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13 pages, 1968 KiB  
Article
Gintonin Stimulates Glucose Uptake in Myocytes: Involvement of Calcium and Extracellular Signal-Regulated Kinase Signaling
by Rami Lee, Kyung-Jong Won, Ji-Hun Kim, Byung-Hwan Lee, Sung-Hee Hwang and Seung-Yeol Nah
Biomolecules 2024, 14(10), 1316; https://doi.org/10.3390/biom14101316 - 17 Oct 2024
Viewed by 83
Abstract
Ginseng has anti-hyperglycemic effects. Gintonin, a glycolipoprotein derived from ginseng, also stimulates insulin release from pancreatic beta cells. However, the role of gintonin in glucose metabolism within skeletal muscle is unknown. Here, we showed the effect of gintonin on glucose uptake, glycogen content, [...] Read more.
Ginseng has anti-hyperglycemic effects. Gintonin, a glycolipoprotein derived from ginseng, also stimulates insulin release from pancreatic beta cells. However, the role of gintonin in glucose metabolism within skeletal muscle is unknown. Here, we showed the effect of gintonin on glucose uptake, glycogen content, glucose transporter (GLUT) 4 expression, and adenosine triphosphate (ATP) content in C2C12 myotubes. Gintonin (3–30 μg/mL) dose-dependently stimulated glucose uptake in myotubes. The expression of GLUT4 on the cell membrane was increased by gintonin treatment. Treatment with 1–3 μg/mL of gintonin increased glycogen content in myotubes, but the content was decreased at 30 μg/mL of gintonin. The ATP content in myotubes increased following treatment with 10–100 μg/mL gintonin. Gintonin transiently elevated intracellular calcium concentrations and increased the phosphorylation of extracellular signal-regulated kinase (ERK). Gintonin-induced transient calcium increases were inhibited by treatment with the lysophosphatidic acid receptor inhibitor Ki16425, the phospholipase C inhibitor U73122, and the inositol 1,4,5-trisphosphate receptor antagonist 2-aminoethoxydiphenyl borate. Gintonin-stimulated glucose uptake was decreased by treatment with U73122, the intracellular calcium chelator 1,2-bis(o-aminophenoxy)ethane-N,N,N′,N′-tetraacetic acid tetra(acetoxymethyl) ester, and the ERK inhibitor PD98059. These results show that gintonin plays a role in glucose metabolism by increasing glucose uptake through transient calcium increases and ERK signaling pathways. Thus, gintonin may be beneficial for glucose metabolism control. Full article
(This article belongs to the Special Issue Therapeutic Potential of Natural Products in Metabolic Diseases)
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Figure 1

Figure 1
<p>Effect of gintonin on the cell viability of myotubes and transient intracellular calcium increases. (<b>A</b>) Cell viability. C2C12 myotubes were treated with gintonin (GT, 0.1–100 μg/mL) or lysophosphatidic acid (10 μM) for 24 h. Then, WST assay was performed. All data are shown as the mean ± SEM (<span class="html-italic">n</span> = 6). (<b>B</b>,<b>C</b>) Transient intracellular calcium increases. Fura-2-AM-incorporated C2C12 myotubes were treated with gintonin (GT, 0.3–30 μg/mL), and intracellular calcium levels were measured by spectrofluorophotometry and calculated. Each arrow in panel (<b>B</b>) represents time points of treatment with gintonin at indicated concentrations. The horizontal length of the upper scale bar corresponds to 100 s (100 s). (<b>D</b>) Inhibitory effects of inhibitors on GT-induced intracellular calcium increase. Fura-2-AM-loaded C2C12 myotubes were pretreated with PTX (100 ng/mL), Ki16425 (10 μM), U73122 (5 μM), or 2-APB (100 μM) for 5 min and then treated with gintonin (GT, 1 μg/mL). All data are shown as the mean ± SEM (<span class="html-italic">n</span> = 3–5); * <span class="html-italic">p</span> &lt; 0.05; ** <span class="html-italic">p</span> &lt; 0.01; *** <span class="html-italic">p</span> &lt; 0.001 vs. untreated control cells (Con). PTX, pertussis toxin; 2-APB, the inositol 1,4,5-trisphosphate receptor antagonist 2-aminoethoxydiphenyl borate.</p>
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<p>Effect of gintonin on glucose uptake in C2C12 myotubes. (<b>A</b>) C2C12 myotubes were treated with gintonin (GT, 3 μg/mL) and 2-NBDG (100 μM) for 0–24 h. (<b>B</b>) The myotubes were treated with gintonin (0.1–30 μg/mL) for 24 h. (<b>C</b>–<b>F</b>) The myotubes were treated with gintonin (GT, 3 μg/mL) and 2-NBDG (100 μM) for 24 h, with or without the addition of inhibitors (Ki16425, 10 μM; U73122, 5 μM; BAPTA-AM, 50 μM; PD98059, 10 μM). Then, 2-NBDG uptake was measured using spectrofluorophotometry. All data are shown as the mean ± SEM. (<span class="html-italic">n</span> = 6); * <span class="html-italic">p</span> &lt; 0.05; ** <span class="html-italic">p</span> &lt; 0.01; *** <span class="html-italic">p</span> &lt; 0.001 vs. time 0 or untreated control cells (Con). <sup>#</sup> <span class="html-italic">p</span> &lt; 0.05; <sup>##</sup> <span class="html-italic">p</span> &lt; 0.01; <sup>###</sup> <span class="html-italic">p</span> &lt; 0.001 vs. GT alone. BAPTA-AM, 1,2-bis(o-aminophenoxy)ethane-N,N,N′,N′-tetraacetic acid tetra(acetoxymethyl) ester.</p>
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<p>Effect of gintonin on ATP and glycogen content in C2C12 myotubes. (<b>A</b>,<b>B</b>) ATP content. (<b>A</b>) C2C12 myotubes were treated with gintonin (GT, 10 μg/mL) for 0–24 h. (<b>B</b>) The myotubes were treated with gintonin (0.1–100 μg/mL) or lysophosphatidic acid (LPA, 10 μM) for 8 h. The ATP content of myotubes was measured using an ATP assay kit. (<b>C</b>) Glycogen content. The myotubes were treated with gintonin (GT, 0.1–30 μg/mL) or insulin (INS, 100 nM), and the glycogen content was measured using a glycogen assay kit. All data are presented as the mean ± SEM (<span class="html-italic">n</span> = 6); * <span class="html-italic">p</span> &lt; 0.05; ** <span class="html-italic">p</span> &lt; 0.01; *** <span class="html-italic">p</span> &lt; 0.001 vs. time 0 or untreated control cells (Con).</p>
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<p>Effect of gintonin on ERK phosphorylation in C2C12 myotubes. (<b>A</b>) C2C12 myotubes were treated with gintonin (GT, 10 μg/mL) for 0–60 min. (<b>B</b>) The myotubes were treated with gintonin (0.3–100 μg/mL) for 10 min. (<b>C</b>) The myotubes were pretreated with inhibitors (Ki16425, 10 μM; PD98059, 10 μM; U73122, 5 μM) for 1 h and then treated with gintonin (3 μg/mL) for 10 min. Phosphorylated ERK and ERK were detected by immunoblotting. All data are shown as the mean ± SEM (n = 4); * <span class="html-italic">p</span> &lt; 0.05; ** <span class="html-italic">p</span> &lt; 0.01; *** <span class="html-italic">p</span> &lt; 0.001 vs. time 0 or untreated control cells (Con). <sup>#</sup> <span class="html-italic">p</span> &lt; 0.05; <sup>##</sup> <span class="html-italic">p</span> &lt; 0.01; <sup>###</sup> <span class="html-italic">p</span> &lt; 0.001 vs. GT alone. p-ERK, phospho-ERK. Original western blot images can be found in <a href="#app1-biomolecules-14-01316" class="html-app">Supplementary File S1</a>.</p>
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<p>Effect of gintonin on GLUT4 expression in total lysates and plasma membrane fractions of C2C12 myotubes. (<b>A</b>) GLUT4 expression in total lysates. (<b>B</b>) GLUT4 expression in the plasma membrane fraction. C2C12 myotubes were treated with gintonin (GT, 10 μg/mL) for 120 min or insulin (INS, 100 nM) for 30 min. GLUT4 expression in total lysates and plasma membrane fraction of C2C12 myotubes was detected by immunoblotting. β-actin and Na<sup>+</sup>/K<sup>+</sup> ATPase were also detected as loading controls. All data are shown as the mean ± SEM (<span class="html-italic">n</span> = 4); ** <span class="html-italic">p</span> &lt; 0.01; *** <span class="html-italic">p</span> &lt; 0.001 vs. untreated control cells (Con). Original western blot images can be found in <a href="#app1-biomolecules-14-01316" class="html-app">Supplementary File S1</a>.</p>
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<p>Possible signaling pathways of gintonin (GT)-induced glucose uptake in C2C12 myotubes. Gintonin induces transient increases in intracellular calcium concentrations and ERK activation via LPA receptor (LPAR) activation. These may lead to increases in the expression and translocation of GLUT4, subsequently increasing glucose uptake. PLC, phospholipase C; ERK, extracellular signal-regulated kinase; GLUT4, glucose transporter type 4.</p>
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18 pages, 12709 KiB  
Article
Bio-Based Self-Healing Epoxy Vitrimers with Dynamic Imine and Disulfide Bonds Derived from Vanillin, Cystamine, and Dimer Diamine
by Itsuki Abe and Mitsuhiro Shibata
Molecules 2024, 29(20), 4839; https://doi.org/10.3390/molecules29204839 - 12 Oct 2024
Viewed by 430
Abstract
The condensation reactions of 4,4′-(ethane-1,2-diylbis (oxy)) bis(3-methoxybenzaldehyde) (VV) with cystamine, 1,6-hexamenthylene diamine, and a dimer diamine (PriamineTM 1075) produced three types of vanillin-derived imine-and disulfide-containing diamines (VC, VH, and VD, respectively). Thermal curing reactions of polyglycerol polyglycidyl ether with VD and mixtures [...] Read more.
The condensation reactions of 4,4′-(ethane-1,2-diylbis (oxy)) bis(3-methoxybenzaldehyde) (VV) with cystamine, 1,6-hexamenthylene diamine, and a dimer diamine (PriamineTM 1075) produced three types of vanillin-derived imine-and disulfide-containing diamines (VC, VH, and VD, respectively). Thermal curing reactions of polyglycerol polyglycidyl ether with VD and mixtures of VC/VD and VH/VD produced bio-based epoxy vitrimers (BEV-VD, BEV-VC/VD, and BEV-VH/VD, respectively). The degree of swelling and gel fraction tests revealed the formation of a network structure, and the crosslinking density increased with a decreasing VD fraction. The glass transition temperature, tensile strength, and tensile modulus of the cured films increased as the VD fraction decreased. In contrast, the thermal degradation temperature of the cured films increased as the VD fraction increased. All the cured films were healed by hot pressing at 120 °C for 2 h under 1 MPa at least three times. The healing efficiencies, based on tensile strength after the first healing treatment, were 75–78%, which gradually decreased as the healing cycle was repeated. When imine-and disulfide-containing BEV-VC/VD and imine-containing BEV-VH/VD with the same VC/VD and VH/VD ratios were used, the former exhibited a slightly higher healing efficiency. Full article
(This article belongs to the Special Issue Synthesis and Characterization of Self-Healing Materials)
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Graphical abstract

Graphical abstract
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<p>The 400 MHz <sup>1</sup>H-NMR spectrum of VC in CDCl<sub>3</sub> at 300 K. Red numeral values represent integral values of respective chemical shift regions.</p>
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<p>The 400 MHz <sup>1</sup>H-NMR spectrum of VH in CDCl<sub>3</sub> at300 K. Red numeral values represent integral values of respective chemical shift regions.</p>
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<p>The 400 MHz <sup>1</sup>H-NMR spectrum of VD in CDCl<sub>3</sub> at 300 K. Red numeral values represent integral values of respective chemical shift regions.</p>
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<p>FT-IR spectra of CTA, HMDA, DDA, VV, VC, VH, and VD.</p>
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<p>DTA curves of mixtures of PGPE/VC, PEGE/VH, and PGPE/VD at an epoxy/NH<sub>2</sub> molar ratio of 2/1.</p>
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<p>FT-IR spectra of PGPE and BEV-VD, BEV-VC/VD, and BEV-VH/VD films.</p>
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<p>(<b>a</b>) <span class="html-italic">Ds</span> and (<b>b</b>) <span class="html-italic">Gf</span> values of the cured films.</p>
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<p>DSC curves of the cured films.</p>
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<p>DMA curves of (<b>a</b>) BEV-VD, BEV-VC/VD-1/3, and BEV-VC/VD-1/1, and (<b>b</b>) BEV-VD, BEV-VH/VD-1/3, and BEV-VH/VD-1/1. The DMA curves indicated by left and right arrows are values of <span class="html-italic">E</span>′ and tan <span class="html-italic">δ</span>, respectively.</p>
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<p>TGA curves of (<b>a</b>) BEV-VD, BEV-VC/VD-1/3, and BEV-VC/VD-1/1, and (<b>b</b>) BEV-VD, BEV-VH/VD-1/3, and BEV-VH/VD-1/1.</p>
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<p>(<b>a</b>) Tensile strength, (<b>b</b>) tensile modulus, and (<b>c</b>) elongation at break of the cured films.</p>
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<p>Healing behavior of the cured film by hot pressing at 120 °C under 1 MPa for 2 h.</p>
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<p>Change in the tensile stress–strain curves of BEV-VD films (<b>a</b>) healed at 120 °C under 1 MPa for 1, 2, and 3 h, and (<b>b</b>) healed at 40, 80, and 120 °C under 1 MPa for 2 h.</p>
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<p>Tensile stress–strain curves of (<b>a</b>) BEV-VD, (<b>b</b>) BEV-VC/VD-1/3, (<b>c</b>) BEV-VC/VD-1/1, (<b>d</b>) BEV-VH/VD-1/3, and (<b>e</b>) BEV-VH/VD-1/1, healed at 120 °C under 1 MPa for 2 h once, twice, and three times.</p>
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<p>Synthesis of VV by the reaction of VN and 1,2-dibromoethane.</p>
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<p>Synthesis of VC, VH, and VD by the reactions of VV with CTA, HMDA, and DDA.</p>
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<p>Preparation of bio-based epoxy vitrimers by the thermal curing reactions of PGPE with VD and mixtures of VC/VD and VH/VD.</p>
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22 pages, 2559 KiB  
Article
Long-Term Forecasting Models of Oil Demand Emerging from the Global Petrochemical Sector
by Raed Al Mestneer and Carlo Andrea Bollino
Energies 2024, 17(20), 5046; https://doi.org/10.3390/en17205046 - 11 Oct 2024
Viewed by 416
Abstract
In the global energy mix by 2040, the growth in demand for oil and gas will be predominantly driven by the petrochemical sector across all regions of the world. The strong performance of this industry is anticipated to necessitate additional volumes of key [...] Read more.
In the global energy mix by 2040, the growth in demand for oil and gas will be predominantly driven by the petrochemical sector across all regions of the world. The strong performance of this industry is anticipated to necessitate additional volumes of key feedstocks. Therefore, understanding the demand dynamics within the petrochemical sector is crucial for policy makers and industry stakeholders to make informed decisions regarding economic diversification, economic planning, and environmental sustainability. However, there is a notable lack of existing literature that explicitly addresses comprehensive regional and product-level demand modeling for petrochemical feedstocks. In this context, this study aims to estimate the demand for four main petrochemical feedstocks (Naphtha, Ethane, Liquefied Petroleum Gas (LPG), and other petrochemical feedstocks) across eight regions of the world. By estimating a total of 30 equations for price and income elasticities of demand in both the short and long term, the study provides detailed insights into the factors driving demand across different regions. The results demonstrate the robustness of the model, with good econometric properties and significant coefficients. In-sample regional simulations revealed small percentage errors across all regional equations, highlighting the model’s accuracy in tracking historical data. For each of the four feedstocks, an aggregate world equation—in other words, one single econometric world equation for each of the four petrochemical feedstocks’ categories mentioned earlier—was also estimated and compared against the aggregation of the regional simulations, with the latter found to track the history of global petrochemical feedstock demand better in-sample than a single econometric world equation. Overall, the study offers valuable contributions to the existing literature by filling a gap in comprehensive demand modeling for petrochemical feedstocks. It underscores the importance of regional and product-level analyses in understanding global demand patterns and informing strategic decisions in the industry. Full article
(This article belongs to the Special Issue Modeling Energy–Environment–Economy Interrelations II)
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Figure 1
<p>Global petrochemical feedstock demand. Source: IEA [<a href="#B5-energies-17-05046" class="html-bibr">5</a>]. Note: The left pie chart of each region indicates feedstock demand, while the right pie chart demonstrates primary chemical production.</p>
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<p>Simulation of actual and fitted values—world total—in-sample 1995 to 2019 (the vertical axis measures the quantity as MMb/d). Source: Authors.</p>
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<p>Simulation of actual and fitted values—ethane—regional values—in-sample 1995–2019 (the vertical axis measures the quantity as MMb/d). Source: Authors.</p>
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<p>Simulation of actual and fitted values—naphtha—regional values—in-sample 1995–2019 (the vertical axis measures the quantity as MMb/d). Source: Authors.</p>
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<p>Simulation of actual and fitted values—LPG—regional values—in-sample 1995–2019 (the vertical axis measures the quantity as MMb/d). Source: Authors.</p>
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<p>Simulation of actual and fitted values—other petrochemical feedstocks—regional values—in-sample 1995–2019 (the vertical axis measures the quantity as MMb/d). Source: Authors.</p>
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13 pages, 2850 KiB  
Article
Thermodynamic Properties of Two Cinnamate Derivatives with Flavor and Fragrance Features
by Vera L. S. Freitas, Carlos A. O. Silva and Maria D. M. C. Ribeiro da Silva
Liquids 2024, 4(4), 689-701; https://doi.org/10.3390/liquids4040038 - 11 Oct 2024
Viewed by 415
Abstract
The standard molar enthalpies of formation in the liquid phase for ethyl (E)-cinnamate and ethyl hydrocinnamate, two cinnamate derivatives with notable flavor and fragrance characteristics, were determined experimentally using combustion calorimetry in an oxygen atmosphere. To derive the gas-phase enthalpies of [...] Read more.
The standard molar enthalpies of formation in the liquid phase for ethyl (E)-cinnamate and ethyl hydrocinnamate, two cinnamate derivatives with notable flavor and fragrance characteristics, were determined experimentally using combustion calorimetry in an oxygen atmosphere. To derive the gas-phase enthalpies of formation for these derivatives, their enthalpies of vaporization were measured using a high-temperature Calvet microcalorimeter and the vacuum drop microcalorimetric technique. Additionally, a computational analysis employing the G3(MP2)//B3LYP composite method was conducted to calculate the gas-phase standard enthalpies of formation at T = 298.15 K for both compounds. These findings enabled a detailed assessment and analysis of the structural and energetic effects of the vinyl and ethane moieties between the phenyl and carboxylic groups in the studied compounds. Considering the structural features of ethyl (E)-cinnamate and ethyl hydrocinnamate, a gas-phase enthalpy of hydrogenation analysis was conducted to explore their energetic profiles more thoroughly. Full article
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Figure 1
<p>Structural formulae of ethyl (<span class="html-italic">E</span>)-cinnamate (<b>A</b>) and ethyl hydrocinnamate (<b>B</b>).</p>
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<p>Conformational composition, χi, for the most stable predominant molecular geometries, corresponding to minima on the potential energy surface, obtained using the G3(MP2)//B3LYP composite method for cinnamate derivatives. Atom color code: grey, C; red, O; and white, H.</p>
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<p>Hydrogenation reactions with corresponding enthalpy of hydrogenation values for the conversion of ethyl (<span class="html-italic">E</span>)-cinnamate to ethyl hydrocinnamate and ethyl (2<span class="html-italic">E</span>)-2-butenoate to ethyl butyrate. Refs. [<a href="#B39-liquids-04-00038" class="html-bibr">39</a>,<a href="#B40-liquids-04-00038" class="html-bibr">40</a>].</p>
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<p>Hydrogenation reactions with corresponding experimental enthalpy of hydrogenation values for the conversion of methyl (<span class="html-italic">E</span>)-cinnamate and methyl (Z)-cinnamate to methyl hydrocinnamate at a temperature of 302 K.</p>
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19 pages, 8467 KiB  
Article
Geochemical Tracing of Seabed Hydrocarbon Seepage in the Yantai Depression, South Yellow Sea Basin
by Jianqiang Wang, Yuxi Zhang, Jian Zhang, Jie Liang, Qingfang Zhao and Heping Dong
J. Mar. Sci. Eng. 2024, 12(10), 1805; https://doi.org/10.3390/jmse12101805 - 10 Oct 2024
Viewed by 413
Abstract
Widespread submarine hydrocarbon seepage can form complex fluid seepage characteristics, with submarine sediment geochemistry effectively recording seepage activities and fluid component changes due to hydrocarbon seepage. This is crucial for offshore oil and gas exploration and understanding global climate change. Therefore, using the [...] Read more.
Widespread submarine hydrocarbon seepage can form complex fluid seepage characteristics, with submarine sediment geochemistry effectively recording seepage activities and fluid component changes due to hydrocarbon seepage. This is crucial for offshore oil and gas exploration and understanding global climate change. Therefore, using the geochemical information of submarine sediments to trace hydrocarbon seepage activities is of great significance. In order to identify the geochemical anomaly characteristics and genetic types of acid-hydrolyzed hydrocarbons in submarine sediments in the Yantai Depression of the South Yellow Sea Basin, Eastern China, and to explore the relationship between these anomalies and deep oil and gas, geochemical columnar samples were taken at 100 stations in the study area. A total of 100 sets of acid-hydrolyzed hydrocarbon data and 26 sets of carbon isotope data were analyzed. The results show that the content of acid-hydrolyzed hydrocarbons at each station is in the following order: methane (AC1) > ethane (AC2) > propane (AC3) > butane (AC4) > pentane (AC5). The determination coefficient between the saturated hydrocarbon indicators exceeds 0.9, indicating that these components have the same source. Data analysis reveals that the genetic type of hydrocarbon gases in the study area is generally thermogenic, with limited microbial contribution to saturated hydrocarbons, indicating deep oil and gas characteristics. The coincidence between the anomalous areas and geological structures indicates that the distribution of these anomalies is closely related to fault distribution. Full article
(This article belongs to the Section Geological Oceanography)
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<p>Location of the study area [<a href="#B46-jmse-12-01805" class="html-bibr">46</a>].</p>
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<p>Frequency distribution of acid-hydrolyzed hydrocarbon methane and ethane contents in submarine sediments. Surface geochemical measurements rarely follow a normal distribution and tend to be skewed [<a href="#B53-jmse-12-01805" class="html-bibr">53</a>]. The acid-soluble hydrocarbon methane histogram exhibits a log-normal distribution, with the first main peak providing background information about the samples and the second main peak indicating anomalous information. By combining the range of the first main peak for methane and ethane, the lower limit of the anomaly was determined using a calculation method (see <a href="#sec5dot1dot1-jmse-12-01805" class="html-sec">Section 5.1.1</a> for the extraction of geochemical anomalies).</p>
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<p>Distribution of acid-hydrolyzed hydrocarbons methane in the Yantai Depression of the South Yellow Sea Basin.</p>
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<p>Distribution of acid-hydrolyzed hydrocarbons ethane in the Yantai Depression of the South Yellow Sea Basin.</p>
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<p>Comparison of w(AC<sub>1</sub>)–w(AC<sub>2</sub>) and w(AC<sub>2</sub>)–w(AC<sub>3</sub>) contents of acid-hydrolyzed hydrocarbons of samples in the South Yellow Sea Basin. (<b>a</b>) Correlation between AC1 and AC2; (<b>b</b>) Correlation between AC2 and AC3.</p>
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<p>Relationship between δ<sup>13</sup>C<sub>1</sub> and dryness coefficient of natural gas (adapted from [<a href="#B64-jmse-12-01805" class="html-bibr">64</a>]).</p>
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<p>Relationship between carbon isotope ratios and thermal maturity the Yantai Depression, South Yellow Sea Basin (adapted from [<a href="#B54-jmse-12-01805" class="html-bibr">54</a>]). (<b>a</b>) Relationship between carbon isotope ratio and thermal maturity of methane-ethane; (<b>b</b>) Relationship between carbon isotope ratio and thermal maturity of ethane- propane.</p>
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<p>Compound-specific carbon isotopic analysis interpretation chart; methane carbon isotope (δ<sup>13</sup>C<sub>1</sub>‰) versus ethane–propane separation in absolute value [(δ<sup>13</sup>C<sub>2</sub> − (δ<sup>13</sup>C<sub>3</sub>)] (modified after [<a href="#B38-jmse-12-01805" class="html-bibr">38</a>]).</p>
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<p>Geochemical classification showing the genesis o in the study area (adapted from [<a href="#B68-jmse-12-01805" class="html-bibr">68</a>]).</p>
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<p>Geophysical response characteristics of seabed hydrocarbon seepage in the Yantai Depression, South Yellow Sea Basin.</p>
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<p>Superimposed plots of faults, anomalies, and source rocks in the Yantai Depression, South Yellow Sea Basin.</p>
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<p>Hydrocarbon seepage model in Yantai depression of the South Yellow Sea Basin.</p>
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14 pages, 8798 KiB  
Article
Characteristics and Origin of Natural Gas in Yongfeng Sub-Sag of Bogda Mountain Front Belt
by Xiangcan Sun, Yi Chen, Xingui Zhou, Zhongkai Bai, Yukun Du, Lei Wen and Kun Yuan
Appl. Sci. 2024, 14(19), 9085; https://doi.org/10.3390/app14199085 - 8 Oct 2024
Viewed by 345
Abstract
By systematically analyzing the natural gas composition, carbon isotopes, and source rock characteristics in the Yongfeng sub-sag of the Bogda Mountain front belt, natural gas characteristics were determined, and the genetic types and sources of natural gas were investigated. The research results indicate [...] Read more.
By systematically analyzing the natural gas composition, carbon isotopes, and source rock characteristics in the Yongfeng sub-sag of the Bogda Mountain front belt, natural gas characteristics were determined, and the genetic types and sources of natural gas were investigated. The research results indicate that methane is the main component of natural gas in the Yongfeng sub-sag, with low levels of heavy hydrocarbons and a high drying coefficient. These characteristics make it dry gas, which refers to natural gas with a methane content of over 95%. The ethane carbon isotope δ13C2 of natural gas is −28.5‰ and belongs to oil type gas. The methane carbon isotope δ13C1 of natural gas is −58.6‰~−59.4‰, has a relatively depleted methane carbon isotope value, shows significant differences from the surrounding natural gas methane carbon isotope, and belongs to the category of biogenic gas. The Permian Lucaogou Formation is the main source rock in the study area, with good organic matter abundance. The microscopic components of kerogen are mainly composed of sapropelic formations and the organic matter type is I–II1. The source rock has a high maturity and has reached the mature stage, mainly consisting of oil and wet gas. The ethane carbon isotope of natural gas in the Yongfeng sub-sag shows as oil type gas, which is consistent with the kerogen type of the Lucaogou Formation source rocks, indicating that the natural gas mainly comes from the Lucaogou Formation source rocks. Based on comprehensive data and information on natural gas composition, carbon isotopes, and burial history of the source rocks, it is believed that some of the crude oil generated from the Lucaogou Formation in the early stage underwent biodegradation due to tectonic uplift, resulting in biogenic methane and the formation of crude oil biodegraded gas. Full article
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<p>Location map of the study area.</p>
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<p>Column of source-reservoir-cap combination in the study area.</p>
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<p>Histogram of TOC (<b>left</b>) and chloroform bitumen A (<b>right</b>) for source rocks in the Lucaogou Formation of Well Xyd1.</p>
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<p>Distribution sequence of natural gas carbon isotope components in different areas in the southern margin of the Junggar Basin [<a href="#B9-applsci-14-09085" class="html-bibr">9</a>].</p>
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<p>Identification diagram of natural gas δ<sup>13</sup>C<sub>1</sub>—δ<sup>13</sup>C<sub>2</sub>—δ<sup>13</sup>C<sub>3</sub> in different areas in the southern margin of the Junggar Basin [<a href="#B19-applsci-14-09085" class="html-bibr">19</a>,<a href="#B21-applsci-14-09085" class="html-bibr">21</a>].</p>
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<p>Characteristics of natural gas light hydrocarbon composition of Well Xyd1. (<b>a</b>) Triangle diagram of natural gas C<sub>7</sub> light hydrocarbons; (<b>b</b>) Triangle diagram of natural gas C<sub>5–7</sub> light hydrocarbons; (<b>c</b>) Triangle diagram of natural gas C<sub>6–7</sub> light hydrocarbons.</p>
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<p>Genetic types of natural gas in different areas of the southern margin of the Junggar Basin [<a href="#B27-applsci-14-09085" class="html-bibr">27</a>].</p>
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11 pages, 1882 KiB  
Article
Antifungal Ability of Novel Silane on Titanium Implant Surface
by Xiaotian Liu, Shuyang Chen, Hao Ding and James Kit Hon Tsoi
Coatings 2024, 14(10), 1277; https://doi.org/10.3390/coatings14101277 - 7 Oct 2024
Viewed by 488
Abstract
Titanium and its alloys are commonly used in dentistry for implants due to their strength, lightweight nature, durability, corrosion resistance, and biocompatibility. These implants can osseointegrate after surface treatments such as SLA, plasma-spray, and nanotubes, providing a stable foundation for prostheses. However, Candida [...] Read more.
Titanium and its alloys are commonly used in dentistry for implants due to their strength, lightweight nature, durability, corrosion resistance, and biocompatibility. These implants can osseointegrate after surface treatments such as SLA, plasma-spray, and nanotubes, providing a stable foundation for prostheses. However, Candida albicans, an opportunistic fungal pathogen, can threaten the success of titanium dental implants, causing oral infections in vulnerable individuals. A dual novel silane blend of 3-acryloxypropyltrimethoxysilane (ACPS) and bis-1,2-(triethoxysilyl)ethane (BTSE) has been shown to improve the shear bond strength in resin cement bonds with titanium and ceramics. This study evaluated the effects of Candida albicans colonization on blended silane-coated SLA-Ti surfaces compared to non-coated SLA-Ti (positive control) and flat titanium (negative control). Candida albicans biofilms were cultured on all surfaces, and it was found that silane-coated SLA-Ti had significantly lower CFU counts than non-coated SLA-Ti. However, no significant differences were observed in the RT-PCR results. In conclusion, a combination of 1.0 vol% ACPS and 0.3 vol% BTSE shows promise as a silane coupling agent with potential antifungal properties for inhibiting Candida albicans proliferation. Full article
(This article belongs to the Special Issue Surface Properties of Dental Materials and Instruments, 2nd Edition)
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<p>Novel silane system used in this study: (<b>a</b>) 3-acryloxypropyltrimethoxysilane (ACPS); (<b>b</b>) bis-1,2-(triethoxysilyl)ethane (BTSE), the crosslinker silane.</p>
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<p>FTIR spectrum of the novel silane solution.</p>
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<p>SEM (<b>upper</b>) and AFM (<b>lower</b>) images and cultured <span class="html-italic">Candida albicans</span> on agar plates (<b>upper right</b>) of (<b>a</b>) cp-Ti; (<b>b</b>) SLA-Ti; and (<b>c</b>) silane-coated SLA-Ti.</p>
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<p>Box plot (min–max, box: Q1–Q3) of the CFU/mL per unit area in this study. The red line indicates the mean CFU counting of the cp-Ti value for an easier comparison.</p>
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<p>Box plot (min–max, box: Q1-Q3) of the Ct per unit area (mm<sup>2</sup>) of the PCR result. The red line indicates the mean CT value of cp-Ti for an easier comparison.</p>
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18 pages, 3157 KiB  
Article
Gas-Phase Studies of NMR Shielding and Indirect Spin–Spin Coupling in 13C-Enriched Ethane and Ethylene
by Marcin Wilczek and Karol Jackowski
Molecules 2024, 29(18), 4460; https://doi.org/10.3390/molecules29184460 - 20 Sep 2024
Viewed by 378
Abstract
13C and 1H NMR spectra were observed as the function of density in 1,2-13C-enriched ethane and ethylene for the pure gaseous compounds and their binary mixtures with xenon and carbon dioxide gases as the solvents. All the chemical shifts [...] Read more.
13C and 1H NMR spectra were observed as the function of density in 1,2-13C-enriched ethane and ethylene for the pure gaseous compounds and their binary mixtures with xenon and carbon dioxide gases as the solvents. All the chemical shifts and indirect spin–spin couplings were linearly dependent on the solvent density. The appropriate NMR parameters (σ and nJ) in isolated 13C2H6 and 13C2H4 molecules and the coefficients responsible for the binary molecular interactions were determined and compared with previous similar measurements and selected calculated shielding data. The newly obtained 13C shielding values in the isolated ethane and ethylene molecules suggest visible secondary isotope effects due to the additional carbon-13 atom. All the investigated shielding parameters depend on intermolecular interactions, and the dependence of 13C shielding is much more marked. In contrast, the indirect spin–spin couplings in 13C2H6 and 13C2H4 molecules are almost independent of solvent molecules. Their nJ values determined in liquids over sixty years ago are generally consistent with the same nJ parameters in isolated 13C2H6 and 13C2H4 molecules. Full article
(This article belongs to the Special Issue Advanced Magnetic Resonance Methods in Materials Chemistry Analysis)
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<p>The 125 MHz <sup>13</sup>C NMR spectrum of ethane gas doubly enriched in carbon-13 and without proton decoupling at the spectrometer field 11.7 T. The sample contains pure <sup>13</sup>C<sub>2</sub>H<sub>6</sub> at an approximate pressure of 40 bar. Pure liquid TMS is an external reference standard for carbon-13 chemical shifts.</p>
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<p>The 500 MHz <sup>1</sup>H NMR spectrum (the A<sub>3</sub>A<sub>3</sub>′ fragment of the A<sub>3</sub>A′<sub>3</sub>XX′ spin system) of the same sample as in <a href="#molecules-29-04460-f001" class="html-fig">Figure 1</a>. The enlarged part shows the complex structure of this spectrum due to all the possible spin-spin couplings between <sup>1</sup>H and <sup>13</sup>C nuclei. Its 50 NMR lines are partially overlapped. Liquid TMS is applied as an external reference standard of proton chemical shifts.</p>
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<p>The 125 MHz <sup>13</sup>C NMR spectrum (at 11.7 T) of ethylene enriched in carbon-13 and without decoupling from protons (the XX′ part of the AA′A″A‴XX′ spin system, with 144 partially overlapping NMR lines). The gas sample contains pure <sup>13</sup>C<sub>2</sub>H<sub>4</sub> gas with a pressure of approx. 45 bar. Liquid TMS is used for the measurements of carbon-13 chemical shifts.</p>
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<p>The 500 MHz <sup>1</sup>H NMR spectrum of the same sample is shown in <a href="#molecules-29-04460-f003" class="html-fig">Figure 3</a>. It is the AA′A″A‴ part of the AA′A″A‴XX′ spin system with 132 mostly overlapping signals. The proton chemical shifts are measured relative to external liquid TMS.</p>
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<p>(<b>a</b>,<b>b</b>) Dependence of the <sup>13</sup>C and <sup>1</sup>H shielding on density observed in pure 1,2-<sup>13</sup>C-ethane and its binary mixtures with carbon dioxide (CO<sub>2</sub>) and xenon (Xe) as the gaseous solvents. The measurements were performed relative to liquid TMS accepting its shielding equal to 186.37 ppm for carbon-13 nuclei (<b>a</b>) and 32.815 ppm for protons (<b>b</b>) [<a href="#B13-molecules-29-04460" class="html-bibr">13</a>]. The error bars are marked by the size of experimental points. Let us note that the protons’ shielding scale is 5 times expanded compared to the <sup>13</sup>C scale for better visibility.</p>
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<p>(<b>a</b>,<b>b</b>) Density-dependent <sup>13</sup>C and <sup>1</sup>H shielding of 1,2-<sup>13</sup>C-ethylene for the pure solute and its gaseous mixtures with CO<sub>2</sub> and Xe. Liquid TMS (σ<sub>C</sub> = 186.37 ppm, σ<sub>H</sub> = 32.815 ppm) was applied as the external reference standard. The error bars are marked by the size of experimental points.</p>
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<p>(<b>a</b>,<b>b</b>) The <sup>1</sup>J(CH) and <sup>1</sup>J(CC) isotropic spin–spin couplings in <sup>13</sup>C<sub>2</sub>H<sub>6</sub> as density functions at 300 K. Both plots show the negligible influence of intermolecular interactions on the one-bond couplings (<sup>1</sup>J(CH) in (<b>a</b>) and <sup>1</sup>J(CC) in (<b>b</b>)) in ethane-<sup>13</sup>C<sub>2</sub>.</p>
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<p>(<b>a</b>,<b>b</b>) The one-bond spin–spin couplings (<sup>1</sup>J(CH) in (<b>a</b>) and <sup>1</sup>J(CC) in (<b>b</b>)) in ethylene-<sup>13</sup>C<sub>2</sub> molecules. Their density dependence on gas density is still minimal but a little more differentiated by solvents than for ethane-<sup>13</sup>C<sub>2</sub>.</p>
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19 pages, 4009 KiB  
Article
Response of Bacterial Community Structure and Function in Rhizosphere Soil on the Photosynthesis of Selected Plant Types C3 and C4 under Bis(2,4,6-tribromophenoxy) Ethane Exposure
by Yixuan Chen, Sen Wang, Yuru Li, Wanyu Liu and Zhenchuan Niu
Agriculture 2024, 14(9), 1637; https://doi.org/10.3390/agriculture14091637 - 18 Sep 2024
Viewed by 630
Abstract
This study investigated the response of a bacterial community’s structure and function in the rhizosphere soil of C3 and C4 plants under bis(2,4,6-tribromophenoxy) ethane (BTBPE) exposure. The bacterial community composition was determined using 16S rRNA sequencing, while FAPROTAX and PICRUSt 2 [...] Read more.
This study investigated the response of a bacterial community’s structure and function in the rhizosphere soil of C3 and C4 plants under bis(2,4,6-tribromophenoxy) ethane (BTBPE) exposure. The bacterial community composition was determined using 16S rRNA sequencing, while FAPROTAX and PICRUSt 2 were employed for functional predictions. Results showed significant differences between C3 and C4 plants in terms of bacterial community structure. C3 plants exhibited higher abundances of Proteobacteria, Bacteroidetes at the phylum level and Sphingomicrobium at the genus level, compared to C4 plants. Conversely, C4 plants had higher abundances of Actinobacteria and Patescibacteria at the phylum level and Nocardioides at the genus level. LEfSe and function prediction analyses revealed that the rhizosphere soil bacteria in C3 plants exhibited significantly higher enrichment in nitrogen fixation functions (p < 0.05), whereas C4 plants showed a significantly higher relative abundance of bacteria and functions related to organic pollutant degradation (p < 0.05). These findings suggest that the rhizosphere soil bacteria of C3 plants exhibit a stronger response to BTBPE exposure in nitrogen metabolism-related processes, while C4 plants possess superior biodegradation ability compared to C3 plants. Full article
(This article belongs to the Topic Plant-Soil Interactions, 2nd Volume)
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<p>α-diversity of soil bacteria in the rhizosphere of different treatments. (<b>a</b>) Chao 1. (<b>b</b>) observed_species. (<b>c</b>) Phylogenetic Diversity (PD)_whole_tree. (<b>d</b>) Shannon. Different letters in the same column indicate significant difference (<span class="html-italic">p</span> &lt; 0.05) (CK1, BTBPE-contaminated soil without plant; SI, <span class="html-italic">Setaria italica</span> (L.) Beauv.; ZM, <span class="html-italic">Zea mays</span> L.; AT, <span class="html-italic">Amaranthus tricolor</span> L.; TA, <span class="html-italic">Triticum aestivum</span> L.; GM, <span class="html-italic">Glycine max</span> (L.) Merr.; MS, <span class="html-italic">Medicago sativa</span> L.; LP, <span class="html-italic">Lolium perenne</span> L.).</p>
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<p>Non-metric multidimensional scaling (NMDS) analysis and Partial Least Squares Discriminant Analysis (PLS-DA) of bacterial communities in rhizosphere soil of different treatments. Ellipses are used to compare the similarity of community structure composition between groups. (<b>a</b>) NMDS analysis of different plants. (<b>b</b>) NMDS analysis of C<sub>3</sub> and C<sub>4</sub> plants. (<b>c</b>) Partial Least Squares Discriminant Analysis (PLS-DA) of different plants. (<b>d</b>) Partial Least Squares Discriminant Analysis (PLS-DA) of C<sub>3</sub> and C<sub>4</sub> plants (CK1, BTBPE-contaminated soil without plant; SI, <span class="html-italic">Setaria italica</span> (L.) Beauv.; ZM, <span class="html-italic">Zea mays</span> L.; AT, <span class="html-italic">Amaranthus tricolor</span> L.; TA, <span class="html-italic">Triticum aestivum</span> L.; GM, <span class="html-italic">Glycine max</span> (L.) Merr.; MS, <span class="html-italic">Medicago sativa</span> L.; LP, <span class="html-italic">Lolium perenne</span> L.).</p>
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<p>Composition characteristics of bacterial phylum (<b>a</b>,<b>b</b>) and genus (<b>c</b>,<b>d</b>) in rhizosphere soil of different treatments (CK1 BTBPE-contaminated soil, SI <span class="html-italic">Setaria italica</span> (L.) Beauv., ZM <span class="html-italic">Zea mays</span> L., AT <span class="html-italic">Amaranthus tricolor</span> L., TA <span class="html-italic">Triticum aestivum</span> L., GM <span class="html-italic">Glycine max</span> (L.) Merr., MS <span class="html-italic">Medicago sativa</span> L., LP <span class="html-italic">Lolium perenne</span> L.).</p>
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<p>Evolutionary branch diagram of bacteria in rhizosphere soil of C<sub>3</sub> and C<sub>4</sub> plants based on LEfSe analysis. The circles radiating from the center represent taxonomic levels from phylum to genus (or species). Each small circle at different taxonomic levels represents a classification at that level, with the diameter of the circle proportional to its relative abundance. The coloring principle is as follows: species with no significant difference are uniformly colored to yellow, while biomarkers of the different species are colored according to their respective groups. Red nodes represent microbial groups that are significant in the red group, and the green nodes represent the microbial groups that are significant in the green group. Other circles follow the same color meaning. The species names represented by the English letters in the figure are displayed in the right legend.</p>
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<p>Difference analysis of FAPROTAX function prediction in soil bacterial communities in rhizosphere of C<sub>3</sub> and C<sub>4</sub> plants.</p>
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<p>Difference in functional prediction of PICRUSt 2 in soil bacterial communities in rhizosphere of C<sub>3</sub> and C<sub>4</sub> plants (KEGG level 2).</p>
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11 pages, 4243 KiB  
Article
Carbonyl Iron Particles’ Enhanced Coating Effect Improves Magnetorheological Fluid’s Dispersion Stability
by Fang Chen, Jie Zhang, Qinkui Guo, Yuchen Liu, Xiaobing Liu, Wenwu Ding, Shengnan Yan, Zhaoqiang Yan and Zhenggui Li
Materials 2024, 17(18), 4449; https://doi.org/10.3390/ma17184449 - 10 Sep 2024
Cited by 1 | Viewed by 510
Abstract
The coating effect of 1,2-bis(triethoxysilyl)ethane (BTES) on carbonyl iron particles (CIPs) was enhanced by etching with hydrochloric acid (HCl) of various concentrations, and magnetorheological fluids (MRFs) with significantly improved dispersion stability were obtained. The microstructures, coating effect, and magnetism of CIPs were examined [...] Read more.
The coating effect of 1,2-bis(triethoxysilyl)ethane (BTES) on carbonyl iron particles (CIPs) was enhanced by etching with hydrochloric acid (HCl) of various concentrations, and magnetorheological fluids (MRFs) with significantly improved dispersion stability were obtained. The microstructures, coating effect, and magnetism of CIPs were examined using scanning electron microscopy (SEM), automatic surface and porosity analysis (BTE), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and a vibrating sample magnetometer (VSM), respectively. Furthermore, the rheological properties and dispersion stability of the MRFs were assessed by a rotating rheometer and a Turbiscan Tower. The results show that as the HCl concentration increased, nanopores appeared on CIPs and then disappeared, and the specific surface area of the particles increased and then decreased. When the concentration of HCl was 0.50 mol/L, the number of nanopores and the specific surface area of particles changed sharply. Not only that, the coated mass of BTES increased greatly and the saturation magnetization of particles decreased sharply. As the coated mass increased, without a magnetic field, the viscosity and shear stress of the MRFs increased, especially when the coated mass was more than 2.45 wt.%; while under a magnetic field, the viscosity and shear stress decreased, and the sedimentation rate of the MRFs decreased from 0.13 to 0.01 mm/h. By controlling the concentration of HCl for etching, the coating effect of CIPs was greatly enhanced, and thus an MRF with superior shear stress and excellent dispersion stability was obtained, which is significant in basic research and MRF-related applications. Full article
(This article belongs to the Section Advanced Composites)
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<p>The etching and coating process of particles.</p>
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<p>SEM images of particles etched by HCl with different concentrations: (<b>a</b>) 0 mol/L, (<b>b</b>) 0.05 mol/L, (<b>c</b>) 0.20 mol/L, (<b>d</b>) 0.50 mol/L, (<b>e</b>) 1.00 mol/L, and (<b>f</b>) 3.00 mol/L.</p>
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<p>SEM images of coated CIPs etched by HCl of different concentrations: (<b>a</b>) 0 mol/L, (<b>b</b>) 0.05 mol/L, (<b>c</b>) 0.20 mol/L, (<b>d</b>) 0.50 mol/L, (<b>e</b>) 1.00 mol/L, and (<b>f</b>) 3.00 mol/L.</p>
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<p>The coating effect of CIPs: (<b>a</b>) FTIR curves and (<b>b</b>) TGA curves.</p>
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<p>Magnetization curves of (<b>a</b>) uncoated particles and (<b>b</b>) coated particles.</p>
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<p>Rheological properties of the MRFs: (<b>a</b>) viscosity vs. shear rate (0 kA/m), (<b>b</b>) shear stress vs. shear rate (0 kA/m), (<b>c</b>) viscosity vs. shear rate (175 kA/m), and (<b>d</b>) shear stress vs. shear rate (175 kA/m).</p>
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<p>Typical Turbiscan spectra of the MRFs: (<b>a</b>) M-1, (<b>b</b>) M-2, (<b>c</b>) M-3, (<b>d</b>) M-4, (<b>e</b>) M-5, and (<b>f</b>) M-6.</p>
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<p>The peak thicknesses variation in particles over 7 days.</p>
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15 pages, 5798 KiB  
Article
Recognition of Artificial Gases Formed during Drill-Bit Metamorphism Using Advanced Mud Gas
by Janaina Andrade de Lima Leon, Henrique Luiz de Barros Penteado, Geoffrey S. Ellis, Alexei Milkov and João Graciano Mendonça Filho
Energies 2024, 17(17), 4383; https://doi.org/10.3390/en17174383 - 2 Sep 2024
Viewed by 707
Abstract
Drill-bit metamorphism (DBM) is the process of thermal degradation of drilling fluid at the interface of the bit and rock due to the overheating of the bit. The heat generated by the drill when drilling into a rock formation promotes the generation of [...] Read more.
Drill-bit metamorphism (DBM) is the process of thermal degradation of drilling fluid at the interface of the bit and rock due to the overheating of the bit. The heat generated by the drill when drilling into a rock formation promotes the generation of artificial hydrocarbon and non-hydrocarbon gas, changing the composition of the gas. The objective of this work is to recognize and evaluate artificial gases originating from DBM in wells targeting oil accumulations in pre-salt carbonates in the Santos Basin, Brazil. For the evaluation, chromatographic data from advanced mud gas equipment, drilling parameters, drill type, and lithology were used. The molar concentrations of gases and gas ratios (especially ethene/ethene+ethane and dryness) were analyzed, which identified the occurrence of DBM. DBM is most severe when wells penetrate igneous and carbonate rocks with diamond-impregnated drill bits. The rate of penetration, weight on bit, and rotation per minute were evaluated together with gas data but did not present good correlations to assist in identifying DBM. The depth intervals over which artificial gases formed during DBM are recognized should not be used to infer pay zones or predict the composition and properties of reservoir fluids because the gas composition is completely changed. Full article
(This article belongs to the Topic Advances in Oil and Gas Wellbore Integrity)
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<p>Regional map of the Santos Basin, showing the location of wells that were drilled using advanced mud gas analysis.</p>
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<p>Generalized process of advanced mud gas extraction and analysis (modified from Ablard et al., 2012 [<a href="#B3-energies-17-04383" class="html-bibr">3</a>]). The schematic illustrates well drilling and mud circulation, positioning of mud extraction probes at the IN and OUT along the mudflow line, and subsequent analysis of the gas inside the mudlogging unit by gas chromatograph and mass spectrometer.</p>
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<p>Mud gas logs for well E3 are divided into four parts including formation tops, lithology, and gas ratios (Well-E3 a panel), ratios C<sub>2</sub>/C<sub>1</sub>, dryness, and ethene/(ethane+ethene) (Well-E3 b panel), gas chromatography (Well-E3 c panel), and normalized alkanes (Well-E3 d panel). See <a href="#energies-17-04383-t002" class="html-table">Table 2</a> for mnemonics of lithological types. Interval with drill-bit metamorphism marked with green arrow. From 5500 until the end of the well, changes were observed in the gas curves, mainly in the igneous rock interval caused by drill-bit metamorphism. In Well-E3 b, we observed an increase in the C<sub>2</sub>/C<sub>1</sub> curve and a decrease in dryness causing the inversion of these two curves. In Well-E3 c, an increase in C<sub>2</sub> is also observed, overlapping C<sub>1</sub> from 5500 m to the end of the well, and in Well-E3 d, the relative percentage of ethane is greater than that of methane depending on the increase in ethylene.</p>
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<p>Mud gas logs for well D3 are divided into four parts including formation tops, lithology, and gas ratios (Well-D3 a panel), ratios C<sub>2</sub>/C<sub>1</sub>, dryness, and ethene/(ethane+ethene) (Well-D3 b panel), and gas chromatography (Well-D3 c panel) and normalized alkanes (Well-D3 d panel). See <a href="#energies-17-04383-t002" class="html-table">Table 2</a> for mnemonics of lithological types.</p>
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<p>The panel is separated into three different wells. Well-B2 (c, d, and b), Well-C2 (c, d, and b), and Well-D5 (c, d, and b) are represented on all the graphs that identify the drill-bit metamorphism in wells B2, C2, and D5. For the three wells, the chromatographic distribution graphs of alkanes (Well-B2 c, Well-C2 c, and Well-D5 c), the concentration of normalized alkanes from C<sub>1</sub> to C<sub>5</sub> (Well-B2 d, Well-C2 d, and Well-D5 d), and ratios (Well-B2 b, Well-C2 b, and Well-D5 b) were evaluated. Comparison between the gas chromatography of wells B2 (Well-B2 c—without drill-bit metamorphism until 5918 m and with drill-bit metamorphism when started the igneous rock), well C2 (Well-C2 c—with drill-bit metamorphism in the interval below 5700 m after changing from PDC to impregnated drill), and well D5 (Well-D5 c—with drill-bit metamorphism throughout the well drilled with the impregnated drill). Interval with drill-bit metamorphism marked with green arrow.</p>
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<p>Correlations between the drilling parameters and the gas ratios that were used for the identification of DBM considering the groups of wells with and without DBM, separated by lithology (ROP x C<sub>2</sub>/C<sub>1</sub>, WOB x ethene/ethene+ethane, and RPM x dryness).</p>
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19 pages, 6825 KiB  
Article
Selectivities of Carbon Dioxide over Ethane in Three Methylimidazolium-Based Ionic Liquids: Experimental Data and Modeling
by Nadir Henni, Amr Henni and Hussameldin Ibrahim
Molecules 2024, 29(17), 4152; https://doi.org/10.3390/molecules29174152 - 1 Sep 2024
Viewed by 759
Abstract
This work focused on the solubility of ethane in three promising ionic liquids {1-Hexyl-3-methylimidazolium bis(trifluormethylsulfonyl) imide [HMIM][Tf2N], 1-Butyl-3-methyl-imidazolium dimethyl-phosphate [BMIM][DMP], and 1-Propyl-3-methylimidazolium bis(trifluoromethyl-sulfonyl)-imide [PMIM][Tf2N]}. The solubilities were measured at 303.15 K to 343.15 K and pressures up to 1.4 MPa using a gravimetric [...] Read more.
This work focused on the solubility of ethane in three promising ionic liquids {1-Hexyl-3-methylimidazolium bis(trifluormethylsulfonyl) imide [HMIM][Tf2N], 1-Butyl-3-methyl-imidazolium dimethyl-phosphate [BMIM][DMP], and 1-Propyl-3-methylimidazolium bis(trifluoromethyl-sulfonyl)-imide [PMIM][Tf2N]}. The solubilities were measured at 303.15 K to 343.15 K and pressures up to 1.4 MPa using a gravimetric microbalance. The overall ranking of ethane solubility in the ionic liquids from highest to lowest is the following: [HMIM][Tf2N] > [PMIM][Tf2N] > [BMIM][DMP]. The Peng–Robinson equation of state was used to model the experimental data using three different mixing rules: van der Waals one, van der Waals two, and Wong–Sandler mixing rules combined with the Non-Random Two-Liquid model. The average absolute deviations for the three mixing rules for the ionic liquids at the three temperatures were 4.39, 2.45, and 2.45%, respectively. Henry’s Law constants for ethane in [BMIM] [DMP] were the highest (lowest solubility) amongst other ionic liquids studied in this work. The solubility ranking for the 3 ILs was confirmed by calculating their overall polarity parameter (N) using COSMO-RS. The selectivity of CO2 over C2H6 was estimated at three temperatures, and the overall ranking of the selectivity was in the following order: [PMIM][Tf2N] > [BMIM][DMP] > [HMIM][Tf2N] > Selexol. Selexol is an efficient and widely used physical solvent in gas sweetening. It has lower selectivity than the three ionic liquids studied. [PMIM][Tf2N], a promising solvent, has the highest selectivity among the three ILs studied and would, therefore, be the best choice if, in addition to carbon dioxide capture, ethane co-absorption was to be avoided. The enthalpy and entropy of solvation at infinite dilution were also estimated. Full article
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<p>Comparison between the measured data for the solubility of C<sub>2</sub>H<sub>6</sub> in [BMIM][PF6] and those reported by Anthony et al. (2005) [<a href="#B6-molecules-29-04152" class="html-bibr">6</a>] at 298.15 K.</p>
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<p>Solubility data for C<sub>2</sub>H<sub>6</sub> in [HMIM][Tf2N] at different temperatures and pressures up to 1.4 MPa: ♦ 303.15 K; ■ 323.15 K; ▲: 343.15 K. Experimental VLE data were correlated with (<b>a</b>) PR + vdW1, (<b>b</b>) PR + vdW2, and (<b>c</b>) PR + WS + NRTL.</p>
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<p>Solubility data of C<sub>2</sub>H<sub>6</sub> in [BMIM][DMP] at different temperatures: ♦ 303.15 K; ■ 323.15 K; ▲ 343.15 K. Experimental VLE data were correlated with (<b>a</b>) PR + vdW1, (<b>b</b>) PR + vdW2, and (<b>c</b>) PR + WS + NRTL.</p>
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<p>Solubility data of C<sub>2</sub>H<sub>6</sub> in [BMIM][DMP] at different temperatures: ♦ 303.15 K; ■ 323.15 K; ▲ 343.15 K. Experimental VLE data were correlated with (<b>a</b>) PR + vdW1, (<b>b</b>) PR + vdW2, and (<b>c</b>) PR + WS + NRTL.</p>
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<p>Solubility data of C<sub>2</sub>H<sub>6</sub> in [PMIM][Tf2N] at different temperatures: ♦ 303.15 K; ■ 323.15 K; ▲ 343.15 K and model correlation: lines with (<b>a</b>) PR + vdW1, (<b>b</b>) PR + vdW2, and (<b>c</b>) PR + WS + NRTL.</p>
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<p>Solubility data of C<sub>2</sub>H<sub>6</sub> in [PMIM][Tf2N] at different temperatures: ♦ 303.15 K; ■ 323.15 K; ▲ 343.15 K and model correlation: lines with (<b>a</b>) PR + vdW1, (<b>b</b>) PR + vdW2, and (<b>c</b>) PR + WS + NRTL.</p>
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<p>Comparison between the solubility of C<sub>2</sub>H<sub>6</sub> in the 3 ILs at 303.15 K.</p>
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<p>Solubility of C<sub>2</sub>H<sub>6</sub> in the two ILs with [Tf2N]-anion at 303.15 K.</p>
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<p>Comparison of Henry’s Law constants for C<sub>2</sub>H<sub>6</sub> in ILs at (<b>a</b>) 303.15 K, (<b>b</b>) 323.15 K, and (<b>c</b>) 343.15 K; red: ionic liquids used in this work and blue: other ILs obtained from the literature summarized by Nath et al. [<a href="#B12-molecules-29-04152" class="html-bibr">12</a>].</p>
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<p>Comparison of CO<sub>2</sub>/C<sub>2</sub>H<sub>6</sub> selectivity in several ionic liquids reported by Nath et al. [<a href="#B12-molecules-29-04152" class="html-bibr">12</a>] at 303.15 K.</p>
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<p>Comparison of CO<sub>2</sub>/C<sub>2</sub>H<sub>6</sub> selectivity in several ionic liquids reported by Nath et al. [<a href="#B12-molecules-29-04152" class="html-bibr">12</a>] at 323.15 K.</p>
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<p>Comparison of CO<sub>2</sub>/C<sub>2</sub>H<sub>6</sub> selectivity with other ionic liquids reported by Nath et al. [<a href="#B12-molecules-29-04152" class="html-bibr">12</a>] at 343.15 K.</p>
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<p>IGA-003 setup.</p>
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22 pages, 14767 KiB  
Article
Experiments and Calculation on New N,N-bis-Tetrahydroacridines
by Madalina-Marina Hrubaru, Constantin Draghici, Francis Aurelien Ngounoue Kamga, Elena Diacu, ThankGod C. Egemonye, Anthony C. Ekennia and Eleonora-Mihaela Ungureanu
Molecules 2024, 29(17), 4082; https://doi.org/10.3390/molecules29174082 - 28 Aug 2024
Viewed by 477
Abstract
Tetrahydroacridines arouse particular interest due to the potential possibilities of application in the medical field and protection against corrosion. Bis-tetrahydroacridines were newly synthesized by Pfitzinger condensation of 5,5′-(ethane-1,2-diyl) diindoline-2,3-dione with several cyclanones. NMR, MS, and FT-IR were used to prove their molecular [...] Read more.
Tetrahydroacridines arouse particular interest due to the potential possibilities of application in the medical field and protection against corrosion. Bis-tetrahydroacridines were newly synthesized by Pfitzinger condensation of 5,5′-(ethane-1,2-diyl) diindoline-2,3-dione with several cyclanones. NMR, MS, and FT-IR were used to prove their molecular structure. In addition, a computer-aided study was performed for the lowest energy conformers of each structure, in vacuum conditions, at ground state using DFT models to assess their electronic properties. UV–Vis and voltammetric methods (cyclic voltammetry, differential pulse voltammetry, and rotating disk electrode voltammetry) were used to investigate their optical and electrochemical properties. The results obtained for these π-conjugated heteroaromatic compounds lead to the conclusion that they have real potential in applications in different fields such as pharmaceuticals and especially as corrosion inhibitors. Full article
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<p>Molecular structure of N,N′-(4,4′-(ethane-1,2-diyl)<span class="html-italic">bis</span>(4,1-phenylene))-<span class="html-italic">bis</span>(2-(hydroxyimino) acetamide) (<b>2</b>).</p>
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<p>Molecular structure of 5,5′-(ethane-1,2-diyl)diindoline-2,3-dione (<b>3</b>).</p>
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<p>Molecular structure of 7,7′-(ethane-1,2-diyl)<span class="html-italic">bis</span>(2,3-dihydro-1H-cyclopenta[b]quinoline-9-carboxylic acid) (<b>4a</b>).</p>
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<p>Structure of 7,7′-(ethane-1,2-diyl)<span class="html-italic">bis</span>(1,2,3,4-tetrahydroacridine-9-carboxylic acid) (<b>4b</b>).</p>
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<p>HOMO, HOMO-1, LUMO, LUMO + 1 plots for compound <b>4a</b>.</p>
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<p>HOMO, HOMO-1, LUMO, LUMO + 1 plots for compound <b>4b</b>.</p>
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<p>DPV vs. CV (0.1 V/s) (<b>a</b>) and RDE vs. DPV (<b>b</b>) curves at different concentrations of <b>4a</b>.</p>
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<p>CV curves in anodic and cathodic scans on variable domains at 0.1 V/s (<b>a</b>) and at variable scan rates in 5 successive CV (0.1 V/s) cathodic scans (<b>b</b>) for [<b>4a</b>] = 1 mM.</p>
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<p>CV curves (0.1 V/s) in the first cathodic scans at variable scan rates (<b>a</b>) and the dependence of current intensity at −2.6 V on CV curves (in the 1st cycle) on scan rate (red line and points) or on the square root of the scan rate (black line and points) (<b>b</b>) for [<b>4a</b>] = 1 mM.</p>
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<p>CV curves in the first 5 cycles of anodic scans at variable scan rates (<b>a</b>), the first cycle at variable scan rate (<b>b</b>), and the dependence of current intensity at 0.3 V on CV curves (in the 1st cycle) on the scan rate (red line and points), or on the square root of the scan rate (black line and points) (<b>c</b>) for [<b>4a</b>] = 1 mM.</p>
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<p>CV curves in the first anodic scans at variable scan rates (<b>a</b>), CV curves in the first anodic scan at variable scan rates (<b>b</b>), and the dependence of current intensity at 0.6 V from the 1st cycle of the CV curves on the scan rate (red line and points) or on the square root of the scan rate (black line and points) (<b>c</b>) for [<b>4a</b>] = 1 mM.</p>
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<p>CV curves (0.1 V/s) in ferrocene solution in 0.1 M TBAP/CH<sub>3</sub>CN on bare GC electrode (...) and on the electrode after 5 cycles in the range of a1 process (<b>a</b>) or a2 process (<b>b</b>) in solution of [<b>4a</b>] = 1 mM.</p>
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<p>CV (0.1 V/s) vs. DPV (<b>a</b>) and DPV vs. RDE (<b>b</b>) curves at different concentrations of <b>4b</b> and variable electrode rotation rates.</p>
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<p>CV curves (0.1 V/s) in anodic and cathodic scans on variable domains (<b>a</b>) and at variable scan rates in 5 successive cathodic and anodic scans (<b>b</b>) for [<b>4b</b>] = 1 mM.</p>
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<p>Anodic and cathodic RDE curves at different concentrations of <b>4b</b> at various rotation rates: 500 rpm (<b>a</b>), 1000 rpm (<b>b</b>), and 1500 rpm (<b>c</b>).</p>
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<p>Synthesis of tetrahydroacridines analogous with 4,4′-(ethane-1,2-diyl)dianiline skeleton; I. CCl<sub>3</sub>-CHO, NH<sub>2</sub>OH, Na<sub>2</sub>SO<sub>4</sub>, T = 95–100 °C; II. H<sub>2</sub>SO<sub>4</sub>, T = 70 °C; III. KOH alcoholic solution, cyclanone (cyclohexanone or cyclopentanone for <b>4a</b> and <b>4b</b>, respectively).</p>
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<p>Fragmentation pattern for ethylene bridged <span class="html-italic">bis</span>-acids.</p>
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15 pages, 4342 KiB  
Article
Development of a Screening Platform for Optimizing Chemical Nanosensor Materials
by Larissa Egger, Lisbeth Reiner, Florentyna Sosada-Ludwikowska, Anton Köck, Hendrik Schlicke, Sören Becker, Öznur Tokmak, Jan Steffen Niehaus, Alexander Blümel, Karl Popovic and Martin Tscherner
Sensors 2024, 24(17), 5565; https://doi.org/10.3390/s24175565 - 28 Aug 2024
Viewed by 574
Abstract
Chemical sensors, relying on changes in the electrical conductance of a gas-sensitive material due to the surrounding gas, typically react with multiple target gases and the resulting response is not specific for a certain analyte species. The purpose of this study was the [...] Read more.
Chemical sensors, relying on changes in the electrical conductance of a gas-sensitive material due to the surrounding gas, typically react with multiple target gases and the resulting response is not specific for a certain analyte species. The purpose of this study was the development of a multi-sensor platform for systematic screening of gas-sensitive nanomaterials. We have developed a specific Si-based platform chip, which integrates a total of 16 sensor structures. Along with a newly developed measurement setup, this multi-sensor platform enables simultaneous performance characterization of up to 16 different sensor materials in parallel in an automated gas measurement setup. In this study, we chose the well-established ultrathin SnO2 films as base material. In order to screen the sensor performance towards type and areal density of nanoparticles on the SnO2 films, the films are functionalized by ESJET printing Au-, NiPt-, and Pd-nanoparticle solutions with five different concentrations. The functionalized sensors have been tested toward the target gases: carbon monoxide and a specific hydrogen carbon gas mixture of acetylene, ethane, ethne, and propene. The measurements have been performed in three different humidity conditions (25%, 50% and 75% r.h.). We have found that all investigated types of NPs (except Pd) increase the responses of the sensors towards CO and HCmix and reach a maximum for an NP type specific concentration. Full article
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<p>2 × 2 cm<sup>2</sup> sized Si-based platform chip integrating 16 sensor devices. The chip enables conductive sensor measurement in a 4-point measurement configuration and exhibits 64 contact pads for the gas sensors; 2 additional pads are required for the Pt100-like temperature sensor. The red rectangle designates the “hot area” heated by the Au-coated Cu-block underneath. The insert shows a final processed 100 × 50 µm<sup>2</sup> sized SnO<sub>2</sub> film; the active sensor area between the electrodes measures 30 × 50 µm<sup>2</sup>.</p>
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<p>(<b>a</b>) Measurement setup (“open state”) consisting of a holder for the platform chip and a lid with gas inlet, electrical connectors, and contact pins. (<b>b</b>): Front view of the lid, which holds two prober heads with a total of 66 contact pins. (<b>c</b>) The platform chip is placed on a massive heater block (fabricated with copper, coated with gold) which heats the central part of the chip from underneath up to 350 °C. As soon as the lid is closed, the pins contact 66 Ti/Pt pads on the platform chip and enable simultaneous characterization of all 16 sensor structures in parallel.</p>
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<p><b>Left</b>: Schematic of an ESJET system. A capillary (“emitter”) with the printing ink and a needle electrode is positioned a short distance above the grounded substrate. <b>Right</b>: ESJET nozzle positioned above a single SnO<sub>2</sub> sensor film on the Si-platform chip; the NP-dot diameter matches the active area of the sensor films, which measures 30 × 50 µm<sup>2</sup>.</p>
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<p>Printing scheme of the NP solutions with different NP concentrations (1:1, 1:2, 1:4, 1:8, 1:16) on the SnO<sub>2</sub> sensor films on the Si-platform chips. Two sensors, respectively, are functionalized with the same NP concentration; six SnO<sub>2</sub> sensor films are not functionalized and form the reference sensors.</p>
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<p>SEM graph of Sensor A, which is functionalized with Au-NPs; the Au-NPs can be clearly seen as white dots.</p>
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<p>Transmission electron microscopy images of the noble metal NP batches used for sensor functionalization. Scale bars: 200 nm (<b>left</b> column), and 50 nm (<b>right</b> column). All particle batches showed approximately spherical particle shapes with average diameters of 5.3 ± 0.5 nm, 4.4 ± 0.5 nm, and 3.3 ± 0.4 nm for the Au, Pd, and NiPt material systems, respectively.</p>
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<p>Typical resistance behavior of bare and an Au-NP functionalized SnO<sub>2</sub> sensors (black and red curves, respectively) during exposure to 50 ppm of CO and HC<sub>mix</sub> at 300 °C operation temperature (bottom red) at 50%, 25% and 75% humidity levels (bottom black).</p>
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<p>Response of bare SnO<sub>2</sub> sensors and SnO<sub>2</sub> sensors functionalized with different concentrations of Au-NP inks towards (<b>a</b>) 50 ppm CO, and (<b>b</b>) 50 ppm HC<sub>mix</sub> at 300 °C operation temperature.</p>
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<p>Response of bare SnO<sub>2</sub> sensors and SnO<sub>2</sub> sensors functionalized with different concentrations of NiPt-NP inks towards (<b>a</b>) 50 ppm CO, and (<b>b</b>) 50 ppm HC<sub>mix</sub> at 300 °C operation temperature.</p>
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<p>Response of bare SnO<sub>2</sub> sensors and SnO<sub>2</sub> sensors functionalized with different concentrations of Pd-NP inks towards (<b>a</b>) 50 ppm CO, and (<b>b</b>) 50 ppm HC<sub>mix</sub> at 300 °C operation temperature.</p>
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<p>Response of sensors functionalized with Au, Pd, and NiPt-NPs with different concentrations towards (<b>a</b>) 50 ppm CO, and (<b>b</b>) 50 ppm HC<sub>mix</sub> at 50% rh and 300 °C operation temperature normalized to the response of bare SnO<sub>2</sub> sensors.</p>
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<p>Proposed CMOS-integrated multi-sensor device. By using proper combinations of MOx film, and types of NPs on the 8 µhps (exemplarily shown for 4 µhps), we will realize a 5 × 5 mm<sup>2</sup> sized multi-gas sensor device capable of simultaneous detection of several target gases.</p>
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15 pages, 1579 KiB  
Article
Characteristic Analysis and Health Risk Assessment of PM2.5 and VOCs in Tianjin Based on High-Resolution Online Data
by Yanqi Huangfu, Feng Wang, Qili Dai, Danni Liang, Guoliang Shi and Yinchang Feng
Toxics 2024, 12(9), 622; https://doi.org/10.3390/toxics12090622 - 23 Aug 2024
Viewed by 553
Abstract
This study leveraged 2019 online data of particulate matter (PM2.5) and volatile organic compounds (VOCs) in Tianjin to analyze atmospheric pollution characteristics. PM2.5 was found to be primarily composed of water-soluble ions, with nitrates as the dominant component, while VOCs [...] Read more.
This study leveraged 2019 online data of particulate matter (PM2.5) and volatile organic compounds (VOCs) in Tianjin to analyze atmospheric pollution characteristics. PM2.5 was found to be primarily composed of water-soluble ions, with nitrates as the dominant component, while VOCs were predominantly alkanes, followed by alkenes and aromatic hydrocarbons, with notable concentrations of propane, ethane, ethylene, toluene, and benzene. The receptor model identified six major sources of PM2.5 and seven major sources of VOCs. The secondary source is the main contribution source, while motor vehicles and coal burning are important primary contribution sources in PM2.5. And, industrial processes and natural gas volatilization were considered major contributors for VOCs. A health risk assessment indicated negligible non-carcinogenic risks but potential carcinogenic risks from trace metals As and Cr, and benzene within VOCs, underscoring the necessity for focused public health measures. A risk attribution analysis attributed As and Cr in PM to coal combustion and vehicular emissions. Benzene in VOCs primarily originates from fuel evaporation, and industrial and vehicular emissions. These findings underscore the potential for reducing health risks from PM and VOCs through enhanced regulation of emissions in coal, industry, and transportation. Such strategies are vital for advancing air quality management and safeguarding public health. Full article
(This article belongs to the Special Issue Source and Components Analysis of Aerosols in Air Pollution)
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<p>Time series of concentrations (<b>a</b>), percentages (<b>b</b>) of VOCs, aerosol concentrations and compounds (<b>c</b>) and meteorological parameters (<b>d</b>).</p>
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<p>Source contribution of VOCs (<b>a</b>) and PM<sub>2.5</sub> (<b>b</b>) in Tianjin.</p>
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<p>Health risks of trace metals in Tianjin. The result of hazard quotient (<b>a</b>) and incremental lifetime cancer risk (<b>b</b>).</p>
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<p>Hazard quotient of VOCS in Tianjin.</p>
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<p>Sources of trace metals with health risk (As and Cr).</p>
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<p>Sources of VOCs with health risk (benzene).</p>
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