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37 pages, 5363 KiB  
Article
Design, Synthesis, Antimicrobial Activity, and Molecular Docking of Novel Thiazoles, Pyrazoles, 1,3-Thiazepinones, and 1,2,4-Triazolopyrimidines Derived from Quinoline-Pyrido[2,3-d] Pyrimidinones
by Ameen Ali Abu-Hashem and Sami A. Al-Hussain
Pharmaceuticals 2024, 17(12), 1632; https://doi.org/10.3390/ph17121632 (registering DOI) - 4 Dec 2024
Abstract
Background: Recently, pyrido[2,3-d] pyrimidine, triazolopyrimidine, thiazolopyrimidine, quinoline, and pyrazole derivatives have gained attention due to their diverse biological activities, including antimicrobial, antioxidant, antitubercular, antitumor, anti-inflammatory, and antiviral effects. Objective: The synthesis of new heterocyclic compounds including 5-quinoline-pyrido[2,3-d] pyrimidinone ( [...] Read more.
Background: Recently, pyrido[2,3-d] pyrimidine, triazolopyrimidine, thiazolopyrimidine, quinoline, and pyrazole derivatives have gained attention due to their diverse biological activities, including antimicrobial, antioxidant, antitubercular, antitumor, anti-inflammatory, and antiviral effects. Objective: The synthesis of new heterocyclic compounds including 5-quinoline-pyrido[2,3-d] pyrimidinone (12, 4, 67), 6-quinoline-pyrido[2,3-d]thiazolo[3,2-a]pyrimidinone (3, 5, 810), 1,2,4-triazole-6-quinoline-pyrido[2,3-d]thiazolo[3,2-a]pyrimidinone (1113), and pyrido[2,3-d]thiazolo[3,2-a]pyrimidine-ethyl-(pyridine)-9-thiaazabenzo[cd]azulenone (14) derivatives was performed with high yields while evaluating antimicrobial activities. Methods: A new series of quinoline-pyrido[2,3-d]thiazolo[3,2-a]pyrimidine derivatives were prepared using a modern style and advanced technology, resulting in high yields of these new compounds. Various reagents were utilized, specifically tailored to the production needs of each compound, through reactions that included alkylation, addition, condensation, acylation, the formation of Schiff bases, and intramolecular cyclization. Results: The chemical structures of the new compounds were determined using spectroscopy analyses, including IR, NMR, and MS, achieving good yields ranging from 68% to 90% under mild conditions in a regular system. All compounds were tested for in vitro antimicrobial activity and compared to standard drugs, specifically cefotaxime sodium and nystatin. The results showed that compounds 10 to 14 exhibited excellent antimicrobial activity, with a minimum inhibitory concentration (MIC) of 1 to 5 µmol/mL, compared to that of the standard drugs, which had MIC values of 1 to 3 µmol/mL. Furthermore, molecular docking studies were conducted to explore the interactions of specific compounds with antimicrobial target proteins. The findings revealed that compounds 10 to 14 displayed significant binding energies, with ΔG values ranging from −7.20 to −11.70 kcal/mol, indicating effective binding to the active sites of antimicrobial protein receptors. Conclusions: The SAR study confirmed a relationship between antimicrobial activity and the tested compounds. Molecular docking demonstrated that compounds 10, 11, 12, 13, and 14 exhibited significant binding energy, effectively interacting with the active sites of antimicrobial protein receptors. This consistent finding supports that these new compounds’ practical and theoretical studies align regarding their antimicrobial activity. Full article
(This article belongs to the Section Medicinal Chemistry)
Show Figures

Figure 1

Figure 1
<p>Some drugs with interesting molecules of Pyrido[2,3-<span class="html-italic">d</span>] pyrimidine derivatives (all of these drugs contain the Pyrido[2,3-<span class="html-italic">d</span>] pyrimidine moiety, so this moiety is red, and all the nitrogen atoms are blue.).</p>
Full article ">Figure 2
<p>Certain drugs contain derivatives of quinoline (all of these drugs contain the quinoline moiety, so this moiety is red, and all the nitrogen atoms are blue).</p>
Full article ">Figure 3
<p>Three-dimensional representations of the compound at the binding pocket of dihydropteroate synthase of <span class="html-italic">S. aureus</span> (PDB: ID 1AD4): (<b>a</b>,<b>b</b>) <b>10</b>; (<b>c</b>,<b>d</b>) <b>11</b>; (<b>e</b>,<b>f</b>) <b>12</b>; (<b>g</b>,<b>h</b>) <b>13;</b> (<b>i</b>,<b>j</b>) <b>14;</b> and (<b>k</b>,<b>l</b>) cefotaxime.</p>
Full article ">Figure 4
<p>Three-dimensional representations of compounds at the binding pocket of DNA gyrase of <span class="html-italic">E. coli</span> (PDB: ID 7P2M): (<b>a</b>,<b>b</b>) <b>10</b>; (<b>c</b>,<b>d</b>) <b>11</b>; (<b>e</b>,<b>f</b>) <b>12</b>; (<b>g</b>,<b>h</b>) <b>13;</b> (<b>i</b>,<b>j</b>) <b>14;</b> and (<b>k</b>,<b>l</b>) cefotaxime.</p>
Full article ">Figure 5
<p>Three-dimensional representations of the compound at the binding pocket of Sortase A in <span class="html-italic">S. pyogenes</span> (PDB: ID 8T8G): (<b>a</b>,<b>b</b>) <b>10</b>; (<b>c</b>,<b>d</b>) <b>11</b>; (<b>e</b>,<b>f</b>) <b>12</b>; (<b>g</b>,<b>h</b>) <b>13</b>; (<b>i</b>,<b>j</b>) <b>14</b>; and (<b>k</b>,<b>l</b>) cefotaxime.</p>
Full article ">Figure 6
<p>Three-dimensional representations of compounds at the binding pocket of KPC-2 carbapenemase of <span class="html-italic">K. pneumoniae</span> (PDB: ID 2OV5): (<b>a</b>,<b>b</b>) <b>10</b>; (<b>c</b>,<b>d</b>) <b>11</b>; (<b>e</b>,<b>f</b>) <b>12</b>; (<b>g</b>,<b>h</b>) <b>13</b>; (<b>i</b>,<b>j</b>) <b>14</b>; and (<b>k</b>,<b>l</b>) cefotaxime.</p>
Full article ">Figure 7
<p>Three-dimensional representations of compound conformations at the binding pocket of sterol 14-alpha demethylase of <span class="html-italic">C. albicans</span> (PDB: ID 5TZ1): (<b>a</b>,<b>b</b>) <b>10</b>; (<b>c</b>,<b>d</b>) <b>11</b>; (<b>e</b>,<b>f</b>) <b>12</b>; (<b>g</b>,<b>h</b>) <b>13</b>; (<b>i</b>,<b>j</b>) <b>14</b>; and (<b>k</b>,<b>l</b>) nystatin.</p>
Full article ">Figure 8
<p>Three-dimensional representations of compound conformations at the binding pocket of the fdc1of <span class="html-italic">A. niger</span> (PDB: ID 4ZA5): (<b>a</b>,<b>b</b>) <b>10</b>; (<b>c</b>,<b>d</b>) <b>11</b>; (<b>e</b>,<b>f</b>) <b>12</b>; (<b>g</b>,<b>h</b>) <b>13;</b> (<b>i</b>,<b>j</b>) <b>14;</b> and (<b>k</b>,<b>l</b>) nystatin.</p>
Full article ">Figure 9
<p>Three-dimensional representations of compound conformations at the binding pocket of AaTPS of <span class="html-italic">Alternaria alternata</span> (PDB: ID 6LCD): (<b>a</b>,<b>b</b>) <b>10</b>; (<b>c</b>,<b>d</b>) <b>11</b>; (<b>e</b>,<b>f</b>) <b>12</b>; (<b>g</b>,<b>h</b>) <b>13</b>; (<b>i</b>,<b>j</b>) <b>14</b> and (<b>k</b>,<b>l</b>) nystatin.</p>
Full article ">Scheme 1
<p>Synthesis of 3-sub-phenyl-6-(quinoline)-pyrido[2,3-<span class="html-italic">d</span>]thiazolo[3,2-<span class="html-italic">a</span>]pyrimidinones (to clarify the type of reagents, one contains chlorine, and the other contains bromine; therefore, they are represented in different colours).</p>
Full article ">Scheme 2
<p>Synthesis of thiazole, pyrazole, and thioxopyrimidine with quinoline-pyrido[2,3-<span class="html-italic">d</span>] pyrimidinone derivatives.</p>
Full article ">Scheme 3
<p>Synthesis of hydroxyimino, 4-sub-(phenyl) acryloyl, and hydrazine-1-carbothio-amide linked to quinoline-pyrido[2,3-<span class="html-italic">d</span>]thiazolo[3,2-<span class="html-italic">a</span>] pyrimidine derivatives.</p>
Full article ">Scheme 4
<p>Synthesis of 1,3-thiazepinone and 1,2,4-triazolopyrimidine linked to quinoline-pyrido[2,3-<span class="html-italic">d</span>]thiazolo[3,2-<span class="html-italic">a</span>] pyrimidine derivatives (arrows illustrate the reaction mechanism and the formation direction of the product).</p>
Full article ">
14 pages, 2385 KiB  
Article
Preparation of Nano- and Microparticles Obtained from Polymerization Reaction and Their Application to Surface Coating of Woody Materials
by Toshinori Shimanouchi, Daichi Hirota, Masafumi Yoshida, Kazuma Yasuhara and Yukitaka Kimura
Appl. Sci. 2024, 14(23), 11326; https://doi.org/10.3390/app142311326 - 4 Dec 2024
Abstract
A surface coating of polymer particles of different hydrophobicity and wide-ranged size is helpful for the surface modification of materials such as woody thin board (WTB) derived from biomass. A preparation method for polymer particles was, in this study, proposed using a capillary-type [...] Read more.
A surface coating of polymer particles of different hydrophobicity and wide-ranged size is helpful for the surface modification of materials such as woody thin board (WTB) derived from biomass. A preparation method for polymer particles was, in this study, proposed using a capillary-type flow system. Under hydrothermal conditions, the refinement of dispersed oil droplets in water (O/W emulsions) and the polymerization reaction could be simultaneously advanced, and polymer particles of polystyrene (PS), polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), and poly-L-lactic acid (PLLA) with a particle size of about 100 nm could be synthesized. The coating of polymer particles gave an improved effect on the water repellency of WTBs due to the hydrophobicity of polymer particles and an alteration of surface roughness, and it also provided long-term stability (more than 6 years). Full article
(This article belongs to the Section Green Sustainable Science and Technology)
Show Figures

Figure 1

Figure 1
<p>(<b>a</b>) Chemical structures of monomers used in this study. (<b>b</b>) Capillary-type flow system for emulsification. Solution I included monomer, AIBN, and Tween 20 (0.006 mM). Solution II was Tween 20 (0.0045 mM). Flow rate ratio of Solutions I and II was 1:2.</p>
Full article ">Figure 2
<p>(<b>a</b>) Cryo-TEM images of O/W emulsion of styrene. (<b>b</b>) TEM image of nanoparticles made of PS. (<b>c</b>) Time course of mean diameter for PS particles. Samples at t = 0 and t &gt; 0 represent O/W emulsion without AIBN and after polymerization reaction, respectively. (<b>d</b>) Diamter distribution of PS<sub>800</sub>, PS<sub>210</sub>, and PS<sub>30</sub>. (<b>e</b>) Comparison of diameter of O/W emulsion with that of polymer particles. PSxx indicates PS with xx nm of final mean diameter.</p>
Full article ">Figure 3
<p>(<b>a</b>) Cryo-TEM images of O/W emulsions of MMA, VA, and LA. Black arrows represent O/W emulsion. (<b>b</b>) TEM images of polymer particles made of PMMA, PVA, and PLLA. (<b>c</b>) Typical time-course of polymerization of O/W emulsions. Flow rate ratio of Solutions I (0.30 mL/min) and II (0.60 mL/min) was 1:2. (<b>d</b>) Comparison of diameter of O/W emulsion with that of polymer particles.</p>
Full article ">Figure 4
<p>(<b>a</b>–<b>e</b>) SEM and (<b>f</b>–<b>h</b>) AFM images of bare WTB and WTBs coated by polystyrene particles with different diameters at two volume fractions (ϕ = 0.005 and 0.020). (<b>f′</b>–<b>h′</b>) Both side and top views of each AFM image. White and black arrows mean the step on the surface. Lines 1–1′, 2–2′, … and 7–7′ mean the step.</p>
Full article ">Figure 5
<p>Box plots of contact angles for WTBs coated by polymer particles at two ϕ values. “Bare” means the WTB without surface modification of polymer particles.</p>
Full article ">Figure 6
<p>A comparison of the contact angle of the WTB surface with the mean diameter of the polymer particles: (<b>a</b>) PS; (<b>b</b>) PMMA; (<b>c</b>) PVA; and (<b>d</b>) PLLA. White and gray keys represent WTBs modified at φ = 0.020 and 0.005, respectively. (<b>e</b>) The relationship between the contact angle limit of WTBs and logP values for each monomer. Dashed curve in (<b>a</b>–<b>d</b>) is a curve fitted with exponential relaxation.</p>
Full article ">Figure 7
<p>Long-term stability of WTBs. (<b>a</b>) WTBs modified with PS of different diameters and (<b>b</b>) four kinds of polymer particles. (<b>c</b>) Remaining ratio of WTBs. Initially, ten WTBs were prepared. Standard errors were calculated from four different experiments for each WTB.</p>
Full article ">
23 pages, 1150 KiB  
Review
Traditionally Used Medicinal Plants of Armenia
by Arpine Ayvazyan and Christian Zidorn
Plants 2024, 13(23), 3411; https://doi.org/10.3390/plants13233411 - 4 Dec 2024
Abstract
The rich and diverse flora of Armenia has been used for medicinal purposes for at least 3000 years. The relevant literature in Armenian, English, and Russian revealed a vast array of used medicinal plants, some of them unique to the Caucasus region. The [...] Read more.
The rich and diverse flora of Armenia has been used for medicinal purposes for at least 3000 years. The relevant literature in Armenian, English, and Russian revealed a vast array of used medicinal plants, some of them unique to the Caucasus region. The usage of medicinal plants confirms the position of Armenia as a country at the crossroads of Asia and Europe because of its traditional usage of medicinal plants from both continents. Literature data in Armenian, English, and Russian on medicinal plants of Armenia were mainly obtained using various electronic databases. From all available sources, 320 Armenian medicinal plant species were extracted with their botanical and local names and traditional uses. The use of medicinal plants by the Armenian people is systematically compiled, including the used plant organs and preparations and the ailments for which the various taxa are/were used. Medicinal plants of Armenia are represented for both wild and cultivated species. Some of the taxa used are unique to Armenia or the Caucasus region, while many other species are also used in various other countries. Some of the species from traditional Armenian medicine are currently being studied using modern methods. Full article
(This article belongs to the Section Phytochemistry)
17 pages, 122861 KiB  
Article
Effect of Dispersed ZrO2 Particles on Microstructure Evolution and Superconducting Properties of Nb-Ti Alloy
by Rafał Idczak, Robert Konieczny, Wojciech Nowak, Wojciech Bartz and Michał Babij
Materials 2024, 17(23), 5946; https://doi.org/10.3390/ma17235946 - 4 Dec 2024
Abstract
The influence of dispersed ZrO2 particles on the microstructure evolution and the superconducting properties of a Nb-Ti alloy was investigated. The studied materials were prepared by different methods including mechanical alloying (MA) and arc-melting. The obtained samples were studied by X-ray diffraction [...] Read more.
The influence of dispersed ZrO2 particles on the microstructure evolution and the superconducting properties of a Nb-Ti alloy was investigated. The studied materials were prepared by different methods including mechanical alloying (MA) and arc-melting. The obtained samples were studied by X-ray diffraction (XRD) and vibrating-sample magnetometer (VSM). It was found that ZrO2 particles can be successively introduced into an Fe-Nb matrix by MA. However, among all prepared samples with a nominal composition of Nb-47wt%Ti-5 wt% ZrO2, only the powders, which were prepared by MA of Nb-47wt%Ti and ZrO2 powders, exhibit superconductivity with critical parameters comparable to those observed in pristine Nb-47wt%Ti alloy. In particular, the determined upper critical field at 0 K μ0Hc2(0) is close to 15.6(1) T. This value is slightly higher than 15.3(3) T obtained for Nb-47wt%Ti and it can be ascribed to the presence of introduced ZrO2 particles in the Nb-Ti matrix. Full article
Show Figures

Figure 1

Figure 1
<p>X-ray diffraction patterns measured for powders A obtained after effective milling times up to <math display="inline"><semantics> <mrow> <mi>t</mi> <mo>=</mo> <mn>80</mn> </mrow> </semantics></math> h. Red dots and black lines represent experimental data, and the result of the Rietveld refinement, respectively, and blue line shows the difference between the two. Green dashes indicate positions of the Bragg reflections. Insets show the Williamson–Hall plot; solid line is a linear fit to data points.</p>
Full article ">Figure 2
<p>The phase composition of powders A and B. The estimated <span class="html-italic">L</span> and <math display="inline"><semantics> <mrow> <mi>C</mi> <mi>ϵ</mi> </mrow> </semantics></math> parameters for the <math display="inline"><semantics> <mrow> <mi>b</mi> <mi>c</mi> <mi>c</mi> </mrow> </semantics></math> phase.</p>
Full article ">Figure 3
<p>X-ray diffraction patterns measured for powders B obtained after effective milling times up to <math display="inline"><semantics> <mrow> <mi>t</mi> <mo>=</mo> <mn>60</mn> </mrow> </semantics></math> h. Red dots and black lines represent experimental data, and the result of the Rietveld refinement, respectively, and blue line shows the difference between the two. Green dashes indicate positions of the Bragg reflections. Insets show the Williamson–Hall plot; a solid line is a linear fit to data points.</p>
Full article ">Figure 4
<p>The SEM micrographs with marked points for EDX microanalysis of the surfaces of the powder B after 20 h of MA.</p>
Full article ">Figure 5
<p>The SEM micrographs with marked points for EDX microanalysis of the surfaces of the powder B after 60 h of MA.</p>
Full article ">Figure 6
<p>The selected temperature dependencies of mass magnetic susceptibility measured for powders A in the range of 2–15 K and in applied magnetic field up to <math display="inline"><semantics> <mrow> <msub> <mi>μ</mi> <mn>0</mn> </msub> <mi>H</mi> </mrow> </semantics></math> = 9 T.</p>
Full article ">Figure 7
<p>Real <math display="inline"><semantics> <msup> <mi>χ</mi> <mo>′</mo> </msup> </semantics></math> and imaginary <math display="inline"><semantics> <msup> <mi>χ</mi> <mrow> <mo>″</mo> </mrow> </msup> </semantics></math> parts of the ac-susceptibility measured in applied magnetic field up to <math display="inline"><semantics> <mrow> <msub> <mi>μ</mi> <mn>0</mn> </msub> <mi>H</mi> </mrow> </semantics></math> = 9 T for powder A after 10 h of MA. Solid curves serve as guides for the eye.</p>
Full article ">Figure 8
<p>Real <math display="inline"><semantics> <msup> <mi>χ</mi> <mo>′</mo> </msup> </semantics></math> and imaginary <math display="inline"><semantics> <msup> <mi>χ</mi> <mrow> <mo>″</mo> </mrow> </msup> </semantics></math> parts of the ac-susceptibility measured in applied magnetic field up to <math display="inline"><semantics> <mrow> <msub> <mi>μ</mi> <mn>0</mn> </msub> <mi>H</mi> </mrow> </semantics></math> = 9 T for powder A after 40 h of MA. Solid curves serve as guides for the eye.</p>
Full article ">Figure 9
<p>The selected temperature dependencies of mass magnetic susceptibility measured for powders B in the range of 2–15 K and in applied magnetic field up to <math display="inline"><semantics> <mrow> <msub> <mi>μ</mi> <mn>0</mn> </msub> <mi>H</mi> </mrow> </semantics></math> = 9 T.</p>
Full article ">Figure 10
<p>Real <math display="inline"><semantics> <msup> <mi>χ</mi> <mo>′</mo> </msup> </semantics></math> and imaginary <math display="inline"><semantics> <msup> <mi>χ</mi> <mrow> <mo>″</mo> </mrow> </msup> </semantics></math> parts of the ac-susceptibility measured in applied magnetic field up to <math display="inline"><semantics> <mrow> <msub> <mi>μ</mi> <mn>0</mn> </msub> <mi>H</mi> </mrow> </semantics></math> = 9 T for powder B after 10 h of MA. Solid curves serve as guides for the eye.</p>
Full article ">Figure 11
<p>Real <math display="inline"><semantics> <msup> <mi>χ</mi> <mo>′</mo> </msup> </semantics></math> and imaginary <math display="inline"><semantics> <msup> <mi>χ</mi> <mrow> <mo>″</mo> </mrow> </msup> </semantics></math> parts of the ac-susceptibility measured in applied magnetic field up to <math display="inline"><semantics> <mrow> <msub> <mi>μ</mi> <mn>0</mn> </msub> <mi>H</mi> </mrow> </semantics></math> = 9 T for powder B after 40 h of MA. Solid curves serve as guides for the eye.</p>
Full article ">Figure 12
<p>Real <math display="inline"><semantics> <msup> <mi>χ</mi> <mo>′</mo> </msup> </semantics></math> and imaginary <math display="inline"><semantics> <msup> <mi>χ</mi> <mrow> <mo>″</mo> </mrow> </msup> </semantics></math> parts of the ac-susceptibility measured in applied magnetic field up to <math display="inline"><semantics> <mrow> <msub> <mi>μ</mi> <mn>0</mn> </msub> <mi>H</mi> </mrow> </semantics></math> = 9 T for powder B after 60 h of MA. Solid curves serve as guides for the eye.</p>
Full article ">Figure 13
<p>Upper critical field of superconducting bcc alloy in powders B as a function of temperature and derived from ac-susceptibility measurements. Solid and dashed lines are simulated WHH curves.</p>
Full article ">Figure 14
<p>The temperature dependencies of mass magnetic susceptibility measured for sample C prepared by arc-melting in the range of 2–15 K and in applied magnetic field up to <math display="inline"><semantics> <mrow> <msub> <mi>μ</mi> <mn>0</mn> </msub> <mi>H</mi> </mrow> </semantics></math> = 9 T.</p>
Full article ">
12 pages, 1561 KiB  
Article
Silver Linings: Electrochemical Characterization of TiO2 Sol-Gel Coating on Ti6Al4V with AgNO3 for Antibacterial Excellence
by Julia Both, Gabriella Stefania Szabó, Alexandra Ciorîță and Liana Maria Mureșan
Coatings 2024, 14(12), 1532; https://doi.org/10.3390/coatings14121532 - 4 Dec 2024
Abstract
This study aimed to synthesize TiO2 and silver-containing TiO2 layers on Ti6Al4V titanium alloy substrates, also known as titanium grade 5 (TiGr5), to provide corrosion resistance and antibacterial activity. The TiO2 layers were prepared through the sol-gel method and dip-coating [...] Read more.
This study aimed to synthesize TiO2 and silver-containing TiO2 layers on Ti6Al4V titanium alloy substrates, also known as titanium grade 5 (TiGr5), to provide corrosion resistance and antibacterial activity. The TiO2 layers were prepared through the sol-gel method and dip-coating technique. Silver introduction into the layers was performed in two different ways. One was the impregnation method by dipping the TiO2 layer-covered metal in aqueous AgNO3 solutions of various concentrations (TiO2/AgNO3), and the other was by direct introduction of AgNO3 into the precursor sol (Ag-TiO2). The two methods for incorporating AgNO3 into the coating matrix are novel, as they preserve silver in its ionic form rather than reducing it to metallic silver. The samples were put through electrochemical characterization, namely potentiodynamic polarization and electrochemical impedance spectroscopy (EIS), and were tested in Hank’s solution, simulating a physiological environment. The behavior of the layers was monitored over time. Also, the thin layers’ thickness and adhesion to the substrate were determined. Microbiological evaluation of the Ag-doped coatings on glass substrates confirmed their significant bactericidal activity against Gram-negative Escherichia coli. Among the two types of coatings, the impregnated coatings demonstrated the most promising electrochemical performance, as evidenced by both EIS and potentiodynamic polarization analyses. Full article
(This article belongs to the Special Issue Advances in Nanostructured Thin Films and Coatings, 2nd Edition)
Show Figures

Figure 1

Figure 1
<p>(<b>A</b>) Nyquist plot and (<b>B</b>) Bode plot of TiGr5 coated with TiO<sub>2</sub> and TiO<sub>2</sub> and impregnated with 10<sup>−1</sup> M, 10<sup>−2</sup> M, and 10<sup>−3</sup> M of AgNO<sub>3</sub>, recorded in Hank’s simulated physiological serum.</p>
Full article ">Figure 2
<p>Comparative Nyquist diagram for long-term study of (<b>A</b>) TiGr5/TiO<sub>2</sub>, (<b>B</b>) TiGr5/Ag-TiO<sub>2</sub>, and (<b>C</b>) TiGr5/TiO<sub>2</sub>/AgNO<sub>3</sub> with AgNO<sub>3</sub> present in both enhanced systems at a concentration of 10<sup>−2</sup> M.</p>
Full article ">Figure 3
<p>Comparative Bode plots for long-term study of (<b>A</b>) TiGr5/TiO<sub>2</sub>, (<b>B</b>) TiGr5/Ag-TiO<sub>2</sub>, and (<b>C</b>) TiGr5/TiO<sub>2</sub>/AgNO<sub>3</sub> with AgNO<sub>3</sub> present in both enhanced systems at a concentration of 10<sup>−2</sup> M.</p>
Full article ">Figure 4
<p>Comparison of the |Z|<sub>0.01Hz</sub> for TiGr5/TiO<sub>2</sub>, TiGr5/Ag-TiO<sub>2</sub>, and TiGr5/TiO<sub>2</sub>/AgNO<sub>3</sub>.</p>
Full article ">Figure 5
<p>Polarization curves of TiGr5, TiGr5/TiO<sub>2</sub>, TiGr5/Ag-TiO<sub>2</sub>, and TiGr5/TiO<sub>2</sub>/AgNO<sub>3</sub> recorded in Hank’s simulated physiological solution.</p>
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<p>Antimicrobial analysis performed on <b>0</b>. Untreated sample in bacterial suspension and medium, <b>1</b>. TiO<sub>2</sub> coating, <b>2</b>–<b>4</b>. TiO<sub>2</sub>/AgNO<sub>3</sub> (10<sup>−3</sup> M, 10<sup>−2</sup> M, 10<sup>−1</sup> M), <b>5</b>. TiGr5/Ag-TiO<sub>2</sub>.</p>
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18 pages, 6357 KiB  
Article
Liposomal and Nanostructured Lipid Nanoformulations of a Pentacyclic Triterpenoid Birch Bark Extract: Structural Characterization and In Vitro Effects on Melanoma B16-F10 and Walker 256 Tumor Cells Apoptosis
by Dumitriţa Rugină, Mihai Adrian Socaciu, Madalina Nistor, Zorita Diaconeasa, Mihai Cenariu, Flaviu Alexandru Tabaran and Carmen Socaciu
Pharmaceuticals 2024, 17(12), 1630; https://doi.org/10.3390/ph17121630 - 4 Dec 2024
Abstract
Background/Objectives: Pentacyclic triterpenoids are increasingly studied as anticancer agents with many advantages compared to synthetic chemotherapeutics. The aim of this study was to prepare liposomal and nanostructured lipid formulations including a standardized extract of silver birch (Betula pendula) outer bark [...] Read more.
Background/Objectives: Pentacyclic triterpenoids are increasingly studied as anticancer agents with many advantages compared to synthetic chemotherapeutics. The aim of this study was to prepare liposomal and nanostructured lipid formulations including a standardized extract of silver birch (Betula pendula) outer bark (TTs) and to evaluate their potential as anticancer agents in vitro, using Melanoma B16-F10 and Walker carcinoma cells. Methods: Appropriate solvents were selected for efficient TTs extraction, and original recipes were used to obtain Pegylated liposomes and nanolipid complexes with entrapped TTs, comparative to pure standards (betulinic acid and doxorubicin) in similar conditions. The composition, morphology, and sizes of all nanoformulations were checked by high-performance liquid chromatography/mass spectrometry, Transmission Electronic Microscopy, and Diffraction Light Scattering. The entrapment efficiency and its impact on cell viability, cell cycle arrest, and apoptosis by flow cytometry was also measured on both cancer cell lines. Conclusions: The standardized TTs, including betulin, lupeol, and betulinic acid, showed good stability and superior activity compared to pure betulinic acid. According to experimental data, TTs showed good entrapment in liposomal and NLC nanoformulations, both delivery systems including natural, biodegradable ingredients and enhanced bioavailability. The apoptosis and necrosis effects were more pronounced for TTs liposomal formulations in both types of cancer cells, with lower cytotoxicity compared to Doxorubicin, and can be correlated with their increased bioavailability. Full article
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<p>Most representative pentacyclic lupane-type triterpenoids in birch bark extracts: structure, molecular weight [MW], and maximal UV absorption.</p>
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<p>Morphology of Lipo and NLC nanoformulations containing AB, TTs, and Doxo, comparative to controls, as determined by TEM. Size distribution diameters (mean ± SD) (nm) of the formulations, the encapsulation efficiency (EE% ± SD), and the PDI values are included. The final concentrations (C<sub>f</sub>) for each nanoformulation including AB, TT, and Doxo were mentioned.</p>
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<p>(<b>a</b>–<b>l</b>) The flow cytometry distribution of cell cycle affected in Melanoma B16-F10 cell population. (<b>a</b>) Non-treated cells. (<b>b</b>,<b>c</b>) After incubation with Lipo and NLC controls. (<b>d</b>–<b>f</b>) After incubation with AB, TTs, and Doxo. (<b>g</b>–<b>i</b>) After incubation with Lipo-AB, Lipo-TTs and Lipo-Doxo. (<b>j</b>–<b>l</b>) After incubation with NLC-AB, NLC-TTs, NLC-Doxo.</p>
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<p>(<b>a</b>–<b>l</b>) The flow cytometry distribution of cell cycle affected in Melanoma B16-F10 cell population. (<b>a</b>) Non-treated cells. (<b>b</b>,<b>c</b>) After incubation with Lipo and NLC controls. (<b>d</b>–<b>f</b>) After incubation with AB, TTs, and Doxo. (<b>g</b>–<b>i</b>) After incubation with Lipo-AB, Lipo-TTs and Lipo-Doxo. (<b>j</b>–<b>l</b>) After incubation with NLC-AB, NLC-TTs, NLC-Doxo.</p>
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<p>(<b>a</b>–<b>l</b>) The flow cytometry distribution of cell cycle affected Walker 256 cacinoma cell population. (<b>a</b>) Non-treated cells. (<b>b</b>,<b>c</b>) After incubation with Lipo and NLC controls. (<b>d</b>–<b>f</b>) After incubation with AB, TTs, and Doxo. (<b>g</b>–<b>i</b>) After incubation with Lipo-AB, Lipo-TTs and Lipo-Doxo. (<b>j</b>–<b>l</b>) After incubation with NLC-AB, NLC-TTs, and NLC-Doxo.</p>
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<p>(<b>a</b>–<b>l</b>) The flow cytometry distribution of cell cycle affected Walker 256 cacinoma cell population. (<b>a</b>) Non-treated cells. (<b>b</b>,<b>c</b>) After incubation with Lipo and NLC controls. (<b>d</b>–<b>f</b>) After incubation with AB, TTs, and Doxo. (<b>g</b>–<b>i</b>) After incubation with Lipo-AB, Lipo-TTs and Lipo-Doxo. (<b>j</b>–<b>l</b>) After incubation with NLC-AB, NLC-TTs, and NLC-Doxo.</p>
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<p>Comparative effects of Lipo- and NLC-nanoformulations and free extracts (TTs, AB and Doxo) on Melanoma B16-F10 (<b>A</b>) and Walker 256 (<b>B</b>) cell cycle.</p>
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<p>Comparative results of Annexin V/propidium iodide-stained flow cytometry for Melanoma B16F10 (<b>a</b>,<b>c</b>,<b>e</b>,<b>g</b>) and Walker 256 cells (<b>b</b>,<b>d</b>,<b>f</b>,<b>h</b>) after 24 h of incubation. (<b>a</b>) Melanoma B16F10 untreated cells; (<b>b</b>) Walker 256 untreated cells; (<b>c</b>,<b>e</b>,<b>g</b>) Melanoma B16F10 incubated with AB, TTs and Doxo; (<b>d</b>,<b>f</b>,<b>h</b>) Walker 256 cells incubated with AB, TTs, and Doxo. Q1 + Q2 = A (early and late apoptosis); Q3—viable cells; Q4—necrosis.</p>
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<p>Comparative results of Annexin V/propidium iodide-stained flow cytometry for Melanoma B16F10 (<b>a</b>,<b>c</b>,<b>e</b>,<b>g</b>) and Walker 256 cells (<b>b</b>,<b>d</b>,<b>f</b>,<b>h</b>) after 24 h of incubation. (<b>a</b>) Melanoma B16F10 untreated cells; (<b>b</b>) Walker 256 untreated cells; (<b>c</b>,<b>e</b>,<b>g</b>) Melanoma B16F10 incubated with AB, TTs and Doxo; (<b>d</b>,<b>f</b>,<b>h</b>) Walker 256 cells incubated with AB, TTs, and Doxo. Q1 + Q2 = A (early and late apoptosis); Q3—viable cells; Q4—necrosis.</p>
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<p>Histograms showing the comparative percentages of apoptotic cells ((<b>A</b>) melanoma B16-F10; (<b>B</b>) Walker 256) and necrotic cells ((<b>C</b>) melanoma B16-F10; (<b>D</b>) Walker 256) after the treatment with different Lipo- and NLC-formulations comparative to free molecules Doxo, AB, and TTs controls. A = Q1 + Q2 (early and late apoptosis); Q4—necrosis.</p>
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20 pages, 9805 KiB  
Article
Evaluation of Shade Integration of a Novel Universal-Shade Flowable Bulk-Filling Resin Composite
by Hirofumi Kaneko, Chiharu Kawamoto, Yu Toida, Ryotaro Yago, Di Wu, Yuan Yuan, Fei Chen, Monica Yamauti, Hidehiko Sano and Atsushi Tomokiyo
Materials 2024, 17(23), 5944; https://doi.org/10.3390/ma17235944 - 4 Dec 2024
Abstract
Background: This study aimed to evaluate the color-matching and light transmission properties of a newly developed aesthetic flowable resin composite, OCFB-001. Methods: Rubber molds containing cylindrical cavities were filled with Estelite Sigma Quick, and 40 resin composite (CR) molds with simulated Class I [...] Read more.
Background: This study aimed to evaluate the color-matching and light transmission properties of a newly developed aesthetic flowable resin composite, OCFB-001. Methods: Rubber molds containing cylindrical cavities were filled with Estelite Sigma Quick, and 40 resin composite (CR) molds with simulated Class I cavities were prepared in shades A1, A2, A3, and A4, resulting in a total of 160 samples. Following bonding procedures, four different flowable resin composites (n = 10) were introduced into the cavities. The color difference (ΔE00) was calculated using two methods. A two-way analysis of variance was performed, and the interaction was significant, so a post hoc analysis was performed for each shade using Bonferroni’s correction. The morphology of the filler in each material was observed via scanning electron microscopy (SEM). Results: In the A1 shade, OCFB-001 demonstrated color differences comparable to those of other materials. However, in the A2, A3, and A4 shades, OCFB-001 exhibited significantly lower color differences (ΔE00) than the other materials, with a more consistent distribution. SEM analysis revealed that the OCFB-001 structure resembled that of Estelite Bulk Fill Flowable. Conclusions: OCFB-001 showed excellent shade matching in the A2, A3, and A4 ranges and good matching in the A1 shade, on par with existing universal-shade flowable bulk-fill resin composites. Full article
(This article belongs to the Special Issue Recent Research in Restorative Dental Materials)
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<p>Diagrammatic representation of the specimen preparation for color measurement. The original acrylic block was placed on a glass slide with the cavity facing upward, filled with silicone impression material in a plastic case, and impressions were taken (<b>A</b>). A plastic case, the original acrylic block and slide glass were removed (<b>B</b>). The silicone mold was stored at room temperature in an incubator for 24 h to ensure complete reaction and to mitigate any potential hydrogen gas release (<b>C</b>). Using rubber molds, 160 frames were created in shades A1, A2, A3, and A4 (<span class="html-italic">n</span> = 40 per shades) by filling the molds with ESQ resin composite. The ESQ resin composite was light-cured with an LED curing unit (<b>D</b>). These cavities with ESQ framing were treated with a chemical-cure adhesive. Then, four types of resin composites were used to fill the simulated cavities (<span class="html-italic">n</span> = 10 per type).The four resin composites were filled in batches and light-cured for 10 s using an LED curing unit at an intensity of 1470 mW/cm<sup>2</sup> (<b>E</b>). The surfaces of the restorations were polished with 400- and 1500-grit silicon carbide waterproof abrasive paper for 30 s (<b>F</b>). The polished specimens were stored in distilled water at 37 °C for 24 h (<b>G</b>). The Lab values were measured by two different methods and the color difference was calculated. Colorimetry was performed by two methods: (a) colorimetry using a colorimeter, and (b) an intraoral camera was used to capture images of specimens with color- and size-matching stickers placed on color reference tiles, which were then measured using image-processing software (digital photo analysis method) (<b>H</b>).</p>
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<p>Photographic conditions (colorimeter).</p>
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<p>Measurement area dimensions (colorimeter). The measurement spot should be selected at least 0.3 mm away from the margin, avoiding the intersection between the four filled and framed resin composites. The four filled resin composites tested and the center of the sample were selected (A). The Frame resin composites, the midpoint between the margin and the edge were selected (B).</p>
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<p>Photographic conditions (digital photo analysis method).</p>
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<p>The typical image with color chart and measurement area dimensions (digital photo analysis method). The measurement spot should be selected at least 0.3 mm away from the margin, avoiding the intersection between the four filled and framed resin composites.</p>
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<p>The color difference between four tested materials and resin composites (colorimeter). The perception threshold (PT) in CIEDE2000 was set at 0.8, and the acceptance threshold (AT) at 1.8. The letter differences indicate significant differences between materials of the same shade (<span class="html-italic">p</span> &lt; 0.05).</p>
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<p>The color difference between the four tested materials and resin composites (digital photo analysis method). The perception threshold (PT) in CIEDE2000 was set at 0.8, and the acceptance threshold (AT) at 1.8. The letter differences indicate significant differences between materials of the same shade (<span class="html-italic">p</span> &lt; 0.05).</p>
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<p>The images of the filled tested resin composites.</p>
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<p>Two-dimensional analysis of light transmittance properties. The horizontal axis of the graph represents the measurement range (°), and the vertical axis represents the intensity (relative value, no unit). The light transmittance of each material was measured five times, with each measurement represented by a distinct line in the graph, differentiated by five colors.</p>
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<p>SEM images display the fillers within the tested resin composites and the resin composite frame. The left column presents images at ×10,000 magnification, while the right column showcases images at ×20,000 magnification. (<b>A</b>,<b>a</b>) OCFB fillers, (<b>B</b>,<b>b</b>) FiBF fillers, (<b>C</b>,<b>c</b>) SDR fillers, (<b>D</b>,<b>d</b>) EsBF fillers, and (<b>E</b>,<b>e</b>) the ESQ resin composite frame.</p>
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<p>Comparison of colorimeters and CASMATCH (the white and black backgrounds). The solid line in the graph shows the color difference of the colorimeter, and the dashed line shows the color difference of the digital photo analysis method. The black color in the error bar indicates the colorimeter and the red color indicates the digital photo analysis method. * In the figure indicates a significant difference between the two groups (<span class="html-italic">p</span> &lt; 0.05).</p>
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18 pages, 6951 KiB  
Review
Glycine-Based [3+2] Cycloaddition for the Synthesis of Pyrrolidine-Containing Polycyclic Compounds
by Tieli Zhou, Xiaofeng Zhang, Desheng Zhan and Wei Zhang
Molecules 2024, 29(23), 5726; https://doi.org/10.3390/molecules29235726 - 4 Dec 2024
Abstract
The synthesis of pyrrolidine compounds with biological interest is an active research topic. Glycine could be a versatile starting material for making pyrrolidine derivatives. This review covers recent works on glycine-based [3+2] cycloaddition and combines other annulation reactions in the one-pot synthesis of [...] Read more.
The synthesis of pyrrolidine compounds with biological interest is an active research topic. Glycine could be a versatile starting material for making pyrrolidine derivatives. This review covers recent works on glycine-based [3+2] cycloaddition and combines other annulation reactions in the one-pot synthesis of pyrrolidine-containing heterocyclic compounds. Synthetic method development, substrate scope, and reaction mechanisms are discussed. Applications of the compounds in drug discovery are briefly mentioned. This paper is helpful for chemists in the development of efficient and sustainable methods for the preparation of bioactive pyrrolidine compounds. Full article
(This article belongs to the Special Issue Cyclization Reactions in the Synthesis of Heterocyclic Compounds)
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<p>Representative pyrrolidine-containing natural products.</p>
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<p>Representative FDA-approved pyrrolidine-containing drugs.</p>
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<p>Pyrrolizidine- and indolizidine-bearing natural products.</p>
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<p>Bioactive compounds containing pyrrolidine.</p>
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<p>Examples of HCV NS5B inhibitors.</p>
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<p>Pyrrolidine-containing fused and spiro natural products.</p>
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<p>Pyrrolidine-containing congregated polycyclic natural products.</p>
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<p>The formation of semi- and non-stabilized AMYs from glycines.</p>
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<p>Synthesis of pyrrolizidines <b>30</b>.</p>
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<p>Synthesis of indolizidines <b>31</b>.</p>
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<p>Preparation of aldehyde <b>35</b>.</p>
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<p>Intermolecular cycloaddition for indolizidine <b>36</b>.</p>
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<p>Preparation of intermediates <b>44</b>, <b>47</b>, and <b>49</b>.</p>
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<p>Synthesis of octahydro-1<span class="html-italic">H</span>-pyrrolo[3,2-<span class="html-italic">c</span>]pyridines and octahydropyrano[4,3-<span class="html-italic">b</span>]pyrroles.</p>
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<p>The synthesis of cis-pentacyclic compounds <b>41</b>.</p>
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<p>Synthesis of <span class="html-italic">trans</span>-pentacyclic compounds <b>42</b> and their bioactivities.</p>
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<p>Two enantiomers of compound <b>42j</b> and their bioactivities.</p>
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<p>Pseudo five-component synthesis of tetracyclic pyrrolizidines <b>73</b>.</p>
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<p>Synthesis of tetracyclic pyrrolizidines <b>74</b>.</p>
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<p>One-pot and two-step synthesis of tetracyclic pyrrolizidines <b>75</b>.</p>
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<p>Double cycloaddition involving glycine and olefinic oxindoles.</p>
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<p>Comparison of maleimides and olefinic oxindoles in double cycloadditions.</p>
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<p>Cyclization and cycloaddition cascade for constructing tricyclic amines.</p>
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<p>Preparation of multi-functional aldehydes <b>99</b>–<b>101</b>.</p>
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<p>The synthesis of tricyclic amines <b>102</b> and <b>103</b>.</p>
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<p>Synthesis of tricyclic amines <b>104</b> and <b>105</b>.</p>
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<p>Preparation of multi-functional compound <b>115</b>.</p>
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<p>Synthesis of aspidosperma alkaloids <b>82</b>, <b>83</b>, and <b>118</b>.</p>
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<p>Preparation of multi-functional aldehydes <b>122</b> (<b>A</b>) and <b>126</b> (<b>B</b>).</p>
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<p>The synthesis of tricyclic amine <b>129</b>.</p>
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<p>The synthesis of tricyclic amine <b>132</b>.</p>
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<p>Preparation of multi-functional aldehydes <b>133</b> and <b>135</b>.</p>
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<p>Synthesis of tricyclic amines <b>136</b>, <b>138</b>, and <b>139</b>.</p>
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<p>Synthesis of tricyclic amines <b>140</b> and <b>141</b>.</p>
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<p>Preparation of multi-functional aldehyde <b>147</b>.</p>
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<p>The synthesis of bridged tricyclic amines <b>148</b> and <b>149</b>.</p>
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<p>The synthesis of bridged tricyclic amines <b>152</b>.</p>
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34 pages, 116270 KiB  
Article
Methods for Quality Assessment of Window View
by Barbara Szybinska Matusiak, Filomena Russo, Mandana Sarey Khanie, Natalia Sokol, Christina Hemauer, Klaus Martiny, Carlo Volf, Siegrun Appelt, Natalia Giraldo Vasquez and Aicha Diakite-Kortlever
Land 2024, 13(12), 2090; https://doi.org/10.3390/land13122090 (registering DOI) - 4 Dec 2024
Abstract
This paper summarises findings from two workshops evaluating a series of views in various settings by an interdisciplinary group of experts. In the first one (Trondheim, June 2022), ten experts visited and assessed views from nine rooms. In the second one (Lausanne, June [...] Read more.
This paper summarises findings from two workshops evaluating a series of views in various settings by an interdisciplinary group of experts. In the first one (Trondheim, June 2022), ten experts visited and assessed views from nine rooms. In the second one (Lausanne, June 2023), eleven experts assessed window views from four spaces. The workshops’ main objective was to develop and test multi-method assessments of window views. During both workshops, participants completed a survey that included close and open-ended questions about the perceived quality of the room and the view. Participants also measured lux level, took photographs, made hand drawings of the view, and answered a questionnaire about their mood and the environmental conditions in the room. After the workshop, point-in-time daylight simulations were performed for the visited rooms. The paper describes, compares, and recommends the use of the aforementioned methods depending on the type and complexity of the view, and the space, the evaluators’ professional background, and the type of collected data. It also discusses the overlap of the methods and estimates the preparation time, time spent on site, and the amount of work after the visit. Finally, it recommends the use of the tested methods depending on the application. Full article
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<p>Summary of Methods. The data related to items 1. to 4. (<a href="#land-13-02090-f001" class="html-fig">Figure 1</a>) was collected in situ during visits to each of the 4 locations, with data analysis performed after all visits were completed. The order for the completion of the tasks related to items 1. to 4. was not prescriptive; however, all tasks needed to be completed during the visit to each of the 4 locations. Items (2A.–2D.) were part of a questionnaire, whilst Item 5. was carried out after the site visits were completed.</p>
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<p>Plan drawings of the rooms (R1: Hotel Lobby, R2: Hotel Room, R3: Motorway Café, R4: Lake Restaurant) with participants’ positions marked and their predominant views. Blue points indicate sitting positions, and red arrows refer to the preferred views captured by the drawing or the photograph. The formats of the photos (different phone cameras) and the sizes of the drawings on the A4 tracing paper vary. The numbers on the photos and drawings refer only to the sitting position of the participants. They indicate how views are changed due to the sitting position of the participant.</p>
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<p>Plan drawings of the rooms (R1: Hotel Lobby, R2: Hotel Room, R3: Motorway Café, R4: Lake Restaurant) with participants’ positions marked and their predominant views. Blue points indicate sitting positions, and red arrows refer to the preferred views captured by the drawing or the photograph. The formats of the photos (different phone cameras) and the sizes of the drawings on the A4 tracing paper vary. The numbers on the photos and drawings refer only to the sitting position of the participants. They indicate how views are changed due to the sitting position of the participant.</p>
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<p>Daylight simulations and in situ illuminance measurements (lux).</p>
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<p>Overview of the scores for view impressions divided among the four evaluated spaces: (<b>a</b>) Hotel Lobby, (<b>b</b>) Hotel Room, (<b>c</b>) Motorway Café, and (<b>d</b>) Lake Restaurant.</p>
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<p>Overview of the scores for room impressions divided among the four evaluated spaces: (<b>a</b>) Hotel Lobby, (<b>b</b>) Hotel Room, (<b>c</b>) Motorway Café, and (<b>d</b>) Lake Restaurant.</p>
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<p>Percentage responses for different spaces in terms of: (<b>a</b>) first impression of the view and (<b>b</b>) overall impression and first impression of the view.</p>
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<p>This plot helps to compare visually the effects of each descriptor: (<b>a</b>) random intercept mode, and (<b>b</b>) random slope model.</p>
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<p>Positive Sentiment Word Frequency Treemap Summary.</p>
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<p>Heatmaps for each room (R1: Hotel Lobby, R2: Hotel Room, R3: Motorway Café, R4: Lake Restaurant) illustrate drawn and rated elements for each room. The intensity of the colours indicates how many participants assess a particular element.</p>
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<p>Heatmaps for each room (R1: Hotel Lobby, R2: Hotel Room, R3: Motorway Café, R4: Lake Restaurant) illustrate drawn and rated elements for each room. The intensity of the colours indicates how many participants assess a particular element.</p>
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<p>Q20. Psychological Comfort—Participants’ Individual Scores and Q21. Environmental Comfort—Participants’ Individual Scores for Rooms 1, 2, 3, and 4. The data from Participant 11 is missing for two of environmental comfort questions, therefore the ‘spider’ plots have open lines.</p>
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<p>Q20. Psychological Comfort—Participants’ Individual Scores and Q21. Environmental Comfort—Participants’ Individual Scores for Rooms 1, 2, 3, and 4. The data from Participant 11 is missing for two of environmental comfort questions, therefore the ‘spider’ plots have open lines.</p>
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<p>Overlap between Methods.</p>
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13 pages, 3345 KiB  
Article
Enhancement of Anti-UV Aging Performance of Asphalt Modified by UV-531/Pigment Violet Composite Light Stabilizers
by Fa Zhang, Yang Liu, Zhenhao Cao, Yifan Liu, Yufang Ren, Haishan Liang, Kunyu Wang, Yanyan Zhang, Jia Wang and Xue Li
Processes 2024, 12(12), 2758; https://doi.org/10.3390/pr12122758 - 4 Dec 2024
Abstract
Ultraviolet (UV) radiation accelerates the aging of asphalt pavements and shortens the service life of the pavement. To effectively mitigate the impact of UV aging on asphalt performance, a novel composite anti-UV aging agent, 2-hydroxy-4-n-octyoxybenzophenone/pigment violet (UV-531/PV), was developed. After UV-accelerated aging, the [...] Read more.
Ultraviolet (UV) radiation accelerates the aging of asphalt pavements and shortens the service life of the pavement. To effectively mitigate the impact of UV aging on asphalt performance, a novel composite anti-UV aging agent, 2-hydroxy-4-n-octyoxybenzophenone/pigment violet (UV-531/PV), was developed. After UV-accelerated aging, the modified asphalt samples were characterized by conventional performance tests, Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), and a dynamic shear rheometer (DSR). The results show that UV-531/PV-composite-modified asphalt maintains excellent conventional properties after UV aging. The FTIR testing showed that the changes in carbonyl index (Ic=o) and sulfoxide index (Is=o) of the composite-modified asphalt were significantly smaller than those of the matrix asphalt, indicating the less oxidation degree of the composite-modified asphalt. The GPC test results showed that the change in molecular weight of the composite-modified asphalt after UV aging was less than that of the matrix asphalt. DSR results showed that UV-531/PV-modified asphalt exhibited higher viscoelasticity and higher rutting resistance than unmodified asphalt. This study proposes a new method for preparing anti-UV aging asphalt, which can be used for micro-surfacing, fog sealing or ultra-thin overlay on road surfaces. Full article
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<p>UV-vis spectra of a—UV-531/PV, b—UV-531 and c—PV.</p>
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<p>Softening point (<b>a</b>), penetration (<b>b</b>), and ductility (<b>c</b>) of matrix asphalt and various modified asphalts before UV.</p>
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<p>Softening point (<b>a</b>), ductility (<b>b</b>), and penetration (<b>c</b>) of matrix asphalt and various modified asphalts after UV aging for different times.</p>
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<p>FTIR spectra of (<b>a</b>) matrix asphalt, (<b>b</b>) UV-531-modified asphalt, (<b>c</b>) PV-modified asphalt, (<b>d</b>) UV-531/PV-composite-modified asphalt and (<b>e</b>) 1800~600 wavenumbers before and after UV aging.</p>
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<p>GPC curves of (<b>a</b>) matrix asphalt and (<b>b</b>) UV-531/PV-composite-modified asphalt before and after aging.</p>
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<p>Storage modulus before and after UV aging of matrix asphalt (<b>a</b>) and UV-531/PV-composite-modified asphalt (<b>b</b>).</p>
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<p>Loss modulus before UV aging of matrix asphalt (<b>a</b>) and UV-531/PV-composite-modified asphalt (<b>b</b>).</p>
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15 pages, 5015 KiB  
Article
Application of Whisker-Toughened Aerogel to Recycling of Used Polyurethane Sheets
by Xiaohua Gu, Jiatong Chen, Shangwen Zhu, Qinglong Zhao, Yanxun Zhang and Qingyong Su
Gels 2024, 10(12), 793; https://doi.org/10.3390/gels10120793 - 4 Dec 2024
Abstract
In this study, a new environmentally friendly and efficient method for recycling and reusing waste polyurethane sheets is proposed. SiO2 aerogel was prepared using the sol–gel method, and mullite whiskers were introduced to enhance its toughness. The whisker-toughened aerogel was used in [...] Read more.
In this study, a new environmentally friendly and efficient method for recycling and reusing waste polyurethane sheets is proposed. SiO2 aerogel was prepared using the sol–gel method, and mullite whiskers were introduced to enhance its toughness. The whisker-toughened aerogel was used in the degradation of waste polyurethane to produce modified recycled polyol, which was subsequently used to prepare recycled polyurethane foam insulation material. Following a series of tests, including Fourier-transform infrared spectroscopy, apparent density, viscosity, heat loss, and thermal conductivity, the results showed that when the aerogel with wt% = 0.9% mullite whiskers and 0.06 g of whisker-toughened aerogel were added, the viscosity was close to that of polyether polyol 4110. The optimal compressive strength of the resulting composite blister structure reached 817.93 MPa, with a thermal conductivity of 0.0228 W·(m·K)−1, demonstrating good thermal stability. These results indicate that the whisker-toughened aerogel effectively reduces the viscosity of the degraded materials and significantly improves the mechanical properties and thermal stability of the regenerated polyurethane thermal insulation materials. This research provides new ideas and new methods for waste polyurethane recycling and offers a new perspective for the research and development of thermal insulation materials. Full article
(This article belongs to the Special Issue Aerogels: Synthesis and Applications)
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<p>Scanning electron microscopy of SiO2 aerogel with different whisker contents: (<b>a</b>) whisker wt% = 0.6%; (<b>b</b>) whisker wt% = 0.9%; (<b>c</b>) whisker wt% = 1.2%.</p>
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<p>Scanning electron microscopy of SiO2 aerogel with different whisker contents: (<b>a</b>) whisker wt% = 0.6%; (<b>b</b>) whisker wt% = 0.9%; (<b>c</b>) whisker wt% = 1.2%.</p>
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<p>Infrared spectra of recycled polyurethane foam with different silica aerogel additions.</p>
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<p>Wall thickness, pore size, and skeleton length of recycled polyurethane foams prepared using silica aerogel with different compositions and additions.</p>
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<p>Micrographs of recycled polyurethane foams prepared with different additive levels: (<b>a</b>) 0.02 g; (<b>b</b>) 0.06 g; (<b>c</b>) 0.1 g.</p>
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<p>Samples of recycled polyurethane foam prepared with different silica aerogel additions (from left to right, with two each of 0.02 g, 0.06 g, and 0.1 g).</p>
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<p>Density of recycled polyurethane foam samples prepared with different silica aerogel additions.</p>
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<p>Compressive strengths of different regenerated polyurethanes prepared from silica aerogels with different compositions and contents.</p>
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<p>Heat loss spectra of recycled polyurethane foams with different silica aerogel additions.</p>
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<p>Mechanism of whisker-toughened silica aerogel-reinforced polyurethane foam.</p>
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<p>Heat insulation mechanism of whisker-toughened silica aerogel-regenerated polyol-based polyurethane nanocomposites.</p>
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<p>Mechanism of silica aerogel preparation using sol–gel method.</p>
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14 pages, 2623 KiB  
Article
Effect of Gold Nanoparticles on Luminescence Enhancement in Antibodies for TORCH Detection
by Cuimei Chen and Ping Ding
Molecules 2024, 29(23), 5722; https://doi.org/10.3390/molecules29235722 - 4 Dec 2024
Abstract
Purposes: To explore the optimization method and application of Au-NP-enhanced luminol––H2O2 luminescence system in TORCH (TOX, RV, CMV, HSVI, and HSVII) detection. Method: 4.5 × 10−5 mmol/L gold nano solution was prepared with chloroauric acid as the reducing agent [...] Read more.
Purposes: To explore the optimization method and application of Au-NP-enhanced luminol––H2O2 luminescence system in TORCH (TOX, RV, CMV, HSVI, and HSVII) detection. Method: 4.5 × 10−5 mmol/L gold nano solution was prepared with chloroauric acid as the reducing agent and trisodium citrate as the stabilizer. After curing for 3 days, Au NPs participate in the luminal–H2O2 luminescence system to detect TORCH antibodies and establish the cut off value. SPSS 18.0 software was used to analyze the TORCH antibodies detected by the nano-gold-enhanced luminol luminescence method and TORCH kit. Additionally, its detection performance is studied. Results: The results of a paired t-test for the absorbance values of samples with and without gold nanoparticles showed that there were statistically significant differences (p < 0.001) between the two methods in the detection of TOX, RV, CMV, HSVI, and HSVII. The luminescence values with the addition of gold nanoparticles were significantly higher than those without gold nanoparticles. Using the Au NP–luminol–H2O2 chemiluminescence method, 127 serum samples were tested for TORCH antibodies. The sensitivities were 84.6%, 83.3%, 90.9%, 85.7%, and 84.6%, while the specificities were 94.7%, 96.5%, 96.6%, 97.3%, and 95.6%, respectively. The sensitivity and specificity of the chemiluminescence method enhanced by gold nanoparticles are significantly improved compared to the chemiluminescence method without enhancers. Conclusions: Au NPs participate in the luminal–H2O2 luminescent system. The absorbance, sensitivity, and specificity of TORCH antibodies show that Au NPs can enhance the luminol–H2O2 luminescent system. Au NP–luminol–H2O2 luminescence system has broad application prospects in the detection of eugenics. Full article
(This article belongs to the Section Nanochemistry)
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<p>(<b>A</b>) UV–vis spectrum of Au NPs; (<b>B</b>) TEM image of Au NPs.</p>
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<p>Effect of curing time on catalytic activity of Au NPs.</p>
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<p>Effect of Au-NPs concentration on the luminescence value of the system.</p>
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<p>Comparison of sensitivity between Au-NP/luminol–H<sub>2</sub>O<sub>2</sub> and non Au-NP/luminol–H<sub>2</sub>O<sub>2</sub>.</p>
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<p>Comparison of specificity between Au-NP/luminol–H<sub>2</sub>O<sub>2</sub> and non Au-NP/luminol–H<sub>2</sub>O<sub>2</sub>.</p>
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<p>Process of Au-NP-enhanced luminol chemiluminescence detection of TORCH antibodies.</p>
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<p>Diagram for formation of HO- free radicals in luminol–H<sub>2</sub>O<sub>2</sub> system.</p>
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12 pages, 4885 KiB  
Communication
Preparation and the Photoelectric Properties of ZnO-SiO2 Films with a Sol–Gel Method Combined with Spin-Coating
by Ziyang Zhou, Weiye Yang, Hongyan Peng and Shihua Zhao
Sensors 2024, 24(23), 7751; https://doi.org/10.3390/s24237751 - 4 Dec 2024
Abstract
This study explores the fabrication of ZnO-SiO2 composite films on silicon substrates via a sol–gel method combined with spin-coating, followed by annealing at various temperatures. The research aims to enhance the UV emission and photoelectric properties of the films. XRD showed that [...] Read more.
This study explores the fabrication of ZnO-SiO2 composite films on silicon substrates via a sol–gel method combined with spin-coating, followed by annealing at various temperatures. The research aims to enhance the UV emission and photoelectric properties of the films. XRD showed that the prepared ZnO sample has a hexagonal structure. SEM images revealed the formation of ZnO nanorods within a dense SiO2 substrate, ranging from 10 μm to 30 μm in length. Photoluminescent analysis showed that the film exhibited strong UV emission centered at 360 nm. The response time measurements indicated that the optimal photoresponse time was approximately 2.9 s. These results suggest the potential of ZnO-SiO2 films as efficient UV-emitting materials with high photoconductivity and a stably reproducible response under visible light, thereby laying the foundation for their application in advanced optoelectronic devices. Full article
(This article belongs to the Section Optical Sensors)
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<p>XRD patterns of the prepared samples annealed at 300 °C, 500 °C, and 700 °C.</p>
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<p>SEM images of ZnO-SiO<sub>2</sub> films annealed at different temperatures: (<b>a</b>) annealed at 300 °C; (<b>b</b>) annealed at 500 °C.</p>
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<p>EDS mapping of ZnO-SiO<sub>2</sub> films annealed at 500 °C: (<b>a</b>) the selected area; (<b>b</b>) Si elemental mapping; (<b>c</b>) Zn elemental mapping; (<b>d</b>) EDS spectrum.</p>
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<p>Raman patterns of annealed at 300 °C, 500 °C, and 700 °C.</p>
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<p>PL spectra of ZnO-SiO<sub>2</sub> films annealed at 300 °C, 500 °C, and 700 °C.</p>
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<p>I-V curves of ZnO-SiO<sub>2</sub> films at different light conditions: (<b>a</b>) dark (<b>b</b>) visible light.</p>
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<p>I-T curves of ZnO-SiO<sub>2</sub> films at the voltage of 9 V.</p>
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<p>Response time measurements by visible light switched on and off at various annealing temperatures.</p>
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<p>A schematic diagram of carrier transport in the ZnO-SiO<sub>2</sub> thin film on a Si substrate under visible light illumination.</p>
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16 pages, 2915 KiB  
Article
Phase Relations in the Pseudo-Binary BiFeO3–EuFeO3 System in the Subsolidus Region Derived from X-Ray Diffraction Data—A Machine Learning Approach
by Vasile-Adrian Surdu and Romuald Győrgy
Inorganics 2024, 12(12), 314; https://doi.org/10.3390/inorganics12120314 - 4 Dec 2024
Abstract
BiFeO3 and EuFeO3 are some of the most studied ferrites and part of the larger category of multiferroic and magnetic compounds. The instabilities reported for BiFeO3 that hinder its use in practical applications can be overcome by substitution with rare-earth [...] Read more.
BiFeO3 and EuFeO3 are some of the most studied ferrites and part of the larger category of multiferroic and magnetic compounds. The instabilities reported for BiFeO3 that hinder its use in practical applications can be overcome by substitution with rare-earth ions, such as Eu3+, on the Bi3+ site. This paper reports on the phase relations in the BiFeO3-EuFeO3 pseudo-binary system, which were not established previously. Solid-state reactions were employed to prepare different compositions according to the nominal formula Bi1−xEuxFeO3 (where x = 0, 0.05, 0.10, 0.15, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1). Phase equilibria were studied at different temperatures between 800 and 1200 °C from X-ray diffraction (XRD) data. The analysis of the XRD patterns by machine learning approaches revealed eight defined clusters and four unclustered points. The validation test showed that most of the points could belong to several clusters and thus, traditional identification was employed. Phase identification and quantification by traditional approaches revealed six crystallization zones on the diagram. Although the machine learning approach offers speed in the process of classification of XRD patterns, validation by the traditional method was necessary for the construction of the phase diagram with high accuracy. Full article
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<p>Binary phase diagram for the Bi<sub>2</sub>O<sub>3</sub>–Fe<sub>2</sub>O<sub>3</sub> oxide system [<a href="#B28-inorganics-12-00314" class="html-bibr">28</a>]. Source: ACerS—NIST Phase Equilibria Diagrams Database.</p>
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<p>Binary phase diagram Eu<sub>2</sub>O<sub>3</sub>–Fe<sub>2</sub>O<sub>3</sub> [<a href="#B57-inorganics-12-00314" class="html-bibr">57</a>]. Structure types: B = B-type Eu<sub>2</sub>O<sub>3</sub>; G = garnet; P = perovskite; S = spinel; α, corundum-type phase. Source: ACerS—NIST Phase Equilibria Diagrams Database.</p>
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<p>Heatmap of the correlation matrix showing the similarities between XRD patterns; red corresponds to large correlation values; blue indicates low or negative correlation.</p>
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<p>Representation of the penalty value versus the linkage number in the KGS test. The orange circle indicates the optimal number of clusters (12) that corresponds to the lowest penalty function value.</p>
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<p>Dendrogram showing the hierarchical agglomeration of diffraction patterns into clusters. Each color corresponds to a different cluster.</p>
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<p>X-ray diffraction patterns grouped according to the hierarchical clustering results (<b>a</b>–<b>i</b>); silhouette plots showing the membership coefficient of XRD patterns to their allocated cluster (<b>j</b>).</p>
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<p>Pseudo-binary BiFeO<sub>3</sub>-EuFeO<sub>3</sub> phase diagram in the subsolidus region, according to the agglomerative hierarchical clustering of XRD patterns. Cluster allocation of each pattern is indicated by the numbers within the squares (1 through 8); the letter “N” corresponds to non-clustered patterns.</p>
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<p>Proposed pseudo-binary BiFeO<sub>3</sub>–EuFeO<sub>3</sub> phase diagram in the subsolidus region based on the traditional processing of XRD patterns (phase identification followed by Rietveld refinement).</p>
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14 pages, 2575 KiB  
Article
Rapid LC-MS/MS Evaluation of Collagen and Elastin Crosslinks in Human and Mouse Lung Tissue with a Novel Bioanalytical Surrogate Matrix Approach
by Sarah M. Lloyd, Elizabeth J. Sande, Kenneth Ruterbories, Stephen P. O’Brien, Yue-Ting Wang, Lucy A. Phillips, Tracy L. Carr, Meghan Clements, Lisa A. Hazelwood, Yu Tian, Yupeng He and Qin C. Ji
Int. J. Mol. Sci. 2024, 25(23), 13026; https://doi.org/10.3390/ijms252313026 - 4 Dec 2024
Viewed by 136
Abstract
Alterations to post-translational crosslinking modifications in the extracellular matrix (ECM) are known to drive the pathogenesis of fibrotic diseases, including idiopathic pulmonary fibrosis (IPF). Thus, the methodology for measuring crosslinking dynamics is valuable for understanding disease progression. The existing crosslinking analysis sample preparation [...] Read more.
Alterations to post-translational crosslinking modifications in the extracellular matrix (ECM) are known to drive the pathogenesis of fibrotic diseases, including idiopathic pulmonary fibrosis (IPF). Thus, the methodology for measuring crosslinking dynamics is valuable for understanding disease progression. The existing crosslinking analysis sample preparation and liquid chromatography tandem mass spectrometry (LC-MS/MS) methods are typically labor-intensive and time-consuming which limits throughput. We, therefore, developed a rapid approach minimizing specialized equipment and hands-on time. The LC-MS/MS sample analysis time was reduced to two minutes per sample. We then improved the analytical integrity of the method by developing a novel surrogate matrix approach for the dihydroxylysinonorleucine (DHLNL) crosslink. By modifying sample preparation, we prepared a tissue-based surrogate matrix with undetectable levels of endogenous DHLNL, providing a strategy for quantifying this crosslink with a more relevant standard matrix. We then applied this rapid methodology to evaluating crosslinking in lung fibrosis. We showed an increase in DHLNL in human IPF lung relative to healthy donors, as well as in a fibrotic mouse model. Finally, we demonstrated that this increase in DHLNL could be mitigated with an anti-fibrotic compound, suggesting that this assay has potential for evaluating pharmaceutical compound efficacy. Full article
(This article belongs to the Special Issue Proteomics and Its Applications in Disease 3.0)
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<p>Structures of bivalent crosslinks analyzed by LC-MS/MS, and their precursors (intermediate imine crosslink structures). Bivalent crosslinks can only be analyzed after their unstable precursors are reduced with sodium borohydride (NaBH<sub>4</sub>).</p>
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<p>Structures of trivalent and tetravalent crosslinks analyzed by LC-MS/MS. Pyr and DPr crosslinks are found on collagen, while Des and IsoDes are specific to elastin.</p>
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<p>Overview of the crosslinking sample preparation procedure. Three fragments per lung for three healthy and three IPF donors were used for method development. Tissue was homogenized and centrifuged. The pellet contained crosslinked ECM. NaBH<sub>4</sub> reduction was performed, followed by three washes. Samples were hydrolyzed overnight (O/N) in HCl, dried down, and resuspended in a stable labeled internal standard (SLIS). Created with <a href="http://BioRender.com" target="_blank">BioRender.com</a>, accessed 8 July 2024.</p>
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<p>Chromatographic elution order, peak resolution, and signal intensities of six crosslinks from a lung tissue sample with the two minute per sample method. Des/Iso represents desmosine and isodesmosine, as these were not separable.</p>
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<p>Development of a relevant surrogate matrix for DHLNL quantitation. Chromatograms of (<b>A</b>) the neat water blank used for the standard generated calibration curves; (<b>B</b>) non-reduced lung tissue, blank DHLNL matrix; and (<b>C</b>) 2.5 ng/mL DHLNL (LLOQ) in an unreduced tissue-based surrogate matrix. The orange arrow points to the DHLNL peak at a retention time of 0.58 min.</p>
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<p>Trends in crosslinking changes are consistent across normalization methods. Values from the LC-MS/MS relative quantification of pyridinoline (Pyr), deoxypyridinoline (Dpr), lysinonorleucine (LNL), hydroxylysino-norleucine (HLNL), dihydroxylysino-norleucine (DHLNL), and desmosine/isodesmosine (Des/Iso) were normalized by (<b>A</b>) tissue fragment weight, (<b>B</b>) hydroxyproline concentration, (<b>C</b>) total protein concentration of homogenized tissue and (<b>D</b>) total protein concentration of the final sample in the stable label internal standard (SLIS). Relative values were then used to calculate the fold change of samples relative to normal healthy control donors. Data are shown as the mean with standard deviation. Each dot represents a biological replicate <span class="html-italic">(n</span> = 3 IPF donor lungs, <span class="html-italic">n</span> = 3 normal healthy lungs (NHL)) and is an average of three technical replicates (<span class="html-italic">n</span> = 3 fragments/donor lung). Statistics are shown for all comparisons, where <span class="html-italic">p</span> &lt; 0.05 (two-way ANOVA, Sidak’s multiple-comparison test, **** <span class="html-italic">p</span> &lt; 0.0001, *** <span class="html-italic">p</span> &lt; 0.001).</p>
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<p>DHLNL crosslinking increases in bleomycin mouse model of lung fibrosis and decreases with antifibrotic compound. Values from the LC-MS/MS relative quantification of pyridinoline (Pyr), deoxypyridinoline (Dpr), lysinonorleucine (LNL), hydroxylysinonorleucine (HLNL), dihydroxylysinonorleucine (DHLNL), and desmosine/isodesmosine (Des/Iso) were normalized by total protein concentration in the homogenate. Relative values were then used to calculate the fold change of the samples relative to the control (Ctrl) which had no bleomycin (Bleo) or SM16 treatment. The Bleo condition had bleomycin but no SM16 treatment. The SM16 group had both bleomycin and SM16 treatment. Data are shown as the mean with standard deviation. Each dot represents a biological replicate (<span class="html-italic">n</span> = 5 mice/condition). Statistics are shown for all comparisons where <span class="html-italic">p</span> &lt; 0.05 (two-way ANOVA, Tukey’s multiple comparison test, **** <span class="html-italic">p</span> &lt; 0.0001, ** <span class="html-italic">p</span> &lt; 0.01).</p>
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