We report the design and development of a novel multifunctional nanostructure, RB-AuSiO2_HSA-DOX, where tri-modal cancer treatment strategies—photothermal therapy (PTT), photodynamic therapy (PDT), chemotherapy—luminescent properties and targeting are integrated into the same scaffold. It consists of a gold core with optical and [...] Read more.
We report the design and development of a novel multifunctional nanostructure, RB-AuSiO2_HSA-DOX, where tri-modal cancer treatment strategies—photothermal therapy (PTT), photodynamic therapy (PDT), chemotherapy—luminescent properties and targeting are integrated into the same scaffold. It consists of a gold core with optical and thermo-plasmonic properties and is covered by a silica shell entrapping a well-known photosensitizer and luminophore, Rose Bengal (RB). The nanoparticle surface was decorated with Human Serum Albumin (HSA) through a covalent conjugation to confer its targeting abilities and as a carrier of Doxorubicin (DOX), one of the most effective anticancer drugs in clinical chemotherapy. The obtained nanostructure was fully characterized through transmission electron microscopy (TEM), dynamic light scattering (DLS) and UV-visible spectroscopy, with a homogeneous and spherical shape, an average diameter of about 60 nm and negative ζ-potential value Singlet oxygen generation and photothermal properties were explored under green light irradiation. The interaction between DOX-HSA anchored on the nanoplatform was investigated by fluorescence spectroscopy and compared to that of DOX-HSA, pointing out different accessibility of the drug molecules to the HSA binding sites, whether the protein is free or bound to the nanoparticle surface. To the best of our knowledge, there are no studies comparing a drug–HSA interaction with that of the same protein anchored to nanoparticles. Furthermore, the uptake of RB-AuSiO2_HSA-DOX into MDA-MB-231 mammary cells was assessed by confocal imaging, highlighting—at early time of incubation and as demonstrated by the increased DOX luminescence displayed within cells—a better internalization of the carried anticancer drug compared to the free one, making the obtained nanostructure a suitable and promising platform for an anticancer multimodal approach. Full article
(This article belongs to the Special Issue External Stimuli-Responsive Nanomaterials for Diagnosis and Treatment)
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<p>(<b>a</b>) Schematic illustration of the implemented nanoplatform (RB-AuSiO<sub>2</sub>_HSA-DOX) with a representative example of DOX/HSA interaction and (<b>b</b>) light-induced processes: (I) photothermal effects due to irradiation at the plasmon resonance wavelength of the gold core; (II) Rose Bengal molecules activation resulting in the generation of singlet oxygen and other reactive oxygen species; (III) chemotherapy agent release. (<b>c</b>) Outline of the therapeutic approaches, working mechanisms and related biological effects addressed with the nanoplatform.</p>
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<p>(<b>a</b>) Representative TEM image of RB-AuSiO<sub>2</sub>_HSA, scale bar = 20 nm. (<b>b</b>) The hydrodynamic diameter of RB-AuSiO<sub>2</sub>_COOH versus RB-AuSiO<sub>2</sub>_HSA. (<b>c</b>) Extinction spectrum of RB-AuSiO<sub>2</sub>_HSA in water. The inset displays the extinction spectra of AuSiO<sub>2</sub>_HSA versus RB-AuSiO<sub>2</sub>_HSA in the range 400–800 nm. (<b>d</b>) Emission spectrum of RB-AuSiO<sub>2</sub>_HSA in water upon excitation at 295 nm. (<b>e</b>) The emission spectrum of RB-AuSiO<sub>2</sub>_HSA in water upon excitation at 520 nm. (<b>f</b>) Time-resolved fluorescence decay of RB versus RB-AuSiO<sub>2</sub>_HSA in water upon excitation at 485 nm.</p>
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<p>(<b>a</b>) Plotting of ABDA absorption at different irradiation times (0–18 min) in water (control) and in the presence of RB, AuSiO<sub>2</sub>_HSA and RB-AuSiO<sub>2</sub>_HSA. (<b>b</b>) Infrared thermal images of (<b>left</b>) water (control) and (<b>right</b>) RB-AuSiO<sub>2</sub>_HSA nanoparticles dispersed in water (light-exposure 520 nm, 90 min).</p>
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<p>(<b>a</b>) Fluorescence emission spectra of HSA (10 μM) in the presence of increasing concentrations of DOX (a–e). (<b>b</b>) Stern-Volmer plot for the interaction of DOX with HSA. The molar concentration of DOX in the samples a–e was 0, 5, 10, 15 and 20 μM; λ<sub>ex</sub> = 295 nm. (<b>c</b>) Fluorescence emission spectra of RB-AuSiO<sub>2</sub>_HSA nanoparticles (1.5 μM) in the presence of increasing concentrations of DOX (f–l). (<b>d</b>) Stern-Volmer plot for the interaction of DOX with HSA-coated nanoparticles. The molar concentration of DOX in the samples f–l was 0, 1.5, 3, 4.5 and 6 μM; λ<sub>ex</sub> = 295 nm.</p>
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<p>Representative confocal microscopy imaging of MDA-MB-231 cells in the presence of RB-AuSiO<sub>2</sub>_HSA-DOX and DOX (red signal). Nucleus were stained with Hoechst (blue signal). Scale bar: 10 µm.</p>
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17 pages, 6416 KiB  
Article
Comparative Study of Transverse Shear Characteristics of Shear-Yielding Bolts and Traditional Bolts Based on Numerical Simulations and Direct Shear Tests
by Jianqiang Xu, Xiaohua Yang, Xueming Jia, Haoyu Zhang and Tiangong Zhang
Buildings 2024, 14(12), 4066; https://doi.org/10.3390/buildings14124066 - 21 Dec 2024
Viewed by 588
Abstract
The shear-yielding bolt is a new type of anchoring structure, and its working mechanism in layered rocks is not yet well understood. To investigate its transverse shear characteristics, this paper takes the shear-yielding bolt as the research subject and uses different anchoring states [...] Read more.
The shear-yielding bolt is a new type of anchoring structure, and its working mechanism in layered rocks is not yet well understood. To investigate its transverse shear characteristics, this paper takes the shear-yielding bolt as the research subject and uses different anchoring states of bolts as variables. A comparative study of shear-yielding bolts and traditional bolts is conducted using the Abaqus numerical simulation software and large-scale direct shear tests. The results show that (1) low-modulus material allows a slight displacement between the structural surface layers, which exerts the friction strength between rock mass layers and avoids stress concentration on the bolt. The shear-yielding bolts reach their peak shear stress in the case of greater displacement, averagely increased by 40% compared to traditional anchor bolts. (2) An increase in the moisture content has less influence on the shear-yielding bolt owing to the material properties. When the moisture content of the structural surface rises from 12% to 20%, for cases where the shear-yielding bolts are used, the peak shear stress decreases by 0.12 kPa, which only accounts for 12% of the original strength. (3) There is an optimum thickness of the low-modulus material in the shear-yielding bolt, considering its effect of releasing shear and the bonding effect between it and the bolt. According to the test results and numerical analysis, the optimum thickness is 15 mm. The results of this research provide a reference and basis for future study and engineering applications of shear-yielding bolts. Full article
(This article belongs to the Special Issue Foundation Treatment and Building Structural Performance Enhancement)
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<p>Schematic presentation of the structure of a traditional bolt.</p>
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<p>Schematic presentation of the structure of a shear-yielding bolt.</p>
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<p>Schematic presentation of experimental specimen.</p>
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<p>The large-scale direct shear test instrument.</p>
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<p>Illustration of experimental procedure: (<b>a</b>) specimen assembly; (<b>b</b>) preparation of structural surface material; (<b>c</b>) insertion of low-modulus material; and (<b>d</b>) completion of test assembly.</p>
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<p>Calculation model and meshing in the simulation: (<b>a</b>) calculation model and (<b>b</b>) meshing.</p>
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<p>Shear force–displacement curves for normal pressures when moisture content is 16% and normal stress is (<b>a</b>) 0.25 MPa, (<b>b</b>) 0.5 MPa, (<b>c</b>) 0.75 MPa, and (<b>d</b>) 1 MPa.</p>
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<p>Shear force–displacement curves for shear-yielding bolt anchoring under different moisture contents and low-modulus material thickness conditions. (<b>a</b>) No anchoring; (<b>b</b>) shear-yielding bolt anchoring; and (<b>c</b>) shear-yielding bolt anchoring with different low-modulus material thicknesses.</p>
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<p>Shear stress distribution of the joint (no anchoring case, normal stress of 0.5 MPa, moisture content of 20%).</p>
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<p>Stress and plastic deformation distribution of the joint (traditional bolt anchoring, normal stress of 0.5 MPa, moisture content of 16%).</p>
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<p>Stress and plastic deformation distribution of the joint (shear-yielding bolt, normal stress of 0.5 MPa, moisture content of 16%).</p>
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<p>Stress and plastic deformation distribution of the joint (shear-yielding bolt, normal stress of 0.5 MPa, moisture content of 16%).</p>
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22 pages, 12852 KiB  
Article
DFT Study of the Stability and Electronic Properties of Ni-Doped Defected (6,0) and (8,0) Single-Walled Carbon Nanotubes
by Valeria Orazi, Rubén Eduardo Ambrusi, Alejandro Morelli, Alfredo Juan and Jorge Mario Marchetti
Materials 2024, 17(24), 6236; https://doi.org/10.3390/ma17246236 - 20 Dec 2024
Viewed by 412
Abstract
The interaction of Ni with (6,0) and (8,0) zigzag carbon nanotube exterior surfaces containing two vacancies was studied using density functional theory (DFT). A two-vacancy defect was analysed in order to anchor Ni, and the pristine nanotube was also considered as a reference [...] Read more.
The interaction of Ni with (6,0) and (8,0) zigzag carbon nanotube exterior surfaces containing two vacancies was studied using density functional theory (DFT). A two-vacancy defect was analysed in order to anchor Ni, and the pristine nanotube was also considered as a reference for each chirality. The adsorbed Ni stability and the nanotube’s geometry and electronic structure were analysed before and after the adsorption. We compared calculations performed using a general gradient functional with those conducted using two semi-classical dispersion methods to assess the van der Waals forces (PBE-D2 and PBE-D3). In addition, the inclusion of the Hubbard parameter for the correction of Ni d electron self-interaction energy was included, and we evaluated energy and electronic structure changes through atomic-level calculations. Adsorption energy, the density of states, and the charge distribution were obtained to establish the Ni binding on the defective nanotube’s dominating mechanisms. The effect of curvature and applied functional influence was also considered. Furthermore, a bonding analysis was performed to complement our comprehension of the interaction between Ni and the nanotube surfaces. The electronic results show that Ni-doped two-vacancy (6,0) and (8,0) carbon nanotubes can be applied for the development of low-resistance contact materials and spintronic devices, respectively. Full article
(This article belongs to the Section Materials Simulation and Design)
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<p>This Figure presents front, lateral, and top views of the optimised structures for a Ni atom adsorbed on (<b>a</b>) pristine (6,0) SWCNT, (<b>b</b>) di-vacancy (6,0) SWCNT, (<b>c</b>) pristine (8,0) SWCNT, and (<b>d</b>) di-vacancy (8,0) SWCNT. The optimisation was performed with PBE-D2 functional.</p>
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<p>DOS of the pristine (6,0) SWCNT, calculated with (<b>a</b>) the PBE-D2 functional and (<b>b</b>) the PBE-D3 functional; and the (6,0) SWCNT with a di-vacancy defect, calculated with (<b>c</b>) the PBE-D2 functional and (<b>d</b>) the PBE-D3 functional.</p>
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<p>DOS of the pristine SWCNT (8,0), calculated with (<b>a</b>) the PBE-D2 functional and (<b>b</b>) the PBE-D3 functional; and the SWCNT (8,0) with a di-vacancy defect, calculated with: (<b>c</b>) the PBE-D2 functional and (<b>d</b>) the PBE-D3 functional.</p>
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<p>The total DOS of the most stable geometry of a Ni atom adsorbed on a pristine (6,0) SWCNT is illustrated in grey, the PDOS onto the C atoms in brown, and the PDOS onto the Ni atom in blue, calculated with (<b>a</b>) the PBE-D2 functional, (<b>b</b>) the PBE-D3 functional, (<b>c</b>) the PBE + U-D2 functional, and (<b>d</b>) the PBE + U-D3 functional.</p>
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<p>Total DOS of the most stable geometry of a Ni atom adsorbed on a pristine (8,0) SWCNT is illustrated in grey, the PDOS onto the C atoms in brown, and the PDOS onto the Ni atom in blue, calculated with (<b>a</b>) the PBE-D2 functional, (<b>b</b>) the PBE-D3 functional, (<b>c</b>) the PBE + U-D2 functional, and (<b>d</b>) the PBE + U-D3 functional.</p>
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<p>The total DOS of a Ni atom adsorbed on a (6,0) SWCNT with a di-vacancy is illustrated in grey, the PDOS onto the C atoms in brown, the PDOS onto the Ni atom in blue, and the DOS of the isolated Ni atom in light-blue dashed lines, calculated with (<b>a</b>) the PBE-D2 functional, (<b>b</b>) the PBE-D3 functional, (<b>c</b>) the PBE + U-D2 functional, and (<b>d</b>) the PBE + U-D3 functional.</p>
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<p>Total DOS of a Ni atom adsorbed on an (8,0) SWCNT with a di-vacancy is illustrated in grey, the PDOS onto the C atoms in brown, the PDOS onto the Ni atom in blue, and the DOS of the isolated Ni atom in light-blue dashed lines, calculated with (<b>a</b>) the PBE-D2 functional, (<b>b</b>) the PBE-D3 functional, (<b>c</b>) the PBE + U-D2 functional, and (<b>d</b>) the PBE + U-D3 functional.</p>
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<p>The PDOS for the orbitals of the system with a Ni atom adsorbed on a SWCNT with a di-vacancy. (6,0) SWCNT system, calculated with (<b>a</b>) the PBE-D2 functional and (<b>c</b>) the PBE + U-D2 functional. (8,0) SWCNT system, calculated with (<b>b</b>) the PBE-D2 functional and (<b>d</b>) the PBE + U-D2 functional. The colours used in the graphs represent the following orbitals: the s-orbital of Ni (black), p-orbital of Ni (green), d-orbital of Ni (blue), s-orbital of C (brown), and p-orbital of C (red). The inset at the top left of each sub-figure provides a zoomed view of the graphs for the energy region between 0 and −3 eV.</p>
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<p>Selected atoms for bond analysis based on BO and OP values for the four systems: (<b>a</b>) Ni adsorbed on pristine (6,0) SWCNT, (<b>b</b>) Ni adsorbed on (6,0) SWCNT with a di-vacancy, (<b>c</b>) Ni adsorbed on pristine (8,0) SWCNT, and (<b>d</b>) Ni adsorbed on (8,0) SWCNT with a di-vacancy.</p>
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<p>BO for selected C-C and Ni-C bonds (see <a href="#materials-17-06236-f009" class="html-fig">Figure 9</a>), calculated before and after Ni adsorption for the optimised systems using PBE-D2 and PBE + U-D2 functionals, for the systems: (<b>a</b>) Ni-(6,0) SWCNT, (<b>b</b>) Ni-2vac-(6,0) SWCNT, (<b>c</b>) Ni-(8,0) SWCNT, and (<b>d</b>) Ni-2vac-(8,0) SWCNT.</p>
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<p>Variation in Bader charges for optimised systems on selected atoms (see <a href="#materials-17-06236-f009" class="html-fig">Figure 9</a>) before and after Ni adsorption using PBE-D2 and PBE + U-D2 functionals, for the systems: (<b>a</b>) Ni-(6,0) SWCNT, (<b>b</b>) Ni-2vac-(6,0) SWCNT, (<b>c</b>) Ni-(8,0) SWCNT, and (<b>d</b>) Ni-2vac-(8,0) SWCNT.</p>
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<p>Isosurfaces of the charge density differences. Isosurface value = 0.05 e/Å<sup>3</sup> (<b>a</b>,<b>b</b>) and 0.08 e/Å<sup>3</sup> (<b>c</b>,<b>d</b>). Electron accumulation (positive) and depletion (negative) regions are indicated in yellow and green, respectively.</p>
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