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13 pages, 9328 KiB  
Article
Light-Controlled Interconvertible Self-Assembly of Non-Photoresponsive Suprastructures
by Wentao Yu, Sudarshana Santhosh Kumar Kothapalli, Zhiyao Yang, Xuwen Guo, Xiaowei Li, Yimin Cai, Wen Feng and Lihua Yuan
Molecules 2024, 29(20), 4842; https://doi.org/10.3390/molecules29204842 - 12 Oct 2024
Viewed by 490
Abstract
Achieving light-induced manipulation of controlled self-assembly in nanosized structures is essential for developing artificially dynamic smart materials. Herein, we demonstrate an approach using a non-photoresponsive hydrogen-bonded (H-bonded) macrocycle to control the self-assembly and disassembly of nanostructures in response to light. The present system [...] Read more.
Achieving light-induced manipulation of controlled self-assembly in nanosized structures is essential for developing artificially dynamic smart materials. Herein, we demonstrate an approach using a non-photoresponsive hydrogen-bonded (H-bonded) macrocycle to control the self-assembly and disassembly of nanostructures in response to light. The present system comprises a photoacid (merocyanine, 1-MEH), a pseudorotaxane formed by two H-bonded macrocycles, dipyridinyl acetylene, and zinc ions. The operation of such a system is examined according to the alternation of self-assembly through proton transfer, which is mediated by the photoacid upon exposure to visible light. The host–guest complexation between the macrocycle and bipyridium guests was investigated by NMR spectroscopy, and one of the guests with the highest affinity for the ring was selected for use as one of the components of the system, which forms the host–guest complex with the ring in a 2:1 stoichiometry. In solution, a dipyridine and the ring, having no interaction with each other, rapidly form a complex in the presence of 1-MEH when exposed to light and thermally relax back to the free ring without entrapped guests after 4 h. Furthermore, the addition of zinc ions to the solution above leads to the formation of a polypseudorotaxane with its morphology responsive to photoirradiation. This work exemplifies the light-controlled alteration of self-assembly in non-photoresponsive systems based on interactions between the guest and the H-bonded macrocycle in the presence of a photoacid. Full article
(This article belongs to the Section Organic Chemistry)
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Figure 1

Figure 1
<p>Partial <sup>1</sup>H NMR spectra (400 MHz, CDCl<sub>3</sub>/CD<sub>3</sub>CN, 1:1, <span class="html-italic">v</span>/<span class="html-italic">v</span>, 298K) of (<b>a</b>) 1.0 mM <b>G2·2H</b>; (<b>b</b>) 1.0 mM <b>1a</b> and 1.0 mM <b>G2·2H</b>; (<b>c</b>) 2.0 mM <b>1a</b> and 1.0 mM <b>G2·2H</b>; (<b>d</b>) 1.0 mM <b>1a</b>.</p>
Full article ">Figure 2
<p>Photoisomerization and thermal relaxation of 1-MEH in a mixed solvent of CHCl<sub>3</sub> and CH<sub>3</sub>CN (1:1, <span class="html-italic">v</span>/<span class="html-italic">v</span>). (<b>A</b>) UV–vis absorption spectra of 1-MEH (50 µM), ∼10 min after irradiation with 450 nm light (transformation into 1-SP), and after keeping the solution in the dark for 2 h after irradiation (reversion to 1-MEH); inset: photos of solutions of 1-MEH and 1-SP. (<b>B</b>) Stacked UV–vis absorption spectra of 1-MEH (50 µM), ∼10 min after irradiation with 450 nm light (transformation into <b>1-SP</b>); (<b>C</b>) Absorption at 435 nm upon irradiation/darkness cycling for 2 h in solution; (<b>D</b>) (<b>a</b>) <sup>1</sup>H NMR (CDCl<sub>3</sub>/CD<sub>3</sub>CN, 1:1, <span class="html-italic">v</span>/<span class="html-italic">v</span>, 298 K, 400 MHz) spectrum of 1-MEH; (<b>b</b>) <sup>1</sup>H NMR (CDCl<sub>3</sub>/CD<sub>3</sub>CN, 1:1, <span class="html-italic">v</span>/<span class="html-italic">v</span>, 298 K, 400 MHz) spectrum of 1-SP.</p>
Full article ">Figure 3
<p>Stacked <sup>1</sup>H NMR spectra (CDCl<sub>3</sub>/CD<sub>3</sub>CN, 1:1, <span class="html-italic">v</span>/<span class="html-italic">v</span>, 298 K, 400 MHz) of (<b>a</b>) 1,2-di(pyridin-4-yl) acetylene; (<b>G2</b>) (<b>b</b>) 1-MEH. (<b>c</b>) <b>G2</b> + 1-MEH (2.4 eq.) before irradiation; (<b>d</b>) solution from (<b>c</b>) irradiated for 10 min with 450 nm light; (<b>e</b>) <b>G2</b> + 1-MEH (2.4 eq.) + <b>1a</b> (2.0 eq.) irradiated for 10 min with 450 nm light; (<b>f</b>) solution from (<b>e</b>) kept under dark for 240 min; (<b>g</b>) <b>G2</b> + 1-MEH (2.4 eq.) + <b>1a</b> before irradiation; (<b>h</b>) H-bonded macrocycle <b>1a</b>. [<b>1a</b>]<sub>0</sub> = [<b>G2</b>]<sub>0</sub> = [1-MEH]<sub>0</sub> = 1.0 mM.</p>
Full article ">Figure 4
<p>Stacked <sup>1</sup>H NMR spectra (400 MHz, CDCl<sub>3</sub>/CD<sub>3</sub>CN, 1:1, <span class="html-italic">v</span>/<span class="html-italic">v</span>, 298 K) of (<b>a</b>) <b>G2</b> (1.0 mM); (<b>b</b>) <b>G2</b> (1.0 mM) and Zn(CH<sub>3</sub>COO)<sub>2</sub> (2.0 mM); (<b>c</b>) <b>1a</b> (2.0 mM) and <b>G2</b> (1.0 mM) and Zn(CH<sub>3</sub>COO)<sub>2</sub> (2.0 mM); (<b>d</b>) <b>1a</b> (1.0 mM).</p>
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<p>Optimized structure at the DFT/B3LYP (PCM, chloroform)/6-31G (d, p) level of complex <b>1a</b> ⊃ <b>G2</b> + Zn<sup>2+</sup>. (H—white, O—red, N—navy blue, C—blue and green, Zn—yellow). (<b>a</b>) Side view of the computational structure; (<b>b</b>) Top view of the computational structure; The dashed purple lines indicate C-H···O hydrogen bonds <b>1</b>–<b>3</b>, where <b>1</b> = 2.15 Å (133.7°), <b>2</b> = 1.96 Å (145.4°), and <b>3</b> = 1.90 Å (140.5°). All peripheral R groups are replaced by CH<sub>3</sub> for simplicity.</p>
Full article ">Figure 6
<p>DLS of <b>1a</b> + <b>G2</b> + Zn<sup>2+</sup> + 1-MEH: (<b>A</b>) Before irradiation; irradiate 10 min; and kept in the dark for 240 min after being irradiated; (<b>B</b>) number of cycles of DLS: alternate operation of exposing to irradiation and being in the dark for 240 min. [<b>G2</b>] = 25 µM. Solvent: CHCl<sub>3</sub>/CH<sub>3</sub>CN = 1:1 (<span class="html-italic">v</span>/<span class="html-italic">v</span>, 298 K).</p>
Full article ">Figure 7
<p>TEM of <b>1a</b> (2.0 eq.) + <b>G2</b> + Zn<sup>2+</sup>(2.0 eq.) + 1-MEH (2.4 eq.): (<b>A</b>) <b>1a</b> (2.0 eq.) + <b>G2</b> + Zn<sup>2+</sup> (2.0 eq.) + 1-MEH (2.4 eq.) before 450 nm irradiation; (<b>B</b>) <b>1a</b> (2.0 eq.) + <b>G2</b> + Zn<sup>2+</sup> (2.0 eq.) + 1-MEH (2.4 eq.) with 450 nm irradiate 10 min; (<b>C</b>) <b>1a</b> (2.0 eq.) + <b>G2</b> + Zn<sup>2+</sup> (2.0 eq.) + 1-MEH (2.4 eq.) kept in the dark for 240 min after being irradiated at 450 nm for 10 min. [<b>G2</b>] = 25 µM. (CHCl<sub>3</sub>/CH<sub>3</sub>CN = 1:1, <span class="html-italic">v</span>/<span class="html-italic">v</span>, 298K).</p>
Full article ">Scheme 1
<p>(<b>A</b>) Chemical structures of H-bonded macrocycle <b>1a</b> and guest molecules <b>G1·2H-G4·2H</b>. (<b>B</b>) Cartoon illustration of the photoacid 1-MEH controlled interconversion of self-assemblies based on polypseudorotaxane <b>2</b>. H-bonded macrocycle <b>1b</b> is used for DFT calculations due to structural simplicity.</p>
Full article ">
16 pages, 5222 KiB  
Review
Application and Challenge of Metalloporphyrin Sensitizers in Noninvasive Dynamic Tumor Therapy
by Jiacheng Ouyang, Dan Li, Lizhen Zhu, Xiaoyuan Cai, Lanlan Liu, Hong Pan and Aiqing Ma
Molecules 2024, 29(20), 4828; https://doi.org/10.3390/molecules29204828 - 11 Oct 2024
Viewed by 404
Abstract
Dynamic tumor therapies (mainly including photodynamic therapy (PDT) and sonodynamic therapy (SDT)) offer new approaches to cancer treatment. They are often characterized by their noninvasive nature, high selectivity, and low toxicity. Sensitizers are crucial for dynamic therapy. Developing efficient sensitizers with good biocompatibility [...] Read more.
Dynamic tumor therapies (mainly including photodynamic therapy (PDT) and sonodynamic therapy (SDT)) offer new approaches to cancer treatment. They are often characterized by their noninvasive nature, high selectivity, and low toxicity. Sensitizers are crucial for dynamic therapy. Developing efficient sensitizers with good biocompatibility and controllability is an important aim in dynamic therapy. Porphyrins and metalloporphyrins attract great attention due to their excellent photophysical properties and low cytotoxicity under non-light. Compared to porphyrins, metalloporphyrins show greater potential for dynamic therapy due to their enhanced photochemical and photophysical properties after metal ions coordinate with porphyrin rings. This paper reviews some metalloporphyrin-based sensitizers used in photo/sonodynamic therapy and combined therapy. In addition, the probable challenges and bottlenecks in clinical translation are also discussed. Full article
(This article belongs to the Special Issue Study on Synthesis and Photochemistry of Dyes)
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Figure 1

Figure 1
<p>Typical structures, i.e., (<b>A</b>) pyrrole, (<b>B</b>) porphyrin, consisting of four pyrrole rings joined by methane bridges, and (<b>C</b>) metalloporphyrin (M = Mn, Fe, Cu, Zn, and so on).</p>
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<p>The possible mechanisms of PDT (<b>A</b>) and SDT (<b>B</b>).</p>
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<p>The photophysical properties and effect of different metal chelation on PoP<sup>41</sup> and Por<sup>42</sup> ligands. (<b>A</b>) Chemical structure of the HPPH lipids (PoP) examined. (<b>B</b>) Fluorescence emission spectra of an equal concentration of indicated PoP liposomes in phosphate-buffered saline. (<b>C</b>) Singlet oxygen generation was assessed indirectly by examining the increase in green fluorescence of a singlet oxygen sensor before and after laser irradiation. (<b>D</b>) Chemical structure of ZnPor, PdPor, and PtPor. (<b>E</b>) The fluorescence intensity detection at the characteristic peak of DCFH (525 nm) irradiated by different complexes as a function of irradiation time.</p>
Full article ">Figure 4
<p>Different metalloporphyrins for enhanced antitumor PDT through assistant reaction and function. (<b>A</b>) TiOP-loaded liposome nanosystem (FA−TiOPs) to photocatalyze H<sub>2</sub>O and H<sub>2</sub>O<sub>2</sub> for antitumor PDT (a) Preparation of FA–TiOPs. (b) Mechanism of in situ supplying ROS under FA–TiOPs photocatalysis [<a href="#B48-molecules-29-04828" class="html-bibr">48</a>]. (<b>B</b>) The enhanced ROS generation evaluation induced by FA-TiOPs under light irradiation. (<b>C</b>) The structure of ZnP1 and ZnP2 [<a href="#B49-molecules-29-04828" class="html-bibr">49</a>]. (<b>D</b>) Scheme of photothermal-assistant PDT-based ZnP2. (<b>E</b>) Scheme of self-supply CuS and (Cu)HMME for photothermal-assistant PDT. I: GSH triggered H<sub>2</sub>S generation; II: The H<sub>2</sub>S triggered CuS production and the resealse of metalloporphyrin ((Cu)HMMe) [<a href="#B50-molecules-29-04828" class="html-bibr">50</a>].</p>
Full article ">Figure 5
<p>Imaging-guided precise tumor treatment with metalloporphyrin-based PDT. (<b>A</b>) The structure of <sup>68</sup>Ga–porphyrin complex [<a href="#B53-molecules-29-04828" class="html-bibr">53</a>]. (<b>B</b>) MR imaging of <sup>68</sup>Ga–porphyrin in tumor site. (<b>C</b>) Schematic illustration of the preparation of Gd–PNPs and their application in FL/MR imaging-guided PDT [<a href="#B55-molecules-29-04828" class="html-bibr">55</a>]. (<b>D</b>) Schematic illustrating the co-assembly of the nanocomposites by ZnTPP and GdTPP for MR/FL bimodal imaging-guided PDT [<a href="#B56-molecules-29-04828" class="html-bibr">56</a>].</p>
Full article ">Figure 5 Cont.
<p>Imaging-guided precise tumor treatment with metalloporphyrin-based PDT. (<b>A</b>) The structure of <sup>68</sup>Ga–porphyrin complex [<a href="#B53-molecules-29-04828" class="html-bibr">53</a>]. (<b>B</b>) MR imaging of <sup>68</sup>Ga–porphyrin in tumor site. (<b>C</b>) Schematic illustration of the preparation of Gd–PNPs and their application in FL/MR imaging-guided PDT [<a href="#B55-molecules-29-04828" class="html-bibr">55</a>]. (<b>D</b>) Schematic illustrating the co-assembly of the nanocomposites by ZnTPP and GdTPP for MR/FL bimodal imaging-guided PDT [<a href="#B56-molecules-29-04828" class="html-bibr">56</a>].</p>
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<p>The SDT effects of some metalloporphyrins with different metal centers and porphyrin ligands. (<b>A</b>) Scheme illustrating the synthesis of MTTP complexes with different metal centers and the corresponding nanocomplexes of HSA for antitumor SDT [<a href="#B73-molecules-29-04828" class="html-bibr">73</a>]. (<b>B</b>) Structural illustration of Mn-PpIX-based sonosensitizer for antitumor SDT [<a href="#B74-molecules-29-04828" class="html-bibr">74</a>]. (<b>C</b>) Schematic illustration of the synthesis of FA–L–CuPP [<a href="#B75-molecules-29-04828" class="html-bibr">75</a>]. (<b>D</b>) The mechanism of Cu(II)NS and Cu(I)NS for SDT [<a href="#B76-molecules-29-04828" class="html-bibr">76</a>].</p>
Full article ">Figure 7
<p>Tumor microenvironment adjustment relevant to SDT effect. (<b>A</b>) MnP-mediated SDT-ICD antitumor [<a href="#B78-molecules-29-04828" class="html-bibr">78</a>]. (<b>B</b>) Schematic of preparation and oxygen-enhanced SDT based on DOX/Mn-TPPS@RBCs [<a href="#B79-molecules-29-04828" class="html-bibr">79</a>]. (<b>C</b>) Oxygen-enhanced SDT based on Fe–porphyrin [<a href="#B80-molecules-29-04828" class="html-bibr">80</a>]. (<b>D</b>) Intracellular NADH oxidization for enhanced SDT effect [<a href="#B81-molecules-29-04828" class="html-bibr">81</a>].</p>
Full article ">
13 pages, 6084 KiB  
Article
Fractional Talbot Lithography for Predesigned Large-Area Liquid-Crystal Alignment
by Zhichao Ji, Zenghua Gan, Yu Wang, Zhijian Liu, Donghao Yang, Yujie Fan, Wenhua Li, Irena Drevensek-Olenik, Yigang Li and Xinzheng Zhang
Materials 2024, 17(19), 4810; https://doi.org/10.3390/ma17194810 - 30 Sep 2024
Viewed by 464
Abstract
To address the increasing demands for cost-effective, large-area, and precisely patterned alignment of liquid crystals, a fractional Talbot lithography alignment technique was proposed. A light intensity distribution with a double spatial frequency of a photomask could be achieved based on the fractional Talbot [...] Read more.
To address the increasing demands for cost-effective, large-area, and precisely patterned alignment of liquid crystals, a fractional Talbot lithography alignment technique was proposed. A light intensity distribution with a double spatial frequency of a photomask could be achieved based on the fractional Talbot effect, which not only enhanced the resolution of lithography but also slashed system costs with remarkable efficiency. To verify the feasibility of the alignment method, we prepared a one-dimensional polymer grating as an alignment layer. A uniform alignment over a large area was achieved thanks to the perfect periodicity and groove depth of several hundred nanometers. The anchoring energy of the alignment layer was 1.82 × 10−4 J/m2, measured using the twist balance method, which surpassed that of conventional rubbing alignment. Furthermore, to demonstrate its ability for non-uniform alignment, we prepared polymer concentric rings as an alignment layer, resulting in a liquid-crystal q-plate with q = 1 and α0 = π/2. This device, with a wide tuning range (phase retardation of ~6π @ 633 nm for 0 to 5 V), was used to generate special optical fields. The results demonstrate that this approach allows for the uniform large-area orientation of liquid-crystal molecules with superior anchoring energy and customizable patterned alignment, which has extensive application value in liquid-crystal displays, generating special optical fields and intricate liquid-crystal topological defects over a large area. Full article
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Figure 1

Figure 1
<p>(<b>a</b>) Calculated intensity distribution behind a 1D grating photomask; three self-images are marked with blue dashed lines at distances of 0, 12.3 μm, and 49.3 μm from the photomask. The spatial intensity profiles at (<b>b</b>) <span class="html-italic">z</span> = 0; (<b>c</b>) <span class="html-italic">z</span> = 12.3 μm = 0.5 <span class="html-italic">Z</span><sub>T</sub>; and (<b>d</b>) <span class="html-italic">z</span> = 49.3 μm = 2 <span class="html-italic">Z</span><sub>T</sub>, the two red dashed lines indicated the periodic change of the optical field.</p>
Full article ">Figure 2
<p>(<b>a</b>) Schematic diagram of the lithography setup; the red box is an enlarged view of the sample. (<b>b</b>) Photograph of the polymer grating; the colorful region shows the wonderful diffraction by the 1D polymer grating.</p>
Full article ">Figure 3
<p>(<b>a</b>) AFM morphology of the polymer grating with 1.5 μm periodicity; (<b>b</b>) contour of the cross-section along the direction of the grating vector; (<b>c</b>) simulated light intensity distribution at a deviation of 0.5 μm from the half Talbot distance.</p>
Full article ">Figure 4
<p>(<b>a</b>) Schematic illustration of the TN cells; TN90-1.5 cell: transmission POM images (<b>b</b>) under crossed configuration and (<b>c</b>) under parallel configuration; TN90-3.0 cell: transmission POM images (<b>d</b>) under crossed configuration and (<b>e</b>) under parallel configuration, the red boxes indicate the areas chose to calculate the relative intensity.</p>
Full article ">Figure 5
<p>(<b>a</b>) Diagram of the groove directions and twisting angles on the inner surfaces of the upper and lower substrates of a 90° twisted liquid-crystal cell; (<b>b</b>) anchoring energies of different orientation techniques.</p>
Full article ">Figure 6
<p>(<b>a</b>) Diagram of liquid-crystal cell and liquid-crystal molecule arrangement; (<b>b</b>) photo of the <span class="html-italic">q</span>-plate, with the white dashed box indicating the structural area; POM images under crossed polarizers with the polarization direction of (<b>c</b>) 0° and (<b>d</b>) 45°, respectively; (<b>e</b>) polarized light images after inserting a quarter-wave plate between the sample and the analyzer.</p>
Full article ">Figure 7
<p>(<b>a</b>) The setup for generating and analyzing special optical fields; the components within the dashed boxes can be changed to realize different functions; (<b>b</b>) normalized transmitted light intensity through a <span class="html-italic">q</span>-plate measured at different voltages; (<b>c</b>) POM images under different voltages: 0 V, 0.5 V, 1.0 V, 2.0 V, and 10 V.</p>
Full article ">Figure 8
<p>Generated beam profiles detected with/without analyzer for different optical retardations and incident light: (<b>a</b>) <span class="html-italic">δ</span> = 3π/2, LCP; (<b>b</b>) <span class="html-italic">δ</span> = π, LCP; (<b>c</b>) <span class="html-italic">δ</span> = π, LP along <span class="html-italic">x</span>-axis; and (<b>d</b>) <span class="html-italic">δ</span> = π, LP with −45°.</p>
Full article ">
20 pages, 9809 KiB  
Article
Small-Size Eight-Element MIMO Metamaterial Antenna with High Isolation Using Modal Significance Method
by Tirado-Mendez Jose Alfredo, Jardon-Aguilar Hildeberto, Flores-Leal Ruben, Rangel-Merino Arturo, Perez-Miguel Angel and Gomez-Villanueva Ricardo
Sensors 2024, 24(19), 6266; https://doi.org/10.3390/s24196266 - 27 Sep 2024
Viewed by 323
Abstract
This article presents a symmetrical reduced-size eight-element MIMO antenna array with high electromagnetic isolation among radiators. The array utilizes easy-to-build techniques to cover the n77 and n78 new radio (NR) bands. It is based on an octagonal double-negative metamaterial split-ring resonator (SRR), which [...] Read more.
This article presents a symmetrical reduced-size eight-element MIMO antenna array with high electromagnetic isolation among radiators. The array utilizes easy-to-build techniques to cover the n77 and n78 new radio (NR) bands. It is based on an octagonal double-negative metamaterial split-ring resonator (SRR), which enables a size reduction of over 50% for the radiators compared to a conventional disc monopole antenna by increasing the slow-wave factor. Additionally, due to the extreme proximity between the radiating elements in the array, the modal significance (MS) method was employed to identify which propagation modes had the most impact on the electromagnetic coupling among elements. This approach aimed to mitigate their effect by using an electromagnetic barrier, thereby enhancing electromagnetic isolation. The electromagnetic barriers, implemented with strip lines, achieved isolation values exceeding 20 dB for adjacent elements (<0.023 λ) and approaching 40 dB for opposite ones (<0.23 λ) after analyzing the surface current distribution by the MS method. The elements are arranged in axial symmetry, forming an octagon with each antenna port located on a side. The array occupies an area of 0.32 λ2 at 3.5 GHz, significantly smaller than previously published works. It exhibits excellent performance for MIMO applications, demonstrating an envelope correlation coefficient (ECC) below 0.0001, a total active reflection coefficient (TARC) lower than −10 dB for various incoming signals with random phases, and a diversity gain (DG) close to 20 dB. Full article
(This article belongs to the Special Issue Intelligent Massive-MIMO Systems and Wireless Communications)
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Figure 1

Figure 1
<p>Comparison of: (<b>a</b>) conventional disc monopole, (<b>b</b>) circular SRR antenna, (<b>c</b>) octagonal SRR antenna.</p>
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<p>Simulated <span class="html-italic">S</span><sub>11</sub> parameter of conventional disc monopole, circular SRR, and octagonal SRR antennas.</p>
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<p>Equivalent circuit of a two embedded-octagonal SRR.</p>
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<p>Comparison of the radiated electric field vector of: (<b>a</b>) circular SRR and (<b>b</b>) octagonal SRR antennas.</p>
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<p>Simulated <span class="html-italic">S</span><sub>21</sub> response of the circular and octagonal SRR pair of radiators.</p>
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<p>Proposal of antenna based on octagonal metamaterial SRR.</p>
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<p>Extracted parameters of (<b>a</b>) Permittivity, (<b>b</b>) Permeability.</p>
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<p><span class="html-italic">S</span><sub>11</sub> parameter of the proposed metamaterial element.</p>
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<p>The 8-element metamaterial MIMO antenna proposal.</p>
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<p>Simulated <span class="html-italic">S</span>-parameters of the 8-element MIMO metamaterial antenna.</p>
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<p>Modal significance of the structure shown in <a href="#sensors-24-06266-f009" class="html-fig">Figure 9</a>.</p>
Full article ">Figure 12
<p>Current distribution for: (<b>a</b>) Mode 1, (<b>b</b>) Mode 3, and (<b>c</b>) Mode 4 and radiation pattern for: (<b>d</b>) Mode 1, (<b>e</b>) Mode 3, (<b>f</b>) Mode 4.</p>
Full article ">Figure 13
<p>(<b>a</b>) Metamaterial MIMO antenna with electromagnetic walls, (<b>b</b>) Modal Significance.</p>
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<p>Current distribution with EM walls for: (<b>a</b>) Mode 1, (<b>b</b>) Mode 3, (<b>c</b>) Mode 4, and radiation patterns for: (<b>d</b>) Mode 1, (<b>e</b>) Mode 3, (<b>f</b>) Mode 4.</p>
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<p>Comparison of simulated <span class="html-italic">S</span>-parameters of the MIMO antenna with and without EM barriers.</p>
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<p>Simulated <span class="html-italic">ECC</span> between antenna 1 and the rest of the antennas.</p>
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<p>Simulated TARC for different <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>θ</mi> </mrow> <mrow> <mn>0</mn> </mrow> </msub> </mrow> </semantics></math>.</p>
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<p>The 8-element MIMO antenna prototype, (<b>a</b>) front view, (<b>b</b>) back view, (<b>c</b>) inside the anechoic chamber.</p>
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<p>Measured <span class="html-italic">S</span>-parameters of the MIMO prototype antenna.</p>
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<p>(<b>a</b>) Measured <span class="html-italic">ECC</span> of the prototype MIMO array, (<b>b</b>) Diversity Gain.</p>
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<p>Measured <span class="html-italic">TARC</span> of the MIMO prototype.</p>
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<p>Normalized gain pattern. (<b>a</b>) H-plane, (<b>b</b>) E-plane.</p>
Full article ">Figure 23
<p>Simulated rE field, (<b>a</b>) total array, (<b>b</b>) independent radiator.</p>
Full article ">
14 pages, 2802 KiB  
Article
A Defect Detection Method for Grading Rings of Transmission Lines Based on Improved YOLOv8
by Siyu Xiang, Linghao Zhang, Yumin Chen, Peike Du, Yao Wang, Yue Xi, Bing Li and Zhenbing Zhao
Energies 2024, 17(19), 4767; https://doi.org/10.3390/en17194767 - 24 Sep 2024
Viewed by 389
Abstract
Detecting defects in aerial images of grading rings collected by drones poses challenges due to the structural similarity between normal and defective samples. The small visual differences make it hard to distinguish defects and extract key features. Additionally, critical defect features often become [...] Read more.
Detecting defects in aerial images of grading rings collected by drones poses challenges due to the structural similarity between normal and defective samples. The small visual differences make it hard to distinguish defects and extract key features. Additionally, critical defect features often become lost during feature fusion. To address these issues, this paper uses YOLOv8 as the baseline model and proposes an improved YOLOv8-based method for detecting grading ring defects in transmission lines. Our approach first integrates the CloAttention and C2f modules into the feature extraction network, enhancing the model’s ability to capture and identify defect features in grading rings. Additionally, we incorporate CARAFE into the feature fusion network to replace the original upsampling module, effectively reducing the loss of critical defect information during the fusion process. Experimental results demonstrate that our method achieves an average detection accuracy of 67.6% for grading ring defects, marking a 6.8% improvement over the baseline model. This improvement significantly enhances the effectiveness of defect detection in transmission line grading rings. Full article
(This article belongs to the Section F: Electrical Engineering)
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<p>Improvement of YOLOv8-M structure diagram.</p>
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<p>Structural diagram of CloAttention.</p>
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<p>Structural diagram of CARAFE.</p>
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<p>Test results of the confusion matrix.</p>
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<p>Test results of different models.</p>
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14 pages, 3706 KiB  
Article
Influence of Tire Parameters on Contact Patch and Axle Force Generation against Short Obstacles Using DOE Approach
by Vikas Birajdar, Seyed Jamaleddin Mostafavi Yazdi, Madhu Kandampadath, Mohammad Behroozi and Javad Baqersad
Vehicles 2024, 6(4), 1690-1703; https://doi.org/10.3390/vehicles6040081 - 24 Sep 2024
Viewed by 361
Abstract
Understanding the behavior of tires on uneven and varied road surfaces poses a substantial challenge for vehicle ride engineers. To accurately predict road load forces on the axle, various numerical ride models must be utilized to incorporate a realistic road enveloping algorithm. This [...] Read more.
Understanding the behavior of tires on uneven and varied road surfaces poses a substantial challenge for vehicle ride engineers. To accurately predict road load forces on the axle, various numerical ride models must be utilized to incorporate a realistic road enveloping algorithm. This algorithm filters the geometries of uneven surfaces and must be seamlessly integrated with a rigid ring model. The complexity of predicting and calculating dynamic tire response increases with varying obstacle dimensions. A two-dimensional, five-degree-of-freedom rigid ring ride model based on Short Wavelength Intermediate Frequency (SWIFT) has been developed, employing a tandem cam enveloping algorithm to filter short wavelength road obstacles. Selecting generalized cam parameters to ensure high accuracy and an enhanced runtime performance poses a challenge in specific ride simulations. A design of experiments (DOE) approach is used to identify key control factors related to the quasi-static tandem cam enveloping model and dynamic rigid ring model, which significantly affect the enveloping response. DOE findings suggest optimization strategies for selecting tire parameters to achieve a high test-to-simulation correlation with improved computational efficiency. Additionally, the study confirms the robustness of these predictions against external noise factors, including variations in tires and road conditions. Full article
(This article belongs to the Special Issue Feature Papers on Advanced Vehicle Technologies)
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<p>Tandem Elliptical Cam Model [<a href="#B4-vehicles-06-00081" class="html-bibr">4</a>].</p>
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<p>Schematic representation of the rigid ring model [<a href="#B4-vehicles-06-00081" class="html-bibr">4</a>].</p>
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<p>Control factors for low-speed simulation (enveloping parameters). (<b>a</b>) Number of Cams. (<b>b</b>) Cam Shape Parameters. (<b>c</b>) Empirical Coefficients.</p>
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<p>Control factors for high-speed simulation (rigid ring parameters).</p>
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<p>Sensitivity of control factors for low-speed simulation (mean of means).</p>
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<p>Sensitivity of control factors for low-speed simulation (mean of SN ratio).</p>
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<p>Sensitivity of control factor’s frequency at peak for longitudinal force with speed 30 kph (mean of means).</p>
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<p>Sensitivity of control factor’s frequency at peak for longitudinal force with speed 30 kph (mean of means).</p>
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<p>Sensitivity index matrix of all control factor for force in longitudinal direction.</p>
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<p>Sensitivity index matrix of all control factors for force in vertical direction.</p>
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26 pages, 7340 KiB  
Article
Versatile Video Coding-Post Processing Feature Fusion: A Post-Processing Convolutional Neural Network with Progressive Feature Fusion for Efficient Video Enhancement
by Tanni Das, Xilong Liang and Kiho Choi
Appl. Sci. 2024, 14(18), 8276; https://doi.org/10.3390/app14188276 - 13 Sep 2024
Viewed by 587
Abstract
Advanced video codecs such as High Efficiency Video Coding/H.265 (HEVC) and Versatile Video Coding/H.266 (VVC) are vital for streaming high-quality online video content, as they compress and transmit data efficiently. However, these codecs can occasionally degrade video quality by adding undesirable artifacts such [...] Read more.
Advanced video codecs such as High Efficiency Video Coding/H.265 (HEVC) and Versatile Video Coding/H.266 (VVC) are vital for streaming high-quality online video content, as they compress and transmit data efficiently. However, these codecs can occasionally degrade video quality by adding undesirable artifacts such as blockiness, blurriness, and ringing, which can detract from the viewer’s experience. To ensure a seamless and engaging video experience, it is essential to remove these artifacts, which improves viewer comfort and engagement. In this paper, we propose a deep feature fusion based convolutional neural network (CNN) architecture (VVC-PPFF) for post-processing approach to further enhance the performance of VVC. The proposed network, VVC-PPFF, harnesses the power of CNNs to enhance decoded frames, significantly improving the coding efficiency of the state-of-the-art VVC video coding standard. By combining deep features from early and later convolution layers, the network learns to extract both low-level and high-level features, resulting in more generalized outputs that adapt to different quantization parameter (QP) values. The proposed VVC-PPFF network achieves outstanding performance, with Bjøntegaard Delta Rate (BD-Rate) improvements of 5.81% and 6.98% for luma components in random access (RA) and low-delay (LD) configurations, respectively, while also boosting peak signal-to-noise ratio (PSNR). Full article
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<p>Enhancing video quality with CNN based post-processing in conventional VVC coding workflow.</p>
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<p>MP4 to YUV conversion and reconstruction using VVenC and VVdeC.</p>
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<p>Illustration of video-to-image conversion process: (<b>a</b>) original videos converted to original images using FFmpeg, and (<b>b</b>) reconstructed videos converted to reconstructed images using FFmpeg.</p>
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<p>Illustration of the conversion process from YUV 4:2:0 format to YUV 4:4:4 format before feeding data into the deep learning network.</p>
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<p>Illustration of down-sampling process of neural network output from YUV 4:4:4 to YUV 4:2:0 format.</p>
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<p>Architecture of the proposed CNN-based post-filtering method, integrating multiple feature extractions for enhanced output refinement.</p>
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<p>Comparative visualization of (<b>b</b>) reconstructed frames from anchor VVC and (<b>c</b>) proposed methods for DaylightRoad2 sequence at QP 42 for RA configuration, alongside the (<b>a</b>) original uncompressed reference frame.</p>
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<p>Comparative visualization of (<b>b</b>) reconstructed frames from anchor VVC and (<b>c</b>) proposed methods for FourPeople sequence at QP 42 for LD configuration, alongside the (<b>a</b>) original uncompressed reference frame.</p>
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<p>RD curve performance comparison for five different test sequences in RA configuration.</p>
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<p>RD curve performance comparison for four different test sequences in LD configuration.</p>
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<p>Visual quality comparison of proposed method with 8 feature extraction blocks for RA and LD scenarios at QP 42: (<b>a</b>) MarketPlace Sequence and (<b>b</b>) PartyScene Sequence.</p>
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<p>Visual quality comparison of proposed method with 12 feature extraction blocks for RA and LD scenarios at QP 42: (<b>a</b>) RitualDance Sequence and (<b>b</b>) Cactus Sequence.</p>
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25 pages, 5506 KiB  
Article
Neurotoxicity, Neuroprotection, In Vitro MAOA/MAOB Inhibitory Activity Assessment, Molecular Docking, and Permeability Assay Studies of Newly Synthesized Hydrazones Containing a Pyrrole Ring
by Maya Georgieva, Emilio Mateev, Iva Valkova, Hristina Kuteva, Diana Tzankova, Denitsa Stefanova, Yordan Yordanov, Karolina Lybomirova, Alexander Zlatkov, Virginia Tzankova and Magdalena Kondeva-Burdina
Molecules 2024, 29(18), 4338; https://doi.org/10.3390/molecules29184338 - 12 Sep 2024
Viewed by 506
Abstract
Neurodegenerative diseases such as Parkinson’s and Alzheimer’s continue to be some of the most significant challenges in modern medicine. Recent research related to the molecular mechanisms of parkinsonism has opened up new approaches to antiparkinsonian therapy. In response to this, we present the [...] Read more.
Neurodegenerative diseases such as Parkinson’s and Alzheimer’s continue to be some of the most significant challenges in modern medicine. Recent research related to the molecular mechanisms of parkinsonism has opened up new approaches to antiparkinsonian therapy. In response to this, we present the evaluation of the potential neuroprotective and MAOA/MAOB inhibitory effects of newly synthesized hydrazones, containing a pyrrole moiety in the carboxyl fragment of the structure. The substances were studied on different brain subcellular fractions, including rat brain synaptosomes, mitochondria, and microsomes. The single application of 50 µM of each compound to the subcellular fractions showed that all substances exhibit a weak neurotoxic effect, with 7b, 7d, and 8d being the least neurotoxic representatives. The corresponding neuroprotective and antioxidant effects were also evaluated in different injury models on subcellular fractions, single out 7b, 7d, and 8d as the most prominent derivatives. A 1 µM concentration of each molecule from the series was also studied for potential hMAOA/hMAOB inhibitory effects. The results revealed a lack of hMAOA activity for all evaluated structures and the appearance of hMAOB effects, with compounds 7b, 7d, and 8d showing effects similar to those of selegiline. The best hMAOB selectivity index (>204) was determined for 7d and 8d, distinguishing these two representatives as the most promising molecules for further studies as potential selective MAOB inhibitors. The performed molecular docking simulations defined the appearance of selective MAOB inhibitory effects based on the interaction of the tested molecules with Tyr398, which is one of the components of the aromatic cage of MAOB and participated in π–π stabilization with the aromatic pyrrole ring. The preliminary PAMPA testing indicated that in relation to the blood–brain barrier (BBB) permeability, the tested pyrrole-based hydrazones may be considered as high permeable, except for 8a and 8e, which were established to be permeable in the medium range with −logP of 5.268 and 5.714, respectively, compared to the applied references. Full article
(This article belongs to the Section Medicinal Chemistry)
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<p>Structures of some MAO inhibitors.</p>
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<p>Structures of the most active molecule <b>12a</b> and its analogues containing a benzaldehyde residue from a previously synthesized series [<a href="#B28-molecules-29-04338" class="html-bibr">28</a>].</p>
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<p>Structures and IDs of the evaluated hydrazones.</p>
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<p>Effect of the test substances applied alone at a concentration of 50 µM on synaptosomal viability. * <span class="html-italic">p</span> &lt; 0.05; ** <span class="html-italic">p</span> &lt; 0.01 vs. control (non-treated synaptosomes).</p>
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<p>Effect of the test substances applied alone at a concentration of 50 µM on the level of glutathione (GSH). * <span class="html-italic">p</span> &lt; 0.05 vs. control (non-treated synaptosomes).</p>
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<p>Effect of test substances applied alone at a concentration of 50 µM on MDA production. ** <span class="html-italic">p</span> &lt; 0.01 vs. control (non-treated mitochondria).</p>
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<p>Effect of test substances applied alone at a concentration of 50 µM on GSH level. * <span class="html-italic">p</span> &lt; 0.05 vs. control (non-treated mitochondria).</p>
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<p>Effect of test substances applied alone, at a concentration of 50 µM, on MDA production. ** <span class="html-italic">p</span> &lt; 0.01 vs. control (non-treated microsomes).</p>
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<p>Effect of substances in combination with 6-OHDA on synaptosomal viability. *** <span class="html-italic">p</span> &lt; 0.001 vs. control (non-treated synaptosomes); + <span class="html-italic">p</span> &lt; 0.05; ++ <span class="html-italic">p</span> &lt; 0.01 vs. 6-OHDA. The green color indicates the most active derivatives.</p>
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<p>Effect of substances, in combination with 6-OHDA, on the level of reduced glutathione (GSH). ** <span class="html-italic">p</span> &lt; 0.001 vs. control (non-treated synaptosomes); + <span class="html-italic">p</span> &lt; 0.05 vs. 6-OHDA. The green color indicates the most active derivatives.</p>
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<p>Effect of substances in combination with <span class="html-italic">t</span>-BuOOH on MDA production. *** <span class="html-italic">p</span> &lt; 0.001 vs. control (non-treated mitochondria); + <span class="html-italic">p</span> &lt; 0.05; ++ <span class="html-italic">p</span> &lt; 0.01 vs. <span class="html-italic">t</span>-BuOOH. The green color indicates the most active derivatives.</p>
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<p>Effect of substances in combination with <span class="html-italic">t</span>-BuOOH on GSH level. ** <span class="html-italic">p</span> &lt; 0.01 vs. control (non-treated mitochondria); + <span class="html-italic">p</span> &lt; 0.05; ++ <span class="html-italic">p</span> &lt; 0.01 vs. <span class="html-italic">t</span>-BuOOH. The green color indicates the most active derivatives.</p>
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<p>Effect of substances under conditions of non-enzyme-induced lipid peroxidation (Fe<sup>2+</sup>/AA). *** <span class="html-italic">p</span> &lt; 0.001 vs. control (non-treated microsomes); ++ <span class="html-italic">p</span> &lt; 0.01; +++ <span class="html-italic">p</span> &lt; 0.001 vs. Fe<sup>2+</sup>/AA. The green color indicates the most active derivatives.</p>
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<p>Effect of newly synthetized hydrazones containing a pyrrole cycle in the carboxyl fragment of the structure (at 1 µM concentration) on the activity of human recombinant MAOA enzyme (<span class="html-italic">h</span>MAOA). *** <span class="html-italic">p</span> &lt; 0.001 vs. control (pure <span class="html-italic">h</span>MAOA).</p>
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<p>Effect of newly synthetized hydrazones containing a pyrrole cycle in the carboxyl fragment of the structure (at 1 µM concentration) on the activity of the human recombinant MAOB enzyme (<span class="html-italic">h</span>MAOB). * <span class="html-italic">p</span> &lt; 0.05; *** <span class="html-italic">p</span> &lt; 0.001 vs. control (pure <span class="html-italic">h</span>MAOB). The green color indicates the most active derivatives.</p>
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<p>Major intermolecular interactions between the active site of MAOB and <b>8d</b>: (<b>a</b>) 3D model; (<b>b</b>) 2D model.</p>
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28 pages, 389 KiB  
Article
A New Method for Constructing Self-Dual Codes over Finite Commutative Rings with Characteristic 2
by Yongsheng Ma, Jizhu Nan and Yuanbo Liu
Mathematics 2024, 12(17), 2731; https://doi.org/10.3390/math12172731 - 31 Aug 2024
Viewed by 702
Abstract
In this work, we present a new method for constructing self-dual codes over finite commutative rings R with characteristic 2. Our method involves searching for k×2k matrices M over R satisfying the conditions that its rows are linearly independent over [...] Read more.
In this work, we present a new method for constructing self-dual codes over finite commutative rings R with characteristic 2. Our method involves searching for k×2k matrices M over R satisfying the conditions that its rows are linearly independent over R and MM=αα for an R-linearly independent vector αRk. Let C be a linear code generated by such a matrix M. We prove that the dual code C of C is also a free linear code with dimension k, as well as C/Hull(C) and C/Hull(C) are one-dimensional free R-modules, where Hull(C) represents the hull of C. Based on these facts, an isometry from Rx+Ry onto R2 is established, assuming that x+Hull(C) and y+Hull(C) are bases for C/Hull(C) and C/Hull(C) over R, respectively. By utilizing this isometry, we introduce a new method for constructing self-dual codes from self-dual codes of length 2 over finite commutative rings with characteristic 2. To determine whether the matrix MM takes the form of αα with α being a linearly independent vector in Rk, a necessary and sufficient condition is provided. Our method differs from the conventional approach, which requires the matrix M to satisfy MM=0. The main advantage of our method is the ability to construct nonfree self-dual codes over finite commutative rings, a task that is typically unachievable using the conventional approach. Therefore, by combining our method with the conventional approach and selecting an appropriate matrix construction, it is possible to produce more self-dual codes, in contrast to using solely the conventional approach. Full article
15 pages, 1575 KiB  
Article
Microsolvation of a Proton by Ar Atoms: Structures and Energetics of ArnH+ Clusters
by María Judit Montes de Oca-Estévez and Rita Prosmiti
Molecules 2024, 29(17), 4084; https://doi.org/10.3390/molecules29174084 - 28 Aug 2024
Viewed by 504
Abstract
We present a computational investigation on the structural arrangements and energetic stabilities of small-size protonated argon clusters, Ar nH +. Using high-level ab initio electronic structure computations, we determined that the linear symmetric triatomic ArH +Ar ion [...] Read more.
We present a computational investigation on the structural arrangements and energetic stabilities of small-size protonated argon clusters, Ar nH +. Using high-level ab initio electronic structure computations, we determined that the linear symmetric triatomic ArH +Ar ion serves as the molecular core for all larger clusters studied. Through harmonic normal-mode analysis for clusters containing up to seven argon atoms, we observed that the proton-shared vibration shifts to lower frequencies, consistent with measurements in gas-phase IRPD and solid Ar-matrix isolation experiments. We explored the sum-of-potentials approach by employing kernel-based machine-learning potential models trained on CCSD(T)-F12 data. These models included expansions of up to two-body, three-body, and four-body terms to represent the underlying interactions as the number of Ar atoms increases. Our results indicate that the four-body contributions are crucial for accurately describing the potential surfaces in clusters with n> 3. Using these potential models and an evolutionary programming method, we analyzed the structural stability of clusters with up to 24 Ar atoms. The most energetically favored Ar nH + structures were identified for magic size clusters at n = 7, 13, and 19, corresponding to the formation of Ar-pentagon rings perpendicular to the ArH +Ar core ion axis. The sequential formation of such regular shell structures is compared to ion yield data from high-resolution mass spectrometry measurements. Our results demonstrate the effectiveness of the developed sum-of-potentials model in describing trends in the nature of bonding during the single proton microsolvation by Ar atoms, encouraging further quantum nuclear studies. Full article
(This article belongs to the Special Issue Advances in Computational and Theoretical Chemistry—2nd Edition)
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<p>Binding energies and bondlengths of the optimized structures (see inset plots) of the Ar<math display="inline"><semantics> <msub> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mi>n</mi> </msub> </semantics></math>H<math display="inline"><semantics> <msup> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mo>+</mo> </msup> </semantics></math> complexes (with <span class="html-italic">n</span> = 1–9) from CCSD(T)/AV6Z (<span class="html-italic">n</span> = 1–2) and MP2/AVQZ (<span class="html-italic">n</span> = 3–9) calculations.</p>
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<p>Interaction CCSD(T)-F12/AVQZ energies (see circle symbols) as a function of <span class="html-italic">R</span> distance at the indicated <math display="inline"><semantics> <mi>θ</mi> </semantics></math> values (see <b>upper</b> panel) and minimum energy path along both <span class="html-italic">R</span> and <math display="inline"><semantics> <mi>θ</mi> </semantics></math> coordinates as a function of <math display="inline"><semantics> <mi>θ</mi> </semantics></math> angles (see <b>lower</b> panel) for the Ar<math display="inline"><semantics> <msub> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mn>3</mn> </msub> </semantics></math>H<math display="inline"><semantics> <msup> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mo>+</mo> </msup> </semantics></math> cation (see inset plot). The corresponding RKHS ML-PES curves are also shown as solid lines, while the dissociation energy is plotted by long-dashed line.</p>
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<p>Histograms of training datasets employed in the hold-out cross-validation scheme for assessing the RKHS ML-PES models. The number of total configurations considered is given in the top of each panel. The left, middle and right side panels correspond to increasing numbers of grid points in <span class="html-italic">R</span>, 20, 40 and 61, respectively, while the orange and maroon colors show datasets with 10 and 19 grid points in <math display="inline"><semantics> <mi>θ</mi> </semantics></math>.</p>
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<p>Histograms of the total and randomly generated testing datasets (see text) employed in hold-out cross-validation scheme for the RKHS ML-PES (<b>left</b> panel). The corresponding RMSE values of the RKHS ML-PES models as a function of the training set size (<b>right</b> panel). The black dashed line indicates the dissociation threshold.</p>
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<p>Correlation plots of the RKHS ML-PES model against the reference CCSD(T)-F12/AVQZ energies for both training (<b>left</b> panel) and testing (<b>right</b> panel) data. The corresponding average RMSE and MAE values along energy are also plotted.</p>
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<p>2D contour plot of the RKHS ML-PES for Ar<math display="inline"><semantics> <msub> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mn>3</mn> </msub> </semantics></math>H<math display="inline"><semantics> <msup> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mo>+</mo> </msup> </semantics></math> complex in the (<math display="inline"><semantics> <mi>θ</mi> </semantics></math>,R)-plane. The equipotential curves are at energies of −39,000 to −38,000 cm<math display="inline"><semantics> <msup> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mrow> <mo>−</mo> <mn>1</mn> </mrow> </msup> </semantics></math> in intervals of 100 cm<math display="inline"><semantics> <msup> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mrow> <mo>−</mo> <mn>1</mn> </mrow> </msup> </semantics></math>.</p>
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<p>Coordinate system used for the Ar<math display="inline"><semantics> <msub> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mi>n</mi> </msub> </semantics></math>H<math display="inline"><semantics> <msup> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mo>+</mo> </msup> </semantics></math> clusters in the sum-of-three-body (<b>left</b> panel) and sum-of-four-body (<b>right</b> panel) potential approaches.</p>
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<p>Potential curves obtained for the Ar<math display="inline"><semantics> <msub> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mi>n</mi> </msub> </semantics></math>H<math display="inline"><semantics> <msup> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mo>+</mo> </msup> </semantics></math> (with <span class="html-italic">n</span> = 2, 3 and 4) clusters using the sum-of-potential approaches of Equations (<a href="#FD4-molecules-29-04084" class="html-disp-formula">4</a>)–(<a href="#FD6-molecules-29-04084" class="html-disp-formula">6</a>) (see color dashed lines), together with the calculated CCSD(T)/CBS[56] (for <span class="html-italic">n</span> = 2) and CCSD(T)-F12/AVQZ (for <span class="html-italic">n</span> = 3 and 4) interaction energies (black circles) as a function of indicated <math display="inline"><semantics> <msub> <mi>R</mi> <mi>i</mi> </msub> </semantics></math> coordinates.</p>
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<p>Schematic representation of selected optimal low-lying structures and their energetics obtained using the V<math display="inline"><semantics> <msub> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mrow> <mn>4</mn> <mi>B</mi> </mrow> </msub> </semantics></math> approach of Equation (<a href="#FD6-molecules-29-04084" class="html-disp-formula">6</a>) and the GA algorithm for the Ar<math display="inline"><semantics> <msub> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mi>n</mi> </msub> </semantics></math>H<math display="inline"><semantics> <msup> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mo>+</mo> </msup> </semantics></math> clusters. Energy values from the MP2/AVQZ optimizations and their ZPE corrections, <math display="inline"><semantics> <msub> <mi mathvariant="script">E</mi> <mi>ZPE</mi> </msub> </semantics></math>, given by the corresponding harmonic approximation, are also shown.</p>
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<p>Computed harmonic frequencies for the indicated Ar<math display="inline"><semantics> <msub> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mi>n</mi> </msub> </semantics></math>H<math display="inline"><semantics> <msup> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mo>+</mo> </msup> </semantics></math> clusters from MP2/AVQZ calculations in comparison with data from gas phase IRPD [<a href="#B8-molecules-29-04084" class="html-bibr">8</a>] and solid Ar-matrix isolation measurements [<a href="#B29-molecules-29-04084" class="html-bibr">29</a>]. The anharmonic fundamental frequency for Ar<math display="inline"><semantics> <msub> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mn>2</mn> </msub> </semantics></math>H<math display="inline"><semantics> <msup> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mo>+</mo> </msup> </semantics></math> from ref. [<a href="#B24-molecules-29-04084" class="html-bibr">24</a>] is also displayed.</p>
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<p>Computed single-atom evaporative energies (green color) of Ar<math display="inline"><semantics> <msub> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mi>n</mi> </msub> </semantics></math>H<math display="inline"><semantics> <msup> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mo>+</mo> </msup> </semantics></math> clusters, their average energy per Ar atom (red color) from the V<math display="inline"><semantics> <msub> <mrow> <mspace width="-2.pt"/> <mo> </mo> </mrow> <mrow> <mn>4</mn> <mi>B</mi> </mrow> </msub> </semantics></math> potential EP optimizations (dashed lines) and MP2/AVQZ calculations (solid lines) as a function of <span class="html-italic">n</span>. Previously reported theoretical dissociation energies [<a href="#B5-molecules-29-04084" class="html-bibr">5</a>] and experimental ion yield values [<a href="#B3-molecules-29-04084" class="html-bibr">3</a>] are also displayed for comparison reasons.</p>
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11 pages, 2114 KiB  
Article
Frustrated Alternative Approaches towards the Synthesis of a Thermally Stable 1,2-Diazacyclobutene
by Gary W. Breton and Kenneth L. Martin
Molecules 2024, 29(17), 4068; https://doi.org/10.3390/molecules29174068 - 28 Aug 2024
Viewed by 344
Abstract
We have previously demonstrated that an appropriately substituted four-membered-ring 1,2-diazacyclobutene is a useful compound in organic synthesis for the introduction of strained 1,2-diazetidine rings. In order to further explore the reactivity of this interesting heterocycle, we sought a method to improve upon the [...] Read more.
We have previously demonstrated that an appropriately substituted four-membered-ring 1,2-diazacyclobutene is a useful compound in organic synthesis for the introduction of strained 1,2-diazetidine rings. In order to further explore the reactivity of this interesting heterocycle, we sought a method to improve upon the poor synthetic yield reported earlier. A novel route involving the synthesis of a similarly substituted 1,2-diazetidine compound followed by free-radical bromination and base-catalyzed debromination appeared promising. While there are some studies on the synthesis of the desired 1,2-diazetidine precursor, when we attempted its synthesis, we instead observed the exclusive formation of an eight-membered “dimer”-like compound. The structure of this compound was confirmed via single-crystal X-ray analysis. Fortunately, an alternative synthetic approach for the formation of the desired 1,2-diazetidine precursor proved successful, and the structure of the precursor has been confirmed via X-ray analysis. However, unfortunately, the required bromination step proved to be more challenging than expected, and ultimately, this route had to be abandoned since the anticipated improvement upon the original yield did not seem promising. Single-crystal X-ray analysis proved pivotal in properly identifying the structures of the synthesized compounds. Full article
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<p>(<b>A</b>) The structure of <b>7</b> and (<b>B</b>) an ORTEP representation of the X-ray crystal structure of <b>7</b> with thermal ellipsoids drawn at 50% probability. Selected bond lengths (Å): N(1)-N(2), 1.420; N(1)-C(1), 1.480; N(1)-C(2), 1.383, C(2)-N(3), 1.388; N(3)-C(3), 1.434; and C(2)-O(1), 1.208. Selected bond angles (°): C(1)-N(1)-N(2), 118.1; C(1)-N(1)-C(2), 118.2; and N(2)-N(1)-C(2), 108.0. Selected dihedral angles (°): N(2)-N(1)-C(2)-N(3), 10.8 and C(2)-N(3)-C(3)-C(4), 138.7.</p>
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<p>ORTEP representation of the X-ray crystal structure of compound <b>3</b> with thermal ellipsoids drawn at 50% probability as visualized (<b>A</b>) from the front and (<b>B</b>) from the side of the structure. Selected bond lengths (Å): C(1)-C(2), 1.538; C(1)-N(1), 1.510; N(1)-N(2), 1.481; N(1)-C(3), 1.395; C(3)-O(1), 1.210; C(3)-N(3), 1.396; and N(3)-C(4), 1.435. Selected bond angles (°): C(1)-N(2)-C(3), 121.0; C(1)-N(1)-N(2), 91.5; and N(1)-C(3)-N(3), 105.9. Select dihedral angles (°): C(1)-C(2)-N(2)-N(1), 1.9 and C(3)-N(3)-C(4)-C(5), 53.2.</p>
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<p>Structure of previously reported diazetidine <b>22</b>.</p>
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<p>(<b>A</b>) Reactivity of diazetine <b>1</b> via Diels–Alder reactions to form 1,2-diazetidines, and its resistance to electrocyclic ring opening; (<b>B</b>) Thermally allowed electrocyclic ring opening of diazetine <b>2</b>.</p>
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<p>Proposed synthesis of <b>1b</b>.</p>
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<p>Literature procedure [<a href="#B5-molecules-29-04068" class="html-bibr">5</a>] for the formation of <b>6</b> (Ar = 4-ClC<sub>6</sub>H<sub>6</sub>) as extended towards the synthesis of <b>3</b>.</p>
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<p>Proposed mechanism for the formation of dimer compound <b>7</b>.</p>
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<p>(<b>A</b>) Shipman’s [<a href="#B6-molecules-29-04068" class="html-bibr">6</a>] cyclization of protected hydrazines (<b>12</b>) to form diazetidines (<b>13</b>). (<b>B</b>) Attempted extension of Shipman’s synthetic method to form <b>3</b>.</p>
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<p>Successful synthesis of <b>3</b> starting from previously reported compound <b>19</b> [<a href="#B7-molecules-29-04068" class="html-bibr">7</a>].</p>
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19 pages, 1353 KiB  
Article
Distributed Identity Authentication with Lenstra–Lenstra–Lovász Algorithm–Ciphertext Policy Attribute-Based Encryption from Lattices: An Efficient Approach Based on Ring Learning with Errors Problem
by Qi Yuan, Hao Yuan, Jing Zhao, Meitong Zhou, Yue Shao, Yanchun Wang and Shuo Zhao
Entropy 2024, 26(9), 729; https://doi.org/10.3390/e26090729 - 27 Aug 2024
Viewed by 452
Abstract
In recent years, research on attribute-based encryption (ABE) has expanded into the quantum domain. Because a traditional single authority can cause the potential single point of failure, an improved lattice-based quantum-resistant identity authentication and policy attribute encryption scheme is proposed, in which the [...] Read more.
In recent years, research on attribute-based encryption (ABE) has expanded into the quantum domain. Because a traditional single authority can cause the potential single point of failure, an improved lattice-based quantum-resistant identity authentication and policy attribute encryption scheme is proposed, in which the generation of random values is optimized by adjusting parameters in the Gaussian sampling algorithm to improve overall performance. Additionally, in the key generation phase, attributes are processed according to their shared nature, which reduces the computational overhead of the authorization authority. In the decryption phase, the basis transformation of the Lenstra–Lenstra–Lovász (LLL) lattice reduction algorithm is utilized to rapidly convert shared matrices into the shortest vector form, which can reduce the computational cost of linear space checks. The experimental results demonstrate that the proposed method not only improves efficiency but also enhances security compared with related schemes. Full article
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<p>The system model of this scheme.</p>
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<p>Time expenditure of each stage in the article.</p>
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<p>Time expenditure between different schemes in each stage.</p>
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22 pages, 2140 KiB  
Article
Synthesis of Self-Checking Circuits for Train Route Traffic Control at Intermediate Stations with Control of Calculations Based on Weight-Based Sum Codes
by Dmitry V. Efanov, Artyom V. Pashukov, Evgenii M. Mikhailiuta, Valery V. Khóroshev, Ruslan B. Abdullaev, Dmitry G. Plotnikov, Aushra V. Banite, Alexander V. Leksashov, Dmitry N. Khomutov, Dilshod Kh. Baratov and Davron Kh. Ruziev
Computation 2024, 12(9), 171; https://doi.org/10.3390/computation12090171 - 26 Aug 2024
Viewed by 568
Abstract
When synthesizing systems for railway interlocking, it is recommended to use automated models to implement the logic of railway automation and remote control units. Finite-state machines (FSMs) can be implemented on any hardware component. When using relay technology, the functional safety of electrical [...] Read more.
When synthesizing systems for railway interlocking, it is recommended to use automated models to implement the logic of railway automation and remote control units. Finite-state machines (FSMs) can be implemented on any hardware component. When using relay technology, the functional safety of electrical interlocking is achieved by using uncontrolled (safety) relays with a high coefficient of asymmetry of failures in types 1 → 0 and 0 → 1. When using programmable components, the use of backup and diverse protection methods is required. This paper presents a flexible approach to synthesizing FSMs for railway automation and remote control units that offer both individual and route-based control. Unlike existing solutions, this proposal considers the pre-failure states of railway automation and remote control units during the finite-state machine synthesis stage. This enables the implementation of self-checking and self-diagnostic modules to manage automation units. By increasing the number of states for individual devices and considering the states of interconnected objects, the transition graphs can be expanded. This expansion allows for the synthesis of the transition graph of the control subsystem and other systems. The authors used a field-programmable gate array (FPGA) to implement a finite-state machine. In this case, the proposal is to encode the states of a finite-state machine using weight-based sum codes in the residue class ring based on a given modulus. The best coverage of errors occurring at the outputs of the logic converter in the structure of the FSM can be ensured by selecting the weighting coefficients and the value of the module. This paper presents an example of synthesizing an FPGA-based FSM using state encoding through modular weight-based sum codes. The operation of the synthesized device was modeled. It was found to operate according to the same algorithm as the real devices. When synthesizing self-checking and self-controlled train control devices, it is recommended to consider the solutions proposed in this paper. Full article
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<p>Single-line passing track plan.</p>
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<p>Transition graph for a single route.</p>
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<p>Transition graph for two routes.</p>
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<p>Block diagram of a <span class="html-italic">D</span>-flip-flop-based FSM.</p>
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<p>A finite-state machine operation simulation. The red line in the Figure indicates the moment of completion of the finite state machine operation when the route is set, followed by its closure and return to the initial state. The green line in the Figure characterizes the moment of completion of the transfer of the system to the protective state (from the red line) and back (from the green line) upon receipt of input data that do not correspond to the logic of the system operation.</p>
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<p>Block diagram of an FSM with embedded control circuits.</p>
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14 pages, 5033 KiB  
Article
The Tribological Properties of Novel Sulfoximine Derivatives as Lubricant Additives
by Jianbin Zhang, Chaoyang Zhang, Yanhua Liu, Libang Feng, Wufang Yang, Xiaowei Pei and Qiangliang Yu
Materials 2024, 17(16), 4145; https://doi.org/10.3390/ma17164145 - 22 Aug 2024
Viewed by 552
Abstract
Introducing an additive is a practical approach to improve the lubrication performance of base oil in the field of tribology. Herein, a series of sulfoximine derivatives was synthesized and incorporated into base oil A51 as additives. The tribological properties of these lubricants were [...] Read more.
Introducing an additive is a practical approach to improve the lubrication performance of base oil in the field of tribology. Herein, a series of sulfoximine derivatives was synthesized and incorporated into base oil A51 as additives. The tribological properties of these lubricants were evaluated at both room and high temperatures, and the result demonstrated that they displayed excellent friction reduction and wear resistance in the friction process under both test conditions. Moreover, the chemical composition of the worn scar surface was inspected using EDS, XPS and TOF-SIMS to explore the lubricating mechanism. It is reasonable to conclude that the synergistic interaction between the aromatic ring scaffolds and elements like N, F, and S facilitated the adsorption of lubricant on the steel block surfaces and forming a tribofilm during the friction process. This tribofilm has a dominant impact on the system’s lubrication performance. This research provides novel oil-soluble lubricant additives, offering a facile approach to formulating high-quality lubricants. Full article
(This article belongs to the Section Thin Films and Interfaces)
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<p>NMR spectra of the lubricant additives for A (<b>A</b>), B (<b>B</b>), and C (<b>C</b>). Character 1 shows the hydrogen spectrum, character 2 represents the carbon spectrum, and the insets in the figure indicate the molecular formula of the additives.</p>
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<p>The friction curve and coefficient of friction (COF) of the lubricant with lubricant additives at high and room temperature (<b>A</b>) and high temperature (<b>B</b>). The applied load was 100 N, the frequency was 25 Hz, and the amplitude was 1 mm during the tribological test.</p>
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<p>Three-dimensional topographic images (<b>A</b>,<b>B</b>) of lubricated worn plates and their wear volume statistics (<b>C</b>,<b>D</b>): (0) A51, (1) 1% A, (2) 1% B, and (3) 1% C. Characters (<b>A</b>,<b>C</b>) indicate room temperature; characters (<b>B</b>,<b>D</b>) indicate high temperature.</p>
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<p>The SEM images of worn scars on steel plates lubricated by (0) A51, (1) 1% A, (2) 1% B, and (3) 1% C. (<b>A</b>,<b>B</b>) (greater magnification) represent room temperature, and (<b>C</b>,<b>D</b>) represent high temperature.</p>
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<p>Chemical elemental analysis of worn scar lubricated by (0) A51, (1) 1% A additive, (2) 1% B additive, and (3) 1% C additive. Surface element distribution diagram (<b>A</b>,<b>C</b>) of area scan and line scan scanning element (<b>B</b>,<b>D</b>) at the center line of the wear spot. (<b>A</b>,<b>B</b>) indicate room temperature, and (<b>C</b>,<b>D</b>) indicate high temperature.</p>
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<p>XPS profiles of the worn surface for C 1s (<b>A</b>), N 1s (<b>B</b>), Fe 2p (<b>C</b>), N 1s (<b>D</b>), S 2p (<b>E</b>), and F 1s (<b>F</b>). The characters 0, 1, 2, and 3 represented A51 base oil, additives A, B, and C; RT indicates room temperature; HT indicates high temperature.</p>
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<p>TOF-SIMS mass spectrometry of positive and negative ions generated by tribofilm on worn steel surfaces lubricated with lubricants containing compound A (<b>A</b>,<b>B</b>), compound B (<b>C</b>,<b>D</b>), and compound C (<b>E</b>,<b>F</b>). The icons (<b>A</b>,<b>C</b>,<b>E</b>) indicate room temperature; (<b>B</b>,<b>D</b>,<b>F</b>) indicate high temperature.</p>
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<p>Schematic diagram of the lubrication mechanism of a lubricant containing synthetic additives. The formation diagram of tribofilm during friction process (<b>A</b>) and the molecular structure of the additives (<b>B</b>).</p>
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<p>The schematic diagram of the synthetic route of two sulfoximine derivatives as lubricating additives for compound B (<b>A</b>) and compound C (<b>B</b>).</p>
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11 pages, 2808 KiB  
Article
Facile Splint-Free Circularization of ssDNA with T4 DNA Ligase by Redesigning the Linear Substrate to Form an Intramolecular Dynamic Nick
by Wenhua Sun, Kunling Hu, Mengqin Liu, Jian Luo, Ran An and Xingguo Liang
Biomolecules 2024, 14(8), 1027; https://doi.org/10.3390/biom14081027 - 18 Aug 2024
Viewed by 816
Abstract
The efficient preparation of single-stranded DNA (ssDNA) rings, as a macromolecular construction approach with topological features, has aroused much interest due to the ssDNA rings’ numerous applications in biotechnology and DNA nanotechnology. However, an extra splint is essential for enzymatic circularization, and by-products [...] Read more.
The efficient preparation of single-stranded DNA (ssDNA) rings, as a macromolecular construction approach with topological features, has aroused much interest due to the ssDNA rings’ numerous applications in biotechnology and DNA nanotechnology. However, an extra splint is essential for enzymatic circularization, and by-products of multimers are usually present at high concentrations. Here, we proposed a simple and robust strategy using permuted precursor (linear ssDNA) for circularization by forming an intramolecular dynamic nick using a part of the linear ssDNA substrate itself as the template. After the simulation of the secondary structure for desired circular ssDNA, the linear ssDNA substrate is designed to have its ends on the duplex part (≥5 bp). By using this permuted substrate with 5′-phosphate, the splint-free circularization is simply carried out by T4 DNA ligase. Very interestingly, formation of only several base pairs (2–4) flanking the nick is enough for ligation, although they form only instantaneously under ligation conditions. More significantly, the 5-bp intramolecular duplex part commonly exists in genomes or functional DNA, demonstrating the high generality of our approach. Our findings are also helpful for understanding the mechanism of enzymatic DNA ligation from the viewpoint of substrate binding. Full article
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Graphical abstract
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<p>Efficient splint-free circularization using the permuted precursor for circularization (PPC) approach. (<b>A</b>) Schematic illustration of two circularization methods. (<b>B</b>) Secondary structure of C0 (simulated by Mfold). (<b>C</b>) Schematic diagram of circularizing L1 by PPC. The mismatched base pairs are also shown considering T4 Dnl can bind about 9-bp duplex at each side of the nick. (<b>D</b>,<b>E</b>) Electrophoresis analysis (12% PAGE) for circularization to prepare C1 by PPC and a previous approach, respectively. Lane 1, L1 (no T4 Dnl). Lane 2, L1 treated with T4 Dnl. Lane 3, the products in Lane 2 were further treated with Exonuclease I and Exonuclease III to remove linear substrate and polymers. Conditions: 10 μM linear ssDNA (20 μM splint in (<b>E</b>)), and 0.5 U/μL T4 Dnl, 0.1× T4 ligase buffer, 25 °C, 12 h. (<b>F</b>) Circularization of L1 at high concentrations. Other conditions: 100 μM L1, 1.0 U/μL T4 Dnl, 0.1× buffer, 30 °C, 72 h. Analyzed by 12% PAGE. Original images can be found in <a href="#app1-biomolecules-14-01027" class="html-app">Supplementary Materials</a>.</p>
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<p>The length limit for efficient circularization. (<b>A</b>) Sequences with different lengths at 5′-side and electrophoresis results. Lane 1, linear substrate. Lane 2, ligation by T4 Dnl. Lane 3, the products in Lane 2 were treated with Exonuclease I and Exonuclease III. Original images can be found in <a href="#app1-biomolecules-14-01027" class="html-app">Supplementary Materials</a>. (<b>B</b>) Circularization and adenylation yields for various sequences in Figure A. Conditions: 0.6 μM ssDNA, and 0.25 U/μL T4 Dnl in 0.1× T4 ligase buffer at 25 °C for 18 h, analyzed by 12% PAGE.</p>
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<p>Effect of nick position on circularization. (<b>A</b>) Designed ends in different positions. (<b>B</b>,<b>C</b>) Circularization results of different nicks at two conditions. The same conditions for (<b>B</b>,<b>C</b>): 0.1× T4 ligase buffer, 25 °C. Different conditions for (<b>B</b>): 0.6 μM ssDNA, 0.25 U/μL T4 Dnl, 18 h; different conditions for (<b>C</b>): 10 μM ssDNA, 1.0 U/μL T4 Dnl, 36 h. Analyzed by 12% PAGE.</p>
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<p>Effect of reaction conditions on circularization and adenylation of linear DNA substrates. (<b>A</b>) Possible secondary structures of L21. (<b>B</b>) Concentration of T4 ligase buffer. Other conditions: 0.6 μM L21, 0.15 U/μL T4 Dnl, 25 °C, 18 h. 1× T4 ligase buffer contains 10 mM MgCl<sub>2</sub>, 0.5 mM ATP, 10 mM DTT and 40 mM Tris-HCl. (<b>C</b>) Temperature. Other conditions: 0.6 μM L21, 0.15 U/μL T4 Dnl, 0.1× buffer, 18 h. (<b>D</b>) Ligation time. Other conditions: 0.6 μM L21, 0.15 U/μL T4 Dnl, 0.1× buffer. Original images can be found in <a href="#app1-biomolecules-14-01027" class="html-app">Supplementary Materials</a>.</p>
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<p>Application of the PPC method for circularization of various linear DNA substrates of L22 (<b>A</b>), L23 (<b>B</b>), L24 (<b>C</b>), L25 (<b>D</b>), and L26 (<b>E</b>). Lane 1, linear substrate; Lane 2, linear substrate treated with T4 Dnl; Lane 3, the products in lane 2 were digested with Exonuclease I and Exonuclease III. Ligation conditions: 0.6 μM linear DNA for L22 and 10 μM for other substrates, 0.5 U/μL T4 Dnl, 0.1× buffer, 25 °C, 24 h. Analyzed by 12% PAGE. Original images can be found in <a href="#app1-biomolecules-14-01027" class="html-app">Supplementary Materials</a>.</p>
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