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14 pages, 2979 KiB  
Article
Ethanol Production Using Zymomonas mobilis and In Situ Extraction in a Capillary Microreactor
by Julia Surkamp, Lennart Wellmann, Stephan Lütz, Katrin Rosenthal and Norbert Kockmann
Micromachines 2024, 15(10), 1255; https://doi.org/10.3390/mi15101255 - 13 Oct 2024
Viewed by 895
Abstract
The bacterium Zymomonas mobilis is investigated as a model organism for the cultivation and separation of ethanol as a product by in situ extraction in continuous flow microreactors. The considered microreactor is the Coiled Flow Inverter (CFI), which consists of a capillary coiled [...] Read more.
The bacterium Zymomonas mobilis is investigated as a model organism for the cultivation and separation of ethanol as a product by in situ extraction in continuous flow microreactors. The considered microreactor is the Coiled Flow Inverter (CFI), which consists of a capillary coiled onto a support structure. Like other microreactors, the CFI benefits from a high surface-to-volume ratio, which enhances mass and heat transfer. Compared to many other microreactors, the CFI offers the advantage of operating without internal structures, which are often used to ensure good mixing. The simplicity of the design makes the CFI particularly suitable for biochemical applications as cells do not get stuck or damaged by internal structures. Despite this simplicity, good mixing is achieved through flow vortices caused by Taylor and Dean vortices. The reaction system consists of two phases, in which the aqueous phase carries the bacterium and an oleyl alcohol phase is used to extract the ethanol produced. Key parameters for evaluation are bacteria growth and the amount of ethanol produced by the microorganism. The results show the suitability of the CFI for microbial production of valuable compounds. A maximum ethanol concentration of 1.26 g L−1 was achieved for the experiment in the CFI. Overall, the cultivation in the CFI led to faster growth of Z. mobilis, resulting in 25% higher ethanol production than in conducted batch experiments. Full article
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Figure 1

Figure 1
<p>Two-phase flow in a straight (<b>a</b>) and in a coiled capillary (<b>b</b>) with particle flow in the continuous phase (<b>c</b>) indicating the nearly parabolic flow profile, adapted from [<a href="#B20-micromachines-15-01255" class="html-bibr">20</a>].</p>
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<p>Experimental setup with (<b>a</b>) schematic representation of a CFI, and (<b>b</b>) realization of the CFI in an acrylic glass container, fabricated in the TU Dortmund workshop.</p>
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<p>(<b>a</b>) T-junction for the generation of the liquid–liquid Taylor flow: The oleyl alcohol flows through the needle and is detached in a co-current flow with the cell suspension. (<b>b</b>) Experimental Setup: 1a and 1b are the peristaltic pumps, 2 is a heat plate, 3 shows the acrylic glass container with the CFI, 4 is the separating funnel.</p>
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<p>Experimental results (blue dots, single experiments) to determine the miscibility gap of the ternary system water, ethanol (EtOH) and oleyl alcohol (OA). The area below the curve encompasses the miscibility gap. <span class="html-italic">φ</span><sub>H2O</sub>, <span class="html-italic">φ</span><sub>OA</sub> and <span class="html-italic">φ</span><sub>EtOH</sub> are the corresponding volume fractions for water, oleyl alcohol, and ethanol. The black dashed lines represent conodes from the literature [<a href="#B29-micromachines-15-01255" class="html-bibr">29</a>].</p>
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<p>Reaction equations for the conversion of ethanol into acetaldehyde catalyzed by an alcohol dehydrogenase (ADH) and subsequent conversion into acetic acid catalyzed by an aldehyde dehydrogenase (Al-DH). The enzymes are used in an ethanol quantification kit to determine ethanol concentrations.</p>
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<p>(<b>a</b>) Plot of the OD<sub>600</sub> values from the various batch experiments as growth curves of <span class="html-italic">Z. mobilis</span>. (<b>b</b>) Plot of the ethanol production within the batch experiments. Experiments were performed in triplicate.</p>
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<p>Flow map for different volumetric flow rates of water and oleyl alcohol. Blue crosses: irregular flow, red dots: stable Taylor Flow, black square: operating point.</p>
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<p>Cell number from the CFI experiments over time. Blue squares: with pre-culture, orange dots: without pre-culture, and red triangles: experiments with silicon oil instead of oleyl alcohol. Experiments were performed in triplicate.</p>
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<p>Ethanol concentrations over time (<b>a</b>) from aqueous phase (cell suspension), and (<b>b</b>) from the organic phase (oleyl alcohol). Blue squares: experiments with pre-cultivation of <span class="html-italic">Z. mobilis</span>, orange dots: experiments without pre-cultivation, red triangles: experiments with silicone oil instead of oleyl alcohol.</p>
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27 pages, 18300 KiB  
Article
Statistical Analysis of Bubble Parameters from a Model Bubble Column with and without Counter-Current Flow
by P. Kováts and K. Zähringer
Fluids 2024, 9(6), 126; https://doi.org/10.3390/fluids9060126 - 28 May 2024
Viewed by 737
Abstract
Bubble columns are widely used in numerous industrial processes because of their advantages in operation, design, and maintenance compared to other multiphase reactor types. In contrast to their simple design, the generated flow conditions inside a bubble column reactor are quite complex, especially [...] Read more.
Bubble columns are widely used in numerous industrial processes because of their advantages in operation, design, and maintenance compared to other multiphase reactor types. In contrast to their simple design, the generated flow conditions inside a bubble column reactor are quite complex, especially in continuous mode with counter-current liquid flow. For the design and optimization of such reactors, precise numerical simulations and modelling are needed. These simulations and models have to be validated with experimental data. For this reason, experiments were carried out in a laboratory-scale bubble column using shadow imaging and particle image velocimetry (PIV) techniques with and without counter-current liquid flow. In the experiments, two types of gases—relatively poorly soluble air and well-soluble CO2—were used and the bubbles were generated with three different capillary diameters. With changing gas and liquid flow rates, overall, 108 different flow conditions were investigated. In addition to the liquid flow fields captured by PIV, shadow imaging data were also statistically evaluated in the measurement volume and bubble parameters such as bubble diameter, velocity, aspect ratio, bubble motion direction, and inclination. The bubble slip velocity was calculated from the measured liquid and bubble velocities. The analysis of these parameters shows that the counter-current liquid flow has a noticeable influence on the bubble parameters, especially on the bubble velocity and motion direction. In the case of CO2 bubbles, remarkable bubble shrinkage was observed with counter-current liquid flow due to the enhanced mass transfer. The results obtained for bubble aspect ratio are compared to known correlations from the literature. The comprehensive and extensive bubble data obtained in this study will now be used as a source for the development of correlations needed in the validation of numerical simulations and models. The data are available from the authors on request. Full article
(This article belongs to the Special Issue Mass Transfer in Multiphase Reactors)
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Figure 1

Figure 1
<p>Experimental setup.</p>
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<p>Bubbly flow field in the bottom half of the column for 6.0 l·h<sup>−1</sup> air bubbles generated from 0.13 mm capillaries: without counter-current (<b>left</b> image pair) and with the highest counter-current liquid flow rate (<b>right</b> image pair). The measurement direction (front view) is on the left and the side view on the right of each image pair.</p>
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<p>Bubbly flow fields in the bottom half of the column for 6.6 l·h<sup>−1</sup> CO<sub>2</sub> bubbles generated from 0.13 mm capillaries: without counter-current (<b>left</b> image pair) and with the highest counter-current liquid flow rate (<b>right</b> image pair). The measurement direction (front view) is on the left and the side view on the right of each image pair.</p>
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<p>Global mean bubble <span class="html-italic">ESD</span> (<b>a</b>) and bubble velocity (<b>b</b>) distributions at different counter-current liquid flow conditions and 10 l·h<sup>−1</sup> air flow rate from 0.18 mm diameter capillaries.</p>
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<p>Bubble parameters evaluated in this study and bubble shapes corresponding to the exemplified aspect ratios.</p>
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<p>Exemplary relationship between bubble aspect ratio <span class="html-italic">E</span> and the equivalent sphere diameter <span class="html-italic">ESD</span> at a 6.4 l·h<sup>−1</sup> CO<sub>2</sub> flow rate, 11.1 l·min<sup>−1</sup> counter-current liquid flow, and 3.6 mm capillary diameter. Yellow circles represent the mean aspect ratio.</p>
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<p>Equivalent sphere diameter <span class="html-italic">ESD</span> of air bubbles as a function of the column height, generated with different capillaries (<b>a</b>) at different liquid “l” (<b>b</b>) and gas “g” volume flow rates (<b>c</b>,<b>d</b>).</p>
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<p>Equivalent sphere diameter <span class="html-italic">ESD</span> of CO<sub>2</sub> bubbles as a function of the column height, generated with different capillaries (<b>a</b>) at different liquid “l” (<b>b</b>) and gas “g” volume flow rates (<b>c</b>,<b>d</b>).</p>
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<p>Bubble velocity of air bubbles as a function of the column height, generated with different capillaries (<b>a</b>) at different liquid “l” (<b>b</b>) and gas “g” volume flow rates (<b>c</b>,<b>d</b>).</p>
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<p>Bubble velocity of CO<sub>2</sub> bubbles as a function of the column height, generated with different capillaries (<b>a</b>) at different liquid “l” (<b>b</b>) and gas “g” volume flow rates (<b>c</b>,<b>d</b>).</p>
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<p>Aspect ratio <span class="html-italic">E</span> of air bubbles as a function of the column height, generated with different capillaries (<b>a</b>) at different liquid “l” (<b>b</b>) and gas “g” volume flow rates (<b>c</b>,<b>d</b>).</p>
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<p>Aspect ratio <span class="html-italic">E</span> of CO<sub>2</sub> bubbles as a function of the column height, generated with different capillaries (<b>a</b>) at different liquid “l” (<b>b</b>) and gas “g” volume flow rates (<b>c</b>,<b>d</b>).</p>
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<p>Streamline visualization of the mean liquid flow structure in the laboratory-scale bubble column at different counter-current liquid flow rates and at a 10 l·h<sup>−1</sup> air flow rate with the 0.18 mm capillaries. The bubbles were introduced at the bottom. The arrows indicate the main liquid flow direction.</p>
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<p>Mean vertical liquid velocity with air bubbles as a function of the column height, generated with different capillaries (<b>a</b>) at different liquid “l” (<b>b</b>) and gas “g” volume flow rates (<b>c</b>,<b>d</b>).</p>
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<p>Mean vertical liquid velocity with CO<sub>2</sub> bubbles as a function of the column height, generated with different capillaries (<b>a</b>) at different liquid “l” (<b>b</b>) and gas “g” volume flow rates (<b>c</b>,<b>d</b>).</p>
Full article ">Figure 15 Cont.
<p>Mean vertical liquid velocity with CO<sub>2</sub> bubbles as a function of the column height, generated with different capillaries (<b>a</b>) at different liquid “l” (<b>b</b>) and gas “g” volume flow rates (<b>c</b>,<b>d</b>).</p>
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<p>Mean slip velocities for air and CO<sub>2</sub> bubbles, generated with 0.18 mm capillaries at 30.8 l·min<sup>−1</sup> liquid and 3.3 mg·s<sup>−1</sup> gas mass flow rates.</p>
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<p>Mean slip velocity with air bubbles as a function of the column height, generated with different capillaries (<b>a</b>) at different liquid “l” (<b>b</b>) and gas “g” volume flow rates (<b>c</b>,<b>d</b>).</p>
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<p>Mean slip velocity with CO<sub>2</sub> bubbles as a function of the column height, generated with different capillaries (<b>a</b>) at different liquid “l” (<b>b</b>) and gas “g” volume flow rates (<b>c</b>,<b>d</b>).</p>
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<p>Relationship between bubble aspect ratio <span class="html-italic">E</span> and equivalent sphere diameter <span class="html-italic">ESD</span> for air bubbles: present measurements and calculations according to [<a href="#B28-fluids-09-00126" class="html-bibr">28</a>,<a href="#B29-fluids-09-00126" class="html-bibr">29</a>].</p>
Full article ">Figure 20
<p>Relationship between bubble aspect ratio <span class="html-italic">E</span> and equivalent sphere diameter <span class="html-italic">ESD</span> for CO<sub>2</sub> bubbles: present measurements and calculations according to [<a href="#B28-fluids-09-00126" class="html-bibr">28</a>,<a href="#B29-fluids-09-00126" class="html-bibr">29</a>].</p>
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17 pages, 4706 KiB  
Article
Improvement of Electrical Conductivity of In Situ Iodine-Doped Polypyrrole Film Using Atmospheric Pressure Plasma Reactor with Capillary Electrodes
by Eun Young Jung, Salman Khalil, Hyojun Jang, Habeeb Olaitan Suleiman, Jae Young Kim, Bhum Jae Shin, Heung-Sik Tae and Choon-Sang Park
Nanomaterials 2024, 14(5), 468; https://doi.org/10.3390/nano14050468 - 4 Mar 2024
Cited by 1 | Viewed by 1360
Abstract
To improve the electrical conductivity of polypyrrole (PPy) nanostructure film through in situ iodine (I2) doping, this study proposes an atmospheric pressure plasma reactor (APPR) where heated I2 dopant vapor is fed through capillary electrodes that serve as electrodes for [...] Read more.
To improve the electrical conductivity of polypyrrole (PPy) nanostructure film through in situ iodine (I2) doping, this study proposes an atmospheric pressure plasma reactor (APPR) where heated I2 dopant vapor is fed through capillary electrodes that serve as electrodes for discharge ignition. A large amount of the heated I2 vapor introduced into the reactor separately from a monomer gas can be effectively activated by an intense plasma via capillary electrodes. In particular, intensive plasma is obtained by properly adjusting the bluff body position in the APPR. Based on the ICCD and OES results, the I2 vapor injected through the capillary nozzle electrode is observed to form I2 charge species. The formed I2 species could directly participate in growing in situ I2-doped PPy films. Thus, in situ I2-doped PPy nanostructure films grown using the proposed APPR exhibit higher thicknesses of 15.3 μm and good electrical conductivities, compared to the corresponding non-doped films. Full article
(This article belongs to the Special Issue Synthesis of Nanostructures in Gas-Discharge Plasma)
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Figure 1
<p>(<b>a</b>) Experimental setup of an APPR with capillary electrodes for in situ I<sub>2</sub> doping, (<b>b</b>) photo image, (<b>c</b>) schematic diagram, and (<b>d</b>) top plane view of the APPR.</p>
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<p>(<b>a</b>) Photos and (<b>b</b>) ICCD images of the plasma discharge produced in the proposed APPR under the two conditions of no doping (Case I) and in situ I<sub>2</sub> doping at hot plate temperature of 35 °C (Case II).</p>
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<p>(<b>a</b>) Photos and (<b>b</b>) ICCD images of the plasma discharge produced in the APPR with three bluff body positions with respect to the glass guide tube.</p>
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<p>OES spectra of the APPR for the two cases of no doping (Case I) and in situ I<sub>2</sub> doping at a hot plate temperature of 35 °C (Case II).</p>
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<p>Characteristics of applied voltage (<b>i</b>), total current in plasma ON (<b>ii</b>) and OFF (<b>iii</b>) state, discharge current (<b>iv</b>), and instantaneous power (<b>v</b>) of the APPR with capillary electrodes measured under optimum conditions for Cases I (<b>a</b>) and II (<b>b</b>).</p>
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<p>Schematic diagram of the proposed mechanism for in situ I<sub>2</sub>-doped PPy nanostructure film growth.</p>
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<p>FTIR spectra of the pyrrole monomer and in situ I<sub>2</sub>-doped PPy nanostructure films grown in the APPR for Cases I and II under optimum conditions.</p>
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<p>Plane-view and cross-section images of the PPy films grown on the silicon substrate for 30 min grown in the APPR under optimum conditions for the two cases, that is, (<b>a</b>) Cases I and (<b>b</b>) II.</p>
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<p>(<b>a</b>) FE-SEM images of the cross-section sample. (<b>b</b>) EDX spectra indicating the analysis positions. (<b>c</b>) Element mapping images obtained through EDX for the in situ I<sub>2</sub>-doped PPy nanostructure film (Case II) grown on a silicon wafer in the APPR for 30 min under optimum conditions.</p>
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<p>Measured changes in the electrical σ of in situ I<sub>2</sub>-doped PPy nanostructure film (Case II) for 14 days.</p>
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12 pages, 1487 KiB  
Article
Thermal Decomposition of Methane in Capillary Tubes of Different Materials: Corundum, Titanium, Nickel, and Stainless Steel
by Mikhail S. Vlaskin, Anatoly V. Grigorenko, Aleksandr O. Dudoladov, Matvey S. Galtsov-Tsientsiala, Vinod Kumar and George E. Valyano
Appl. Sci. 2023, 13(23), 12663; https://doi.org/10.3390/app132312663 - 25 Nov 2023
Cited by 1 | Viewed by 1174
Abstract
The effect of capillary tube material on the process of thermal decomposition of methane at 1100 °C and methane supply at a rate of 2 L/h without the use of catalysts was studied. The materials used were corundum, titanium, nickel, and stainless steel. [...] Read more.
The effect of capillary tube material on the process of thermal decomposition of methane at 1100 °C and methane supply at a rate of 2 L/h without the use of catalysts was studied. The materials used were corundum, titanium, nickel, and stainless steel. The reactor was a capillary tube, which was heated from the outside with a propane burner; the length of the heating zone was about 8 cm. It was found that the efficiency of methane decomposition decreases in a number of materials: Al2O3 > Ni > Ti > stainless steel. The highest hydrogen yield (73.35 vol. %) was achieved in the experiment with a corundum tube with an inner diameter of 4 mm, and the lowest (27.75 vol. %) was achieved in the experiment with a stainless steel tube with a diameter of 6 mm. Nickel and titanium showed worse hydrogen yield results than corundum: for nickel, the volume content of hydrogen after pyrolysis was 71.27%, and for titanium, 41.51%. Full article
(This article belongs to the Special Issue Sustainable Biomass Energy: Recent Technologies and Applications)
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Figure 1
<p>Scheme of an experimental plant for methane pyrolysis in tubes of various materials [<a href="#B34-applsci-13-12663" class="html-bibr">34</a>]: 1—a cylinder with methane; 2—reducer; 3—rotameter; 4—tube (reactor); 5—T-shaped pipe; 6—T-shaped pipe insulation; 7—filter; 8—gas sampling chamber; 9—pyrometer; 10—propane–butane cylinder; 11—reducer; 12—propane–butane flow control valve; 13—burner.</p>
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<p>The contents of CH<sub>4</sub> and H<sub>2</sub> in the gaseous product of methane pyrolysis at 1100 °C in tubes of different materials.</p>
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<p>SEM images of carbon obtained via pyrolysis of methane at a process temperature of 1100 °C and a methane flow rate of 2 L/h in a corundum tube, with a resolution of 3 μm (enlargement ×50,000) (<b>A</b>), 1 μm (enlargement ×100,000) (<b>B</b>), and 0.5 μm (enlargement ×200,000) (<b>C</b>).</p>
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26 pages, 33311 KiB  
Article
Single-Bubble Rising in Shear-Thinning and Elastoviscoplastic Fluids Using a Geometric Volume of Fluid Algorithm
by Ahmad Fakhari and Célio Fernandes
Polymers 2023, 15(16), 3437; https://doi.org/10.3390/polym15163437 - 17 Aug 2023
Viewed by 1487
Abstract
The motion of air bubbles within a liquid plays a crucial role in various aspects including heat transfer and material quality. In the context of non-Newtonian fluids, such as elastoviscoplastic fluids, the presence of air bubbles significantly influences the viscosity of the liquid. [...] Read more.
The motion of air bubbles within a liquid plays a crucial role in various aspects including heat transfer and material quality. In the context of non-Newtonian fluids, such as elastoviscoplastic fluids, the presence of air bubbles significantly influences the viscosity of the liquid. This study presents the development of an interface-capturing method for multiphase viscoelastic fluid flow simulations. The proposed algorithm utilizes a geometric volume of fluid (isoAdvector) approach and incorporates a reconstructed distance function (RDF) to determine interface curvature instead of relying on volume fraction gradients. Additionally, a piecewise linear interface construction (PLIC) scheme is employed in conjunction with the RDF-based interface reconstruction for improved accuracy and robustness. The validation of the multiphase viscoelastic PLIC-RDF isoAdvector (MVP-RIA) algorithm involved simulations of the buoyancy-driven rise of a bubble in fluids with varying degrees of rheological complexity. First, the newly developed algorithm was applied to investigate the buoyancy-driven rise of a bubble in a Newtonian fluid on an unbounded domain. The results show excellent agreement with experimental and theoretical findings, capturing the bubble shape and velocity accurately. Next, the algorithm was extended to simulate the buoyancy-driven rise of a bubble in a viscoelastic shear-thinning fluid described by the Giesekus constitutive model. As the influence of normal stress surpasses surface tension, the bubble shape undergoes a transition to a prolate or teardrop shape, often exhibiting a cusp at the bubble tail. This is in contrast to the spherical, ellipsoidal, or spherical-cap shapes observed in the first case study with a bubble in a Newtonian fluid. Lastly, the algorithm was employed to study the buoyancy-driven rise of a bubble in an unbounded elastoviscoplastic medium, modeled using the Saramito–Herschel–Bulkley constitutive equation. It was observed that in very small air bubbles within the elastoviscoplastic fluid, the dominance of elasticity and capillary forces restricts the degree of bubble deformation. As the bubble volume increases, lateral stretching becomes prominent, resulting in the emergence of two tails. Ultimately, a highly elongated bubble shape with sharper tails is observed. The results show that by applying the newly developed MVP-RIA algorithm, with a tangible coarser grid compared to the algebraic VOF method, an accurate solution is achieved. This will open doors to plenty of applications such as bubble columns in reactors, oil and gas mixtures, 3D printing, polymer processing, etc. Full article
(This article belongs to the Section Polymer Physics and Theory)
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Graphical abstract

Graphical abstract
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<p>The geometry and boundary conditions for the buoyancy-driven rise of a bubble in a Newtonian fluid.</p>
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<p>Comparison of our predicted bubble rise velocity with experimental data reported by Maxworthy et al. [<a href="#B6-polymers-15-03437" class="html-bibr">6</a>] and numerical simulation results by Tsamopoulos et al. [<a href="#B7-polymers-15-03437" class="html-bibr">7</a>]. The comparison is performed for two selected values of <math display="inline"><semantics> <mrow> <mi>M</mi> <mi>o</mi> </mrow> </semantics></math> number, representing different flow conditions in a Newtonian liquid.</p>
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<p>Contour plots of the fluid’s volume fraction for <math display="inline"><semantics> <mrow> <mi>M</mi> <mi>o</mi> <mo>=</mo> <mn>2.174</mn> <mo>×</mo> <msup> <mn>10</mn> <mrow> <mo>−</mo> <mn>7</mn> </mrow> </msup> </mrow> </semantics></math> (<b>left</b>) and <math display="inline"><semantics> <mrow> <mi>M</mi> <mi>o</mi> <mo>=</mo> <mn>3.769</mn> <mo>×</mo> <msup> <mn>10</mn> <mrow> <mo>−</mo> <mn>4</mn> </mrow> </msup> </mrow> </semantics></math> (<b>right</b>) with <math display="inline"><semantics> <mrow> <mi>d</mi> <mo>=</mo> <mn>0.7</mn> <mspace width="3.33333pt"/> </mrow> </semantics></math>mm (<b>top</b>) and <math display="inline"><semantics> <mrow> <mi>d</mi> <mo>=</mo> <mn>6</mn> <mspace width="3.33333pt"/> </mrow> </semantics></math>mm (<b>bottom</b>).</p>
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<p>The geometry and boundary conditions for the buoyancy-driven rise of a bubble through a viscoelastic shear-thinning fluid.</p>
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<p>Comparison of our predicted bubble rise velocity with experimental data reported by Pilz and Brenn [<a href="#B74-polymers-15-03437" class="html-bibr">74</a>] and numerical simulation results by Ji et al. [<a href="#B9-polymers-15-03437" class="html-bibr">9</a>]. The comparison is conducted for various initial bubble volumes as they ascend through a shear-thinning viscoelastic fluid described by the Giesekus constitutive model.</p>
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<p>Contour plots of the fluid’s volume fraction for initial bubble volumes of <math display="inline"><semantics> <mrow> <msub> <mi>V</mi> <mi>b</mi> </msub> <mo>=</mo> <mn>40</mn> <mo>,</mo> <mspace width="3.33333pt"/> <mn>50</mn> <mo>,</mo> <mspace width="3.33333pt"/> <mn>100</mn> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <mn>400</mn> <mspace width="3.33333pt"/> </mrow> </semantics></math>mm<math display="inline"><semantics> <msup> <mrow/> <mn>3</mn> </msup> </semantics></math> as they ascend through a shear-thinning viscoelastic fluid described by the Giesekus constitutive model.</p>
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<p>Contour plots illustrating the magnitude of the natural logarithm <math display="inline"><semantics> <mi mathvariant="bold-italic">θ</mi> </semantics></math> of the conformation tensor are presented for various initial bubble volumes, including (<b>a</b>) <math display="inline"><semantics> <mrow> <msub> <mi>V</mi> <mi>b</mi> </msub> <mo>=</mo> <mn>40</mn> </mrow> </semantics></math>, (<b>b</b>) <math display="inline"><semantics> <mrow> <msub> <mi>V</mi> <mi>b</mi> </msub> <mo>=</mo> <mn>50</mn> </mrow> </semantics></math>, (<b>c</b>) <math display="inline"><semantics> <mrow> <msub> <mi>V</mi> <mi>b</mi> </msub> <mo>=</mo> <mn>100</mn> </mrow> </semantics></math>, and (<b>d</b>) <math display="inline"><semantics> <mrow> <msub> <mi>V</mi> <mi>b</mi> </msub> <mo>=</mo> <mn>400</mn> </mrow> </semantics></math> mm<math display="inline"><semantics> <msup> <mrow/> <mn>3</mn> </msup> </semantics></math>, when they ascend through a shear-thinning viscoelastic fluid described by the Giesekus constitutive model.</p>
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<p>Bubble steady-state velocity <math display="inline"><semantics> <msup> <mi>U</mi> <mo>*</mo> </msup> </semantics></math> as a function of the bubble initial radius <math display="inline"><semantics> <msub> <mi>R</mi> <mrow> <mi>e</mi> <mi>f</mi> <mi>f</mi> </mrow> </msub> </semantics></math>. The dot-dashed line represent the results obtained with our MVP-RIA algorithm, the dashed line represent the results obtained with the ALE algorithm from Moschopoulos et al. [<a href="#B79-polymers-15-03437" class="html-bibr">79</a>] while the symbols represent the experimental data from Lopez et al. [<a href="#B80-polymers-15-03437" class="html-bibr">80</a>].</p>
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<p>(<b>a</b>) Experimental bubble shape by Lopez et al. [<a href="#B80-polymers-15-03437" class="html-bibr">80</a>] (black and white), and the numerical simulation of Moschopoulos et al. [<a href="#B79-polymers-15-03437" class="html-bibr">79</a>] (red line), (<b>b</b>) Contour plots of the natural logarithm <math display="inline"><semantics> <mi mathvariant="bold-italic">θ</mi> </semantics></math> of the conformation tensor for <math display="inline"><semantics> <mrow> <msub> <mi>R</mi> <mrow> <mi>e</mi> <mi>f</mi> <mi>f</mi> </mrow> </msub> <mo>=</mo> <mn>0.004</mn> <mspace width="3.33333pt"/> </mrow> </semantics></math>m obtained with the newly developed MVP-RIA algorithm.</p>
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<p>(<b>a</b>) Experimental bubble shape by Lopez et al. [<a href="#B80-polymers-15-03437" class="html-bibr">80</a>] (black and white), and the numerical simulation of Moschopoulos et al. [<a href="#B79-polymers-15-03437" class="html-bibr">79</a>] (red line), (<b>b</b>) Contour plots of the natural logarithm <math display="inline"><semantics> <mi mathvariant="bold-italic">θ</mi> </semantics></math> of the conformation tensor for <math display="inline"><semantics> <mrow> <msub> <mi>R</mi> <mrow> <mi>e</mi> <mi>f</mi> <mi>f</mi> </mrow> </msub> <mo>=</mo> <mn>0.0107</mn> <mspace width="3.33333pt"/> </mrow> </semantics></math>m obtained with the newly developed MVP-RIA algorithm.</p>
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<p>(<b>a</b>) Experimental bubble shape by Lopez et al. [<a href="#B80-polymers-15-03437" class="html-bibr">80</a>] (black and white), and the numerical simulation of Moschopoulos et al. [<a href="#B79-polymers-15-03437" class="html-bibr">79</a>] (red line), (<b>b</b>) Contour plots of the natural logarithm <math display="inline"><semantics> <mi mathvariant="bold-italic">θ</mi> </semantics></math> of the conformation tensor for <math display="inline"><semantics> <mrow> <msub> <mi>R</mi> <mrow> <mi>e</mi> <mi>f</mi> <mi>f</mi> </mrow> </msub> <mo>=</mo> <mn>0.0163</mn> <mspace width="3.33333pt"/> </mrow> </semantics></math>m obtained with the newly developed MVP-RIA algorithm.</p>
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17 pages, 3006 KiB  
Article
The Formation of Small Amounts of Cyclopropane during Pulsed Pyrolysis of C4–C5 Acyclic Alkanes in the Adiabatic Compression Reactor
by Igor V. Bilera
Reactions 2023, 4(3), 381-397; https://doi.org/10.3390/reactions4030023 - 19 Jul 2023
Cited by 2 | Viewed by 1341
Abstract
During high-temperature pulse pyrolysis of acyclic butanes and pentanes under adiabatic compression conditions, cyclopropane, a stressed cyclic hydrocarbon, was found among the reaction products in small quantities for the first time. The analysis of the reaction products was performed by gas chromatography using [...] Read more.
During high-temperature pulse pyrolysis of acyclic butanes and pentanes under adiabatic compression conditions, cyclopropane, a stressed cyclic hydrocarbon, was found among the reaction products in small quantities for the first time. The analysis of the reaction products was performed by gas chromatography using three capillary columns of different polarity, selectivity and sufficient efficiency. The identification of reaction products, including cyclopropane, was performed using retention times of individual substances and model mixtures, as well as comparing chromatograms with reference chromatograms from the literature and the ScanView Application Database. It was shown that the chromatographic peak attributed to cyclopropane could not be a ghost peak. Additional confirmation of this conclusion was obtained in a series of experiments on the pyrolysis of n-butane at a reduced initial temperature of the adiabatic compression reactor (from 120 °C to 50 °C) and a modified mode of GC analysis. Cyclopropane yields as a function of maximum temperature have a bell-shaped asymmetric dependence. The maximum value of the yield of cyclopropane increases with the transition from normal alkanes to isoalkanes, and from pentanes to butanes; for n-pentane, 0.009 wt. %, and for isobutene, ≈0.017 wt. %. During the pulse pyrolysis of isobutane, n-butane, isopentane and n-pentane, cyclopropane is not a primary product. Further theoretical and experimental studies are needed to establish the mechanism of cyclopropane formation during pyrolysis of C4–C5 acyclic alkanes. Full article
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Figure 1

Figure 1
<p>Schematic diagram of the experimental setup. 1—cylinder, 2—piston, 3—a compression degree indicator, 4—driver gas receiver, 5—valve, 6—manometer, 7—back-pressure valve, 8—feedstock container, 9—air thermostat, 10—pressure transducer, 11—charge amplifier, 12—analog-to-digital converter, 13—personal computer, 14 and 15—gas chromatographs, 16—heated capillary.</p>
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<p>Comparison of pressure dependencies during adiabatic compression of a mixture of 2.0% vol. <span class="html-italic">n</span>-butane, 98% argon. <span class="html-italic">T</span><sub>0</sub> = 393 K (120 °C). Pressures of driver gas: <span class="html-italic">1</span>—12.0 atm; <span class="html-italic">2</span>—10.0 atm; <span class="html-italic">3</span>—7.0 atm. Skip 2 points on the pressure dependences.</p>
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<p>Separations of C<sub>1</sub>–C<sub>3</sub> hydrocarbons on the CP-Al<sub>2</sub>O<sub>3</sub>/KCl PLOT column. Blue line—reference mixture 15 ppm cyclopropane in Ar, red line—reference mixture 15 ppm cyclopropane + 15 ppm propylene in Ar, green line—reference mixture 15 ppm C<sub>n</sub>H<sub>m</sub> in N<sub>2</sub>. Peaks: <span class="html-italic">1</span> = methane; <span class="html-italic">2</span> = ethane; <span class="html-italic">3</span> = ethylene; <span class="html-italic">4</span> = propane; <span class="html-italic">5</span> = cyclopropane; <span class="html-italic">6</span> = propylene; <span class="html-italic">7</span> = acetylene; <span class="html-italic">8</span> = <span class="html-italic">n</span>-butane.</p>
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<p>Separations of C<sub>3</sub> hydrocarbons on (<b>a</b>) the CP-Al<sub>2</sub>O<sub>3</sub>/KCl PLOT, (<b>b</b>) the CP-PoraBOND Q and (<b>c</b>) the CP-PoraPLOT U columns. Blue line—products of <span class="html-italic">n</span>-butane pyrolysis, red line—reference mixture <span class="html-italic">cyclo</span>-C<sub>3</sub>H<sub>6</sub>/15 ppm C<sub>3</sub>H<sub>6</sub> in Ar, green line—reference mixture 15 ppm C<sub>n</sub>H<sub>m</sub> in N<sub>2</sub>. Note that the larger peaks are off-scale to allow observation of the minor substances. Peaks: <span class="html-italic">1</span> = methane; <span class="html-italic">2</span> = ethane; <span class="html-italic">3</span> = ethylene; <span class="html-italic">4</span> = propane; <span class="html-italic">5</span> = cyclopropane; 6 = propylene; <span class="html-italic">7</span> = acetylene; <span class="html-italic">8</span> = allene; <span class="html-italic">9</span> = isobutane; <span class="html-italic">10</span> = <span class="html-italic">n</span>-butane, <span class="html-italic">11</span> = methylacetylene, <span class="html-italic">12</span> = unknown substance.</p>
Full article ">Figure 4 Cont.
<p>Separations of C<sub>3</sub> hydrocarbons on (<b>a</b>) the CP-Al<sub>2</sub>O<sub>3</sub>/KCl PLOT, (<b>b</b>) the CP-PoraBOND Q and (<b>c</b>) the CP-PoraPLOT U columns. Blue line—products of <span class="html-italic">n</span>-butane pyrolysis, red line—reference mixture <span class="html-italic">cyclo</span>-C<sub>3</sub>H<sub>6</sub>/15 ppm C<sub>3</sub>H<sub>6</sub> in Ar, green line—reference mixture 15 ppm C<sub>n</sub>H<sub>m</sub> in N<sub>2</sub>. Note that the larger peaks are off-scale to allow observation of the minor substances. Peaks: <span class="html-italic">1</span> = methane; <span class="html-italic">2</span> = ethane; <span class="html-italic">3</span> = ethylene; <span class="html-italic">4</span> = propane; <span class="html-italic">5</span> = cyclopropane; 6 = propylene; <span class="html-italic">7</span> = acetylene; <span class="html-italic">8</span> = allene; <span class="html-italic">9</span> = isobutane; <span class="html-italic">10</span> = <span class="html-italic">n</span>-butane, <span class="html-italic">11</span> = methylacetylene, <span class="html-italic">12</span> = unknown substance.</p>
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<p>Representative chromatogram from (<b>a</b>) the CP-Al<sub>2</sub>O<sub>3</sub>/KCl PLOT and (<b>b</b>) the CP-PoraBOND Q columns, zoomed view. The analysis conditions have changed (see text). Blue line—products of <span class="html-italic">n</span>-butane pyrolysis (additional series at <span class="html-italic">T</span><sub>0</sub> = 323 K), red line—reference mixture <span class="html-italic">cyclo</span>-C<sub>3</sub>H<sub>6</sub>/15 ppm C<sub>3</sub>H<sub>6</sub> in Ar, green line—reference mixture 15 ppm C<sub>n</sub>H<sub>m</sub> in N<sub>2</sub>. Note that the larger peaks are off-scale to allow observation of the minor products. Identified compounds: <span class="html-italic">1</span> = methane; <span class="html-italic">2</span> = ethane; <span class="html-italic">3</span> = ethylene; <span class="html-italic">4</span> = propane; <span class="html-italic">5</span> = cyclopropane; 6 = propylene; <span class="html-italic">7</span> = acetylene; <span class="html-italic">8</span> = allene; <span class="html-italic">9</span> = isobutane; <span class="html-italic">10</span> = <span class="html-italic">n</span>-butane, <span class="html-italic">11</span> = methylacetylene.</p>
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<p>Temperature dependence of the cyclopropane yield (<b>a</b>) and Y<sub>c-C3H6</sub>/Y<sub>C3H6</sub> (<b>b</b>). Open squares (1), closed squares (2), open circle (3) and closed circles (4) represent the weight content of cyclopropane produced during the pyrolysis of isobutane, <span class="html-italic">n</span>-butane, isopentane and <span class="html-italic">n</span>-pentane, respectively. Initial temperature <span class="html-italic">T</span><sub>0</sub> = 393 K.</p>
Full article ">Figure 7
<p>Selectivity of the cyclopropane. Symbols (1)–(4) are the same as in <a href="#reactions-04-00023-f006" class="html-fig">Figure 6</a>. The closed rhombus (2a) represents the selectivity of the cyclopropane produced during the pyrolysis of <span class="html-italic">n</span>-butane at the initial temperature <span class="html-italic">T</span><sub>0</sub> = 323 K.</p>
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13 pages, 4578 KiB  
Article
Graphene Oxide Paper Manipulation of Micro-Reactor Drops
by Zhixiong Song, Eric Shen Lin, Md Hemayet Uddin, Hassan Ali Abid, Jian Wern Ong and Tuck Wah Ng
Micromachines 2023, 14(7), 1306; https://doi.org/10.3390/mi14071306 - 26 Jun 2023
Viewed by 1421
Abstract
Digital microfluidics, which relies on the movement of drops, is relatively immune to clogging problems, making it suited for micro-reactor applications. Here, graphene oxide paper of 100 μm thickness, fabricated by blade coating sedimented dispersions onto roughened substrates, followed by drying and mechanical [...] Read more.
Digital microfluidics, which relies on the movement of drops, is relatively immune to clogging problems, making it suited for micro-reactor applications. Here, graphene oxide paper of 100 μm thickness, fabricated by blade coating sedimented dispersions onto roughened substrates, followed by drying and mechanical exfoliation, was found to be relatively free of cracks and curling. It also exhibited high wettability and elasto-capillary characteristics. Possessing low enough stiffness, it could rapidly and totally self-wrap water drops of 20 μL volume placed 2 mm from its edge when oriented between 0 and 60° to the horizontal. This complete wrapping behavior allowed drops to be translated via movement of the paper over long distances without dislodgement notwithstanding accelerations and decelerations. An amount of 2 drops that were wrapped with separate papers, when collided with each other at speeds up to 0.64 m/s, were found to eschew coalescence. This portends the development of robust digital microfluidic approaches for micro-reactors. Full article
(This article belongs to the Section B:Biology and Biomedicine)
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Figure 1

Figure 1
<p>The geometry of an elastic sheet that is deformed by the capillary forces of a drop.</p>
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<p>Experiments conducted to investigate the edge wrapping behavior of GO paper in which (<b>a</b>) the paper is located horizontally on a superhydrophobic platform and on which a water drop is dispensed at various distances <span class="html-italic">x</span> from the edge, as well as when (<b>b</b>) the paper is located on a superhydrophobic platform at various inclination angles <span class="html-italic">α</span> to the horizontal and a water drop is dispensed at a fixed distance <span class="html-italic">x</span> from the edge.</p>
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<p>The GO solution spread by blade coating (<b>A</b>) significantly reduced in thickness after drying (<b>B</b>). The mechanically exfoliated GO paper was found to be highly flattened (<b>C</b>).</p>
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<p>Typical optical profilometry trace of the GO paper with the height distributions in the X-X and Y-Y sections included.</p>
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<p>Scanning electron microscopy images of GO paper under the magnification times of (<b>A</b>) 250×, (<b>B</b>) 650×, (<b>C</b>) 1500×, and (<b>D</b>) 20,000× magnifications. Under high magnifications, microscopic defects can be seen populating the surface, which are likely template transferred from the roughened PVC substrate.</p>
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<p>Recorded image (<b>A</b>) of water spreading on GO paper which shows the presence of main (red line) and capillary (black) contact lines. The spreading distance versus time of both lines adhere to the power law (<b>B</b>).</p>
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<p>Water drops of 20 μL volume being wrapped by GO paper with lengths of (<b>A</b>) 4.5, (<b>B</b>) 5.6, (<b>C</b>) 6.7, and (<b>D</b>) 8.9 mm.</p>
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<p>Plots of distance d between tips against the dimensionless drop volumes as described in Equation (2).</p>
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<p>The time evolution of wrapping with GO paper of width of 3.2 mm with a 20 μL water located at distances of 2.1, 3.3, 4.5, and 5.8 mm from 1 end.</p>
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<p>Sequence of images showing how a 20 μL water drop placed 3.3 mm from the edge is gradually wrapped after time lapses of 90, 290, and 300 s.</p>
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<p>A 20 μL drop placed on a superhydrophobic surface was able to be picked up by the GO paper oriented 90° to the horizontal but without wrapping occurring (<b>A</b>). The location of the GO paper at angles not exceeding 60° to the horizontal was able to achieve drop pick-up with wrapping (<b>B</b>).</p>
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<p>Sequence of images illustrating the color change when 2 drops, initially colored with red and blue dyes, respectively (<b>A</b>), interact with each other to yield a mixed purple color 1 s (<b>B</b>), 10 s (<b>C</b>), and 100 s (<b>D</b>) after contacting each other.</p>
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<p>Sequence of images illustrating two drops wrapped at the ends of GO papers being able to be moved rapidly and over long distances (<b>A</b>). When they are made to collide with each other with speeds up to 0.64 m/s, the drops do not coalescence with each other (<b>B</b>).</p>
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9 pages, 2442 KiB  
Article
Spontaneous Phase Segregation Enabling Clogging Aversion in Continuous Flow Microfluidic Synthesis of Nanocrystals Supported on Reduced Graphene Oxide
by Dumei Wang, Dongtang Zhang, Yanan Wang, Guangsheng Guo, Xiayan Wang and Yugang Sun
Nanomaterials 2022, 12(23), 4315; https://doi.org/10.3390/nano12234315 - 5 Dec 2022
Cited by 1 | Viewed by 1698
Abstract
Eliminating clogging in capillary tube reactors is critical but challenging for enabling continuous-flow microfluidic synthesis of nanoparticles. Creating immiscible segments in a microfluidic flow is a promising approach to maintaining a continuous flow in the microfluidic channel because the segments with low surface [...] Read more.
Eliminating clogging in capillary tube reactors is critical but challenging for enabling continuous-flow microfluidic synthesis of nanoparticles. Creating immiscible segments in a microfluidic flow is a promising approach to maintaining a continuous flow in the microfluidic channel because the segments with low surface energy do not adsorb onto the internal wall of the microchannel. Herein we report the spontaneous self-agglomeration of reduced graphene oxide (rGO) nanosheets in polyol flow, which arises because the reduction of graphene oxide (GO) nanosheets by hot polyol changes the nanosheets from hydrophilic to hydrophobic. The agglomerated rGO nanosheets form immiscible solid segments in the polyol flow, realizing the liquid–solid segmented flow to enable clogging aversion in continuous-flow microfluidic synthesis. Simultaneous reduction of precursor species in hot polyol deposits nanocrystals uniformly dispersed on the rGO nanosheets even without surfactant. Cuprous oxide (Cu2O) nanocubes of varying edge lengths and ultrafine metal nanoparticles of platinum (Pt) and palladium (Pd) dispersed on rGO nanosheets have been continuously synthesized using the liquid–solid segmented flow microfluidic method, shedding light on the promise of microfluidic reactors in synthesizing functional nanomaterials. Full article
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Graphical abstract

Graphical abstract
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<p>Schematic illustration of the major evolution steps involved spontaneous phase segregation of rGO-supported nanocrystal agglomerates during the simultaneous formation of nanocrystals and reduction of GO in hot polyols.</p>
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<p>(<b>a</b>) Photo of a section of the capillary tube in the cooling zone. (<b>b</b>,<b>c</b>) Time-dependent laser scattering intensity as the TEG dispersion of GO nanosheets flows in the capillary tube. The temperature in the heating zone was 250 °C.</p>
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<p>TEM images (left frames) and size histograms (right frames) of the Cu<sub>2</sub>O/rGO composites (i.e., Cu<sub>2</sub>O nanocrystals dispersed on rGO nanosheets) synthesized at different temperatures: (<b>a</b>) 220 °C, (<b>b</b>) 250 °C, (<b>c</b>) 280 °C, (<b>d</b>) 300 °C, (<b>e</b>) 330 °C, and (<b>f</b>) 350 °C. The corresponding products are labeled as (<b>a</b>) Cu<sub>2</sub>O/rGO-220, (<b>b</b>) Cu<sub>2</sub>O/rGO-250, (<b>c</b>) Cu<sub>2</sub>O/rGO-280, (<b>d</b>) Cu<sub>2</sub>O/rGO-300, (<b>e</b>) Cu<sub>2</sub>O/rGO-330, and (<b>f</b>) Cu<sub>2</sub>O/rGO-350, respectively. The statistical histograms of size distributions of the major nanocrystals were determined by analyzing the edge lengths (<span class="html-italic">l</span>) of 200 randomly selected nanoparticles. Note: The dominating nanocrystals in the Cu<sub>2</sub>O/rGO-350 sample shown in (<b>f</b>) were Cu, even though the sample label was still “Cu<sub>2</sub>O” to show the consistency with the samples synthesized at different temperatures.</p>
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<p>(<b>a</b>) XRD patterns and (<b>b</b>) elemental compositions of the Cu<sub>2</sub>O/rGO composite particles synthesized at different reaction temperatures.</p>
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<p>(<b>a</b>,<b>c</b>) TEM images and (<b>b</b>,<b>d</b>) statistical histograms of size distributions of the synthesized metal nanocrystals on rGO nanosheets: (<b>a</b>,<b>b</b>) Pt/rGO and (<b>c</b>,<b>d</b>) Pd/rGO. The reaction temperature was 220 °C. The statistical histograms of size distributions of the major nanocrystals were determined by analyzing the diameter (<span class="html-italic">d</span>) of 200 randomly selected nanoparticles.</p>
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35 pages, 8646 KiB  
Review
Ten Years Milestones in Xanthine Oxidase Inhibitors Discovery: Febuxostat-Based Inhibitors Trends, Bifunctional Derivatives, and Automatized Screening Assays
by Miguel F. S. de Abreu, Camila A. Wegermann, Millena S. Ceroullo, Isabella G. M. Sant’Anna and Renato C. S. Lessa
Organics 2022, 3(4), 380-414; https://doi.org/10.3390/org3040026 - 10 Oct 2022
Cited by 5 | Viewed by 3166
Abstract
Xanthine oxidase (XO) is an enzyme involved in the oxidative process of hypoxanthine and xanthine to uric acid (UA). This process also produces reactive oxygen species (ROS) as byproducts. Both UA and ROS are dangerous for human health, and some health conditions trigger [...] Read more.
Xanthine oxidase (XO) is an enzyme involved in the oxidative process of hypoxanthine and xanthine to uric acid (UA). This process also produces reactive oxygen species (ROS) as byproducts. Both UA and ROS are dangerous for human health, and some health conditions trigger upregulation of XO activity, which results in many diseases (cancer, atherosclerosis, hepatitis, gout, and others) given the worsened scenario of ROS and UA overproduction. So, XO became an attractive target to produce and discover novel selective drugs based on febuxostat, the most recent XO inhibitor out of only two approved by FDA. Under this context, high-performance liquid chromatography (HPLC) and capillary electrophoresis (CE) have been successfully applied to rapidly and easily screen for bioactive compounds, isolated or in complex natural matrixes, that act as enzyme inhibitors through the use of an immobilized enzyme reactor (IMER). This article’s goal is to present advances comprising febuxostat-based XO inhibitors as a new trend, bifunctional moieties capable of inhibiting XO and modulating ROS activity, and in-flow techniques employing an IMER in HPLC and CE to screen for synthetic and natural compounds that act as XO inhibitors. Full article
(This article belongs to the Collection Advanced Research Papers in Organics)
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Figure 1
<p>Allopurinol, febuxostat, topiroxostat and Y-700 molecular structures and docking sites.</p>
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<p>(<bold>A</bold>) Unidimensional and (<bold>B</bold>) bidimensional HPLC approaches for in-flow screening of XO inhibitors.</p>
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<p>Capillary for CE containing gold nanoparticles with immobilized XO for inhibitors screening [<xref ref-type="bibr" rid="B23-organics-03-00026">23</xref>].</p>
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<p>XO and ADA co-immobilized in gold nanoparticles inside the initial portion of a capillary for inhibitors screening by CE [<xref ref-type="bibr" rid="B75-organics-03-00026">75</xref>].</p>
Full article ">Scheme 1
<p>XO and XD enzymatic reactions.</p>
Full article ">Scheme 2
<p>Synthesis of the indolethiazoles selected examples <bold>1a</bold>–<bold>g</bold> analogs of febuxostat and its in vitro XO inhibition potential in terms of IC<sub>50</sub> [<xref ref-type="bibr" rid="B38-organics-03-00026">38</xref>]. HBTU = Hexafluorophosphate Benzotriazole Tetramethyl Uronium.</p>
Full article ">Scheme 3
<p>Synthesis of selenazole derivatives <bold>2a</bold>–<bold>f</bold> and <bold>3a</bold>–<bold>m</bold> [<xref ref-type="bibr" rid="B39-organics-03-00026">39</xref>].</p>
Full article ">Scheme 4
<p>Synthesis of 1-phenyl-pyrazole-4-carboxylic acids class I derivatives <bold>4a</bold>–<bold>e</bold>, <bold>5a</bold>–<bold>e</bold> and class II derivatives <bold>6a</bold>–<bold>f</bold>, <bold>7f</bold>,<bold>g</bold>, <bold>8f</bold>,<bold>g</bold> [<xref ref-type="bibr" rid="B40-organics-03-00026">40</xref>]. DMCDA = trans-N,N′-dimethyl-1,2-cyclohexane-diamine. PCA = 3-trifluoropyrazol-4-carboxylic acid or 3-methyl-4-carboxylic acid or <italic>H</italic>-pyrazol-4-carboxylic acid.</p>
Full article ">Scheme 5
<p>1-hydroxy (<bold>9a</bold>–<bold>k</bold>) and 1-methoxy (<bold>10a</bold>–<bold>k</bold>) 4-methyl-2-phenyl-1<italic>H</italic>-imidazole-5-carboxylic acid derivatives [<xref ref-type="bibr" rid="B41-organics-03-00026">41</xref>].</p>
Full article ">Scheme 6
<p>2-phenyl-5-methyl-2<italic>H</italic>-1,2,3-triazole-4-carboxylic acid (<bold>11a</bold>–<bold>h</bold>, <bold>12a</bold>–<bold>h</bold>) and carbohydrazide (<bold>13e</bold>,<bold>f</bold>, <bold>14e</bold>,<bold>f</bold>) derivatives [<xref ref-type="bibr" rid="B42-organics-03-00026">42</xref>].</p>
Full article ">Scheme 7
<p>1-phenyl-1<italic>H</italic>-1,2,3-triazole-4-carboxylic acid derivatives <bold>15a</bold>–<bold>s</bold> [<xref ref-type="bibr" rid="B43-organics-03-00026">43</xref>].</p>
Full article ">Scheme 8
<p>Synthetic procedure employing microwave to obtain the novel phenyl thiazole derivatives <bold>16a</bold>–<bold>h</bold> and its XO inhibitory activities in terms of in vitro IC<sub>50</sub> [<xref ref-type="bibr" rid="B44-organics-03-00026">44</xref>].</p>
Full article ">Scheme 9
<p>Selected 1,2,3-triazole derivatives <bold>17a</bold>–<bold>p</bold> synthesis protocol [<xref ref-type="bibr" rid="B45-organics-03-00026">45</xref>].</p>
Full article ">Scheme 10
<p>2-mercapto-6-phenylpyrimidine-4-carboxylic acid derivatives <bold>18a</bold>–<bold>c</bold>, <bold>19a</bold>–<bold>c</bold>, <bold>20a</bold>–<bold>e</bold>, <bold>21a</bold>–<bold>e</bold> [<xref ref-type="bibr" rid="B26-organics-03-00026">26</xref>].</p>
Full article ">Scheme 11
<p>Six-membered heterocycles pyridazine derivatives <bold>22a</bold>–<bold>o</bold>, carboxylic acid derivatives <bold>23c</bold>,<bold>d</bold>,<bold>h</bold> [<xref ref-type="bibr" rid="B46-organics-03-00026">46</xref>].</p>
Full article ">Scheme 12
<p>Synthesis of the isocytosine derivatives <bold>22</bold>–<bold>31</bold> and <bold>32</bold>–<bold>42</bold> as XO inhibitors [<xref ref-type="bibr" rid="B47-organics-03-00026">47</xref>,<xref ref-type="bibr" rid="B48-organics-03-00026">48</xref>].</p>
Full article ">Scheme 13
<p>Febuxostat derivatives <bold>45a</bold>–<bold>z</bold> containing a tetrazole nucleus as replacement of the original cyano group [<xref ref-type="bibr" rid="B49-organics-03-00026">49</xref>]. DEEMM = Diethyl ethoxymethylenemalonate.</p>
Full article ">Scheme 14
<p>Synthesis of derivatives <bold>46a</bold>–<bold>w</bold> and its amide-reverse counterparts <bold>47f</bold>,<bold>h</bold>,<bold>l</bold>,<bold>n</bold> (synthesis not shown) comprising the bioisosteric replacement of the febuxostat cyano group by the 1,2,3,4-tetrazole [<xref ref-type="bibr" rid="B50-organics-03-00026">50</xref>].</p>
Full article ">Scheme 15
<p>Isonicotinamide (<bold>48a</bold>–<bold>s</bold>), nicotinamide (<bold>49a</bold>–<bold>o</bold>), picolinamide (<bold>50b</bold>,<bold>i</bold>,<bold>j</bold>,<bold>m</bold>,<bold>n</bold>) and benzamide (<bold>51</bold>) derivatives [<xref ref-type="bibr" rid="B51-organics-03-00026">51</xref>].</p>
Full article ">Scheme 16
<p>Topiroxostat-based isomeric family of derivatives <bold>52a</bold>–<bold>g</bold> and <bold>53a</bold>–<bold>g</bold> [<xref ref-type="bibr" rid="B52-organics-03-00026">52</xref>].</p>
Full article ">Scheme 17
<p>Synthesis of the novel febuxostat-topiroxostat hybrid derivatives <bold>54a</bold>–<bold>p</bold> with an isosteric replacement of the amide linker by an 1,2,3-triazole nucleus [<xref ref-type="bibr" rid="B53-organics-03-00026">53</xref>].</p>
Full article ">Scheme 18
<p>Different functionalized febuxostat derivatives <bold>55a</bold>–<bold>f</bold>, <bold>56a</bold>–<bold>b</bold>, <bold>57</bold>, <bold>58a</bold>–<bold>f and 59b</bold>,<bold>d</bold> in the carboxylic acid termination [<xref ref-type="bibr" rid="B54-organics-03-00026">54</xref>].</p>
Full article ">Scheme 19
<p>Barbiturates <bold>60a</bold> and <bold>60b</bold> in vitro potential for XO inhibition and in vitro antioxidant potential. n.d. = not determined [<xref ref-type="bibr" rid="B55-organics-03-00026">55</xref>].</p>
Full article ">Scheme 20
<p>Synthesis protocol for the obtainment of the 2-arylbenzo[b]furan derivatives <bold>61a</bold>–<bold>f</bold>, <bold>62a</bold>–<bold>f</bold>, <bold>63a</bold>–<bold>f</bold> and <bold>64a</bold>–<bold>f</bold> [<xref ref-type="bibr" rid="B58-organics-03-00026">58</xref>].</p>
Full article ">Scheme 21
<p>Synthesis protocol for the obtainment of the 2-arylbenzo[b]furan derivatives <bold>66a</bold>–<bold>d</bold>, <bold>67a</bold>–<bold>d</bold> and <bold>68a</bold>–<bold>d</bold> [<xref ref-type="bibr" rid="B59-organics-03-00026">59</xref>].</p>
Full article ">Scheme 22
<p>Hesperidin derivatives (3HDa<sub>1–3</sub> and 4HDb<sub>1–3</sub>) synthesis and its in vitro XO inhibition, H<sub>2</sub>O<sub>2</sub> and DPPH radical scavenging potential in terms of IC<sub>50</sub> [<xref ref-type="bibr" rid="B61-organics-03-00026">61</xref>].</p>
Full article ">Scheme 23
<p>Synthesized benzimidazoles derivatives (B3, B6, B9) and their in vitro XO activity in terms of IC<sub>50</sub> and antioxidant activity [<xref ref-type="bibr" rid="B64-organics-03-00026">64</xref>].</p>
Full article ">Scheme 24
<p>Synthesized deazaguanines derivatives screened for XO inhibition and its inhibition efficiency [<xref ref-type="bibr" rid="B72-organics-03-00026">72</xref>].</p>
Full article ">
18 pages, 8161 KiB  
Article
Validation of Easy Fabrication Methods for PDMS-Based Microfluidic (Bio)Reactors
by Josef Vogt and Katrin Rosenthal
Sci 2022, 4(4), 36; https://doi.org/10.3390/sci4040036 - 21 Sep 2022
Cited by 2 | Viewed by 2534
Abstract
The common method for producing casting molds for the fabrication of polydimethylsiloxane (PDMS) chips is standard photolithography. This technique offers high resolution from hundreds of nanometers to a few micrometers. However, this mold fabrication method is costly, time-consuming, and might require clean room [...] Read more.
The common method for producing casting molds for the fabrication of polydimethylsiloxane (PDMS) chips is standard photolithography. This technique offers high resolution from hundreds of nanometers to a few micrometers. However, this mold fabrication method is costly, time-consuming, and might require clean room facilities. Additionally, there is a need for non-micromechanics experts, who do not have specialized equipment to easily and quickly prototype chips themselves. Simple, so-called, makerspace technologies are increasingly being explored as alternatives that have potential to enable anyone to fabricate microfluidic structures. We therefore tested simple fabrication methods for a PDMS-based microfluidic device. On the one hand, channels were replicated from capillaries and tape. On the other hand, different mold fabrication methods, namely laser cutting, fused layer 3D printing, stereolithographic 3D printing, and computer numerical control (CNC) milling, were validated in terms of machine accuracy and tightness. Most of these methods are already known, but the incorporation and retention of particles with sizes in the micrometer range have been less investigated. We therefore tested two different types of particles, which are actually common carriers for the immobilization of enzymes, so that the resulting reactor could ultimately be used as a microfluidic bioreactor. Furthermore, CNC milling provide the most reliable casting mold fabrication method. After some optimization steps with regard to manufacturing settings and post-processing polishing, the chips were tested for the retention of two different particle types (spherical and non-spherical particles). In this way, we successfully tested the obtained PDMS-based microfluidic chips for their potential applicability as (bio)reactors with enzyme immobilization carrier beads. Full article
(This article belongs to the Special Issue Feature Papers 2021 Editors Collection)
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<p>Cured polydimethylsiloxane (PDMS) with a ratio of 10:1 to its curing agent.</p>
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<p>Different microfluidic chip designs in Inventor Professional 2012. (<bold>a</bold>) Constriction in width (60 µm). (<bold>b</bold>) Constriction in height (60 µm). Magnification of (<bold>c</bold>) the constriction in width (60 µm), and (<bold>d</bold>) constriction in height (60 µm).</p>
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<p>Particles used for the chip application. (<bold>a</bold>) Non-spherical particles. (<bold>b</bold>) Spherical particles. Pictures are 40× magnified.</p>
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<p>Cases for PDMS pouring. (<bold>a</bold>) Cases with adhesive tape. (<bold>b</bold>) Polylactic acid (PLA) cases with a 90° upstand. (<bold>c</bold>) PLA cases with a 130°, 120° and 110° side wall inclination angle.</p>
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<p>Set-up of the microfluidic chip analysis. (<bold>a</bold>) Overall set-up of the microfluidic device including the syringe pumps as liquid reservoirs and the chip on the microscope. (<bold>b</bold>) Chip mounted on the microscope with liquid inlet and outlet.</p>
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<p>PDMS fabrication methods using capillaries and tape. (<bold>a</bold>) Capillaries and adhesive tape coated with PDMS. (<bold>b</bold>) Hardened PDMS with removed capillaries and adhesive tape. (<bold>c</bold>) Structured PDMS bonded to glass.</p>
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<p>Microfluidic chip from capillaries (<bold>a</bold>) and adhesive tape (<bold>b</bold>) at 10× magnification.</p>
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<p>Casting mold fabricated out of ABS with the Ultimaker S5. (<bold>a</bold>) Casting mold. (<bold>b</bold>) 3D picture of the sieve taken from the casting mold at the transition of the lower to the higher channel structure.</p>
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<p>Surface area, next to a channel, of a microfluidic chip replicated from a casting mold fabricated with the Ultimaker S5. (<bold>a</bold>) 10× magnified. (<bold>b</bold>) 10× magnified with fluorescence visualization of rhodamine B solution—fluid flow along the grooves leaking from the channel at the upper side of the picture.</p>
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<p>Sieve structure and particle retention with a microfluidic chip fabricated with the Ultimaker S5. (<bold>a</bold>) Sieve structure. (<bold>b</bold>) Sieve structure with retained spherical particles (Ø: 45–165 μm).</p>
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<p>Sieve of a microfluidic chip replicated from a casting mold exposed to acetone vapor. (<bold>a</bold>) Sieve structure. (<bold>b</bold>) Surface next to the channel. (<bold>c</bold>) Sieve structure with retained spherical particles.</p>
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<p>Casting mold fabricated out of black resin with the Form 2. (<bold>a</bold>) Casting mold and (<bold>b</bold>) 3D picture of the sieve taken from the casting mold at the transition of the lower to the higher channel structure.</p>
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<p>Microfluidic chip replicated from a Form 2-printed casting mold. (<bold>a</bold>) Leakage around channels visualized with fluorescent rhodamine B solution. (<bold>b</bold>) Sieve visualized with fluorescent rhodamine B solution. (<bold>c</bold>) Sieve with retained particles.</p>
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<p>Inventor Professional 2012 design of a gasket (140 µm wide and 25 µm deep) aligned to the channel and sieve.</p>
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<p>Microfluidic chip replicated from a Form 2 printed casting mold including a gasket. (<bold>a</bold>) Gasket between the channel (upper part) and leaky bond of glass and PDMS. (<bold>b</bold>) Sieve with retained particles. (<bold>c</bold>) Leakage around channels visualized with fluorescent rhodamine B solution.</p>
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<p>ABS casting mold fabricated with laser exposure.</p>
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<p>Microfluidic chip replicated from a laser-engraved casting mold. (<bold>a</bold>) Non-leaky channel visualized with fluorescent rhodamine B solution. (<bold>b</bold>) Enlarged channel after acetone vapor polishing.</p>
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<p>ABS casting molds fabricated with a milling machine. (<bold>a</bold>) Different offsets of 0.1 mm, 0.4 mm, and 0.7 mm from left to right. (<bold>b</bold>) Narrow sieve 3D picture. (<bold>c</bold>) Flat sieve 3D picture taken from the casting mold at the transition of the lower to the higher channel structure.</p>
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<p>Microfluidic chip replica fabricated through milling on ABS. (<bold>a</bold>) Leakage visualized with fluorescent rhodamine B solution. (<bold>b</bold>) Narrow sieve retaining spherical particles. (<bold>c</bold>) Narrow sieve retaining non-spherical particles.</p>
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<p>Microfluidic chip replica fabricated through milling on ABS and polished in acetone vapor. (<bold>a</bold>) Channel filled with non-spherical particles. (<bold>b</bold>) Narrow sieve retaining non-spherical particles. (<bold>c</bold>) Narrow sieve retaining spherical particles.</p>
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<p>Microfluidic chip replica fabricated through milling on ABS. (<bold>a</bold>) Flat sieve retaining spherical particles. (<bold>b</bold>) Flat sieve retaining non-spherical particles. (<bold>c</bold>) Acetone polished flat sieve retaining non-spherical particles.</p>
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<p>Acetone dipping polished casting mold fabricated through milling on ABS. (<bold>a</bold>) Mold after acetone polishing and air drying. (<bold>b</bold>) Mold after acetone polishing and pressurized gas drying.</p>
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<p>Acetone polishing of ABS casting molds fabricated by milling. (<bold>a</bold>) ABS casting mold exposed to acetone vapor for 30 s. (<bold>b</bold>) Setup for acetone vapor polishing.</p>
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16 pages, 2937 KiB  
Article
An Integrated, Real-Time Convective PCR System for Isolation, Amplification, and Detection of Nucleic Acids
by Guijun Miao, Meng Guo, Ke Li, Xiangzhong Ye, Michael G. Mauk, Shengxiang Ge, Ningshao Xia, Duli Yu and Xianbo Qiu
Chemosensors 2022, 10(7), 271; https://doi.org/10.3390/chemosensors10070271 - 11 Jul 2022
Cited by 5 | Viewed by 2731
Abstract
Convective PCR (CPCR) can perform rapid nucleic acid amplification by inducing thermal convection to continuously, cyclically driving reagent between different zones of the reactor for spatially separate melting, annealing, and extending in a capillary tube with constant heating temperatures at different locations. CPCR [...] Read more.
Convective PCR (CPCR) can perform rapid nucleic acid amplification by inducing thermal convection to continuously, cyclically driving reagent between different zones of the reactor for spatially separate melting, annealing, and extending in a capillary tube with constant heating temperatures at different locations. CPCR is promoted by incorporating an FTA membrane filter into the capillary tube, which constructs a single convective PCR reactor for both sample preparation and amplification. To simplify fluid control in sample preparation, lysed sample or wash buffer is driven through the membrane filter through centrifugation. A movable resistance heater is used to heat the capillary tube for amplification, and meanwhile, a smartphone camera is adopted to monitor in situ fluorescence signal from the reaction. Different from other existing CPCR systems with the described simple, easy-to-use, integrated, real-time microfluidic CPCR system, rapid nucleic acid analysis can be performed from sample to answer. A couple of critical issues, including wash scheme and reaction temperature, are analyzed for optimized system performance. It is demonstrated that influenza A virus with the reasonable concentration down to 1.0 TCID50/mL can be successfully detected by the integrated microfluidic system within 45 min. Full article
(This article belongs to the Special Issue State of the Art in Nucleic Acid Detection)
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<p>Single CPCR reactor equipped with a solid phase membrane for sample preparation. (<b>A</b>) Schematic depiction of real-time CPCR with an FTA membrane; (<b>B</b>) a photograph of capillary tube equipped with an FTA membrane.</p>
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<p>Integrated PCR reactor module. (<b>A</b>) Schematic depiction of integrated PCR reactor; (<b>B</b>) a photograph of the CPCR reactor module made from PMMA.</p>
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<p>Centrifugation-based fluid control to CPCR reactor module. (<b>A</b>) Schematic depiction of CPCR reactor module with centrifugation; (<b>B</b>) schematic depiction of sample preparation process based on centrifugation.</p>
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<p>Integrated Microfluidic CPCR NAAT System. (<b>A</b>) A photograph of CPCR device in this paper; (<b>B</b>) a smartphone and in-situ fluorescent signal collected; (<b>C</b>) schematic depiction of CPCR device with centrifugation, heating and fluorescence detection modules.</p>
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<p>Thermal time-response of the temperature calibration capillary tube.</p>
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<p>CPCR with H1N1 templates. In details: (<b>A</b>) end-point fluorescent images of amplicons with different wash options; (<b>B</b>) analyzed real-time fluorescence curves with different wash options, the solid line, dashed line, and dotted line, respectively, correspond to different wash options of 80/160 μL, 40/80 μL, and 20/40 μL of purification buffer/TE buffer.</p>
Full article ">Figure 7
<p>CPCR with H1N1 virus templates. In details: (<b>A</b>) end-point fluorescent images of amplicons with different heating temperatures; (<b>B</b>) analyzed real-time fluorescence curves with different heating temperatures, the long-dashed line, dotted line, solid line, short-dashed line, and dashed and dotted line, respectively, correspond to experiments with different setpoint temperatures, 99 °C, 97 °C, 95 °C, 93 °C, and 91 °C.</p>
Full article ">Figure 8
<p>Real-time CPCR with H1N1 templates. Real-time curves of intensity of fluorescence signal with diluted samples. In details: (<b>A</b>) end-point fluorescent images of amplicons with different concentrations and a negative control (NC); (<b>B</b>) analyzed real-time fluorescence curves, the short-dashed line, dashed and dotted line, long dashed line, solid line, and dotted line, respectively, correspond to negative control (NC), and samples with different concentrations from 1.0 to 1000 TCID<sub>50</sub>/mL.</p>
Full article ">
18 pages, 4895 KiB  
Article
An Analysis of Bubble Migration in Horizontal Thermo-Capillarity Using the VOF Modeling
by Ranjith Kumar, Yu-Chen Lin, Chia-Wei Lin, Ming-Chieh Lin and Hua-Yi Hsu
Appl. Sci. 2022, 12(9), 4355; https://doi.org/10.3390/app12094355 - 25 Apr 2022
Cited by 7 | Viewed by 1780
Abstract
Due to various engineering applications, spontaneous bubble movement on the heated surface has brought huge attention. This work numerically studied the bubble migration driven by the thermo-capillary force under the temperature gradients perpendicular to the gravity direction. This problem is constructed in a [...] Read more.
Due to various engineering applications, spontaneous bubble movement on the heated surface has brought huge attention. This work numerically studied the bubble migration driven by the thermo-capillary force under the temperature gradients perpendicular to the gravity direction. This problem is constructed in a two-dimensional domain, and the volume of fluid (VOF) method is adopted to capture the properties of the bubble interface between the vapor and the liquid. One still vapor bubble is initially positioned at the center of the liquid domain, and the temperature gradient is applied to two side walls. The results show that the bubble with a size greater than the capillary length can only oscillate near the initial position even with a larger temperature gradient. The deformation of the bubble such as spheroid and spherical cap can be found around this regime. However, the movement of the bubble with a size smaller than the capillary length is significant under a higher temperature gradient, and it remains a spherical shape. The coefficient of thermo-capillary force (CTh) is defined within this work, and it is found that a larger Weber number (We) accomplishes a larger CTh. This work may provide more precise guidance for smart bubble manipulation and critical heat flux estimation for future nuclear reactor design. Full article
(This article belongs to the Special Issue Recent Advances in Flow Control)
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<p>Illustration of the computation model with boundary conditions indicated.</p>
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<p>Transient bubble position with a radius <span class="html-italic">R</span> = 0.005 m and <math display="inline"><semantics> <mrow> <mo>∇</mo> <mi>T</mi> </mrow> </semantics></math> = 8.33 × 10<sup>2</sup> · K/m.</p>
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<p>Schematic representation of the movement of the bubbles with different bubble radii in the <span class="html-italic">x</span>-direction under different longitudinal temperature gradients (<b>a</b>) <math display="inline"><semantics> <mrow> <mo>Δ</mo> <mi>T</mi> <mo>=</mo> <mn>0</mn> <mrow> <mo> </mo> <mi mathvariant="normal">K</mi> </mrow> </mrow> </semantics></math>, (<b>b</b>) <math display="inline"><semantics> <mrow> <mo>Δ</mo> <mi>T</mi> <mo>=</mo> <mn>20</mn> <mrow> <mo> </mo> <mi mathvariant="normal">K</mi> </mrow> </mrow> </semantics></math>, (<b>c</b>) <math display="inline"><semantics> <mrow> <mo>Δ</mo> <mi>T</mi> <mo>=</mo> <mn>40</mn> <mrow> <mo> </mo> <mi mathvariant="normal">K</mi> </mrow> </mrow> </semantics></math>, (<b>d</b>) <math display="inline"><semantics> <mrow> <mo>Δ</mo> <mi>T</mi> <mo>=</mo> <mn>60</mn> <mrow> <mo> </mo> <mi mathvariant="normal">K</mi> </mrow> </mrow> </semantics></math>, (<b>e</b>) and (<b>f</b>) <math display="inline"><semantics> <mrow> <mo>Δ</mo> <mi>T</mi> <mo>=</mo> <mn>100</mn> <mrow> <mo> </mo> <mi mathvariant="normal">K</mi> </mrow> </mrow> </semantics></math>.</p>
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<p>Schematic representation of centroid positions of bubble along the <span class="html-italic">x</span>-axis with different bubble radii of (<b>a</b>) <span class="html-italic">R</span> = 0.01 m, (<b>b</b>) <span class="html-italic">R</span> = 0.015 m, (<b>c</b>) <span class="html-italic">R</span> = 0.025 m, (<b>d</b>) <span class="html-italic">R</span> = 0.035 m and (<b>e</b>) <span class="html-italic">R</span> = 0.05 m.</p>
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<p>Simulation results of the rising velocity and bubble shape for different bubble radii.</p>
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<p>The rising velocity of bubbles compared with the referenced values.</p>
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<p>Schematic representation of the movement of the bubbles with different bubble radii in the <span class="html-italic">x</span>-direction under different lateral temperature gradients (<b>a</b>) <math display="inline"><semantics> <mrow> <mo>Δ</mo> <mi>T</mi> <mo>=</mo> <mn>0</mn> <mrow> <mo> </mo> <mi mathvariant="normal">K</mi> </mrow> </mrow> </semantics></math>, (<b>b</b>) <math display="inline"><semantics> <mrow> <mo>Δ</mo> <mi>T</mi> <mo>=</mo> <mn>20</mn> <mrow> <mo> </mo> <mi mathvariant="normal">K</mi> </mrow> </mrow> </semantics></math>, (<b>c</b>) <math display="inline"><semantics> <mrow> <mo>Δ</mo> <mi>T</mi> <mo>=</mo> <mn>40</mn> <mrow> <mo> </mo> <mi mathvariant="normal">K</mi> </mrow> </mrow> </semantics></math>, (<b>d</b>) <math display="inline"><semantics> <mrow> <mo>Δ</mo> <mi>T</mi> <mo>=</mo> <mn>60</mn> <mrow> <mo> </mo> <mi mathvariant="normal">K</mi> </mrow> </mrow> </semantics></math>, (<b>e</b>) <math display="inline"><semantics> <mrow> <mo>Δ</mo> <mi>T</mi> <mo>=</mo> <mn>80</mn> <mrow> <mo> </mo> <mi mathvariant="normal">K</mi> </mrow> </mrow> </semantics></math> and (<b>f</b>) <math display="inline"><semantics> <mrow> <mo>Δ</mo> <mi>T</mi> <mo>=</mo> <mn>100</mn> <mrow> <mo> </mo> <mi mathvariant="normal">K</mi> </mrow> </mrow> </semantics></math>.</p>
Full article ">Figure 7 Cont.
<p>Schematic representation of the movement of the bubbles with different bubble radii in the <span class="html-italic">x</span>-direction under different lateral temperature gradients (<b>a</b>) <math display="inline"><semantics> <mrow> <mo>Δ</mo> <mi>T</mi> <mo>=</mo> <mn>0</mn> <mrow> <mo> </mo> <mi mathvariant="normal">K</mi> </mrow> </mrow> </semantics></math>, (<b>b</b>) <math display="inline"><semantics> <mrow> <mo>Δ</mo> <mi>T</mi> <mo>=</mo> <mn>20</mn> <mrow> <mo> </mo> <mi mathvariant="normal">K</mi> </mrow> </mrow> </semantics></math>, (<b>c</b>) <math display="inline"><semantics> <mrow> <mo>Δ</mo> <mi>T</mi> <mo>=</mo> <mn>40</mn> <mrow> <mo> </mo> <mi mathvariant="normal">K</mi> </mrow> </mrow> </semantics></math>, (<b>d</b>) <math display="inline"><semantics> <mrow> <mo>Δ</mo> <mi>T</mi> <mo>=</mo> <mn>60</mn> <mrow> <mo> </mo> <mi mathvariant="normal">K</mi> </mrow> </mrow> </semantics></math>, (<b>e</b>) <math display="inline"><semantics> <mrow> <mo>Δ</mo> <mi>T</mi> <mo>=</mo> <mn>80</mn> <mrow> <mo> </mo> <mi mathvariant="normal">K</mi> </mrow> </mrow> </semantics></math> and (<b>f</b>) <math display="inline"><semantics> <mrow> <mo>Δ</mo> <mi>T</mi> <mo>=</mo> <mn>100</mn> <mrow> <mo> </mo> <mi mathvariant="normal">K</mi> </mrow> </mrow> </semantics></math>.</p>
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<p>Schematic representation of the movement of the centroid positions of bubbles in the <span class="html-italic">x</span>-direction with different bubble radii, (<b>a</b>) <span class="html-italic">R</span> = 0.0045 m, (<b>b</b>) <span class="html-italic">R</span> = 0.005 m, (<b>c</b>) <span class="html-italic">R</span> = 0.006 m, (<b>d</b>) <span class="html-italic">R</span> = 0.007 m, (<b>e</b>) <span class="html-italic">R</span> = 0.008 m and (<b>f</b>) <span class="html-italic">R</span> = 0.01 m.</p>
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<p>The transient state of the bubble with radius <span class="html-italic">R</span> = 0.006 m and <math display="inline"><semantics> <mrow> <mo>Δ</mo> <mi>T</mi> <mo>=</mo> <mn>40</mn> <mrow> <mo> </mo> <mi mathvariant="normal">K</mi> </mrow> </mrow> </semantics></math> (<b>a</b>) Velocity field (<b>b</b>) Temperature field, and (<b>c</b>) pressure field.</p>
Full article ">Figure 9 Cont.
<p>The transient state of the bubble with radius <span class="html-italic">R</span> = 0.006 m and <math display="inline"><semantics> <mrow> <mo>Δ</mo> <mi>T</mi> <mo>=</mo> <mn>40</mn> <mrow> <mo> </mo> <mi mathvariant="normal">K</mi> </mrow> </mrow> </semantics></math> (<b>a</b>) Velocity field (<b>b</b>) Temperature field, and (<b>c</b>) pressure field.</p>
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<p>Relation between thermo-capillary coefficient (<math display="inline"><semantics> <mrow> <msub> <mi>C</mi> <mrow> <mi>T</mi> <mi>h</mi> </mrow> </msub> </mrow> </semantics></math>) and the Weber number (<span class="html-italic">We</span>).</p>
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<p>Thermo-capillary coefficient (<span class="html-italic">C<sub>Th</sub></span>) vs. the Weber number (<span class="html-italic">We</span>) for <span class="html-italic">R</span> = 0.0045 m.</p>
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<p>Thermo-capillary coefficient (<span class="html-italic">C<sub>Th</sub></span>) vs. the Weber number (<span class="html-italic">We</span>) for <span class="html-italic">R</span> = 0.008 m.</p>
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<p>Thermo-capillary coefficient (<span class="html-italic">C<sub>Th</sub></span>) vs. the Weber number (<span class="html-italic">We</span>) for <span class="html-italic">R</span> = 0.03 m.</p>
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13 pages, 1589 KiB  
Article
Responses of Nitrogen Removal, Extracellular Polymeric Substances (EPSs), and Physicochemical Properties of Activated Sludge to Different Free Ammonia (FA) Concentrations
by Hongwei Sun, Yiran Li, Wei Tang, Huanhuan Chang, Cuizhong Chen and Chenjian Cai
Water 2022, 14(4), 620; https://doi.org/10.3390/w14040620 - 17 Feb 2022
Cited by 4 | Viewed by 2037
Abstract
To investigate the effect of free ammonia (FA) on the nitrogen removal performance, extracellular polymeric substances (EPSs), and physicochemical properties of activated sludge, four laboratory-scale sequencing batch reactors (SBRs) were operated at FA concentrations of 0.5, 5, 10, and 15 mg/L (R0.5 [...] Read more.
To investigate the effect of free ammonia (FA) on the nitrogen removal performance, extracellular polymeric substances (EPSs), and physicochemical properties of activated sludge, four laboratory-scale sequencing batch reactors (SBRs) were operated at FA concentrations of 0.5, 5, 10, and 15 mg/L (R0.5, R5, R10, and R15, respectively). Results showed that nitrogen removal and the production of EPSs and their components (including polysaccharides, proteins, and nucleic acid) significantly increased with the increased FA concentration from 0.5 to 10 mg/L; however, they decreased with a further increase in FA to 15 mg/L. Moreover, the capillary suction time (CST), specific resistance of filtration (SRF), and sludge volume index (SVI) decreased when FA concentration increased, indicating that better settleability and dewaterability of activated sludge was obtained. Additionally, a path diagram showed that Nitrosomonas was positively correlated, while Denitratisoma was negatively correlated with EPSs and their components. Thauera was positively correlated, while Zoogloea was negatively correlated with the settleability and de-waterability of activated sludge. Full article
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<p>Long-term performance of SBR system under four kinds of FA concentrations. (<b>a</b>) NH<sub>4</sub><sup>+</sup>-N concentration and removal efficiency; (<b>b</b>) NO<sub>2</sub><sup>−</sup>-N concentration and NiAR; and (<b>c</b>) NO<sub>3</sub><sup>−</sup>-N concentration and NaAR.</p>
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<p>Effect of FA concentrations of the influent on the contents of three fractions of EPS and their components at the end of nitrification.</p>
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<p>Variation between nitrogen and EPSs and their components during a typical cycle under four kinds of FA concentrations: (<b>a</b>) R<sub>0.5</sub>; (<b>b</b>) R<sub>5</sub>; (<b>c</b>) R<sub>10</sub>; and (<b>d</b>) R<sub>15</sub>.</p>
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<p>Effect of FA concentration on the values of (<b>a</b>) CST; (<b>b</b>) SVI; and (<b>c</b>) SRF. Different letters indicate significant differences between different treatments. at the 0.05 level, testing by one-way ANOVA.</p>
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<p>(<b>a</b>) Path diagram estimating the correlations between the constants of sludge properties, EPSs and their components, and abundances of the functional gene/species. Solid and dotted lines represent the positive and negative correlations, respectively. The thickness of the line represents the strength of the correlation. (<b>b</b>) VPA of contribution of sludge properties, FA, and EPS to the shaping of predicted microbial functions.</p>
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17 pages, 8248 KiB  
Article
Improvement of Nanostructured Polythiophene Film Uniformity Using a Cruciform Electrode and Substrate Rotation in Atmospheric Pressure Plasma Polymerization
by Jae Young Kim, Hyo Jun Jang, Gyu Tae Bae, Choon-Sang Park, Eun Young Jung and Heung-Sik Tae
Nanomaterials 2022, 12(1), 32; https://doi.org/10.3390/nano12010032 - 23 Dec 2021
Cited by 4 | Viewed by 2727
Abstract
In atmospheric pressure (AP) plasma polymerization, increasing the effective volume of the plasma medium by expanding the plasma-generating region within the plasma reactor is considered a simple method to create regular and uniform polymer films. Here, we propose a newly designed AP plasma [...] Read more.
In atmospheric pressure (AP) plasma polymerization, increasing the effective volume of the plasma medium by expanding the plasma-generating region within the plasma reactor is considered a simple method to create regular and uniform polymer films. Here, we propose a newly designed AP plasma reactor with a cruciform wire electrode that can expand the discharge volume. Based on the plasma vessel configuration, which consists of a wide tube and a substrate stand, two tungsten wires crossed at 90 degrees are used as a common powered electrode in consideration of two-dimensional spatial expansion. In the wire electrode, which is partially covered by a glass capillary, discharge occurs at the boundary where the capillary terminates, so that the discharge region is divided into fourths along the cruciform electrode and the discharge volume can successfully expand. It is confirmed that although a discharge imbalance in the four regions of the AP plasma reactor can adversely affect the uniformity of the polymerized, nanostructured polymer film, rotating the substrate using a turntable can significantly improve the film uniformity. With this AP plasma reactor, nanostructured polythiophene (PTh) films are synthesized and the morphology and chemical properties of the PTh nanostructure, as well as the PTh-film uniformity and electrical properties, are investigated in detail. Full article
(This article belongs to the Special Issue Plasma-Enabled Synthesis of Nanostructured Surfaces and Nanoparticles)
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Figure 1
<p>Schematic diagram of the AP plasma polymerization system combined with gas supply, AP plasma reactor, and high-voltage power supply.</p>
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<p>Optical observation (digital photographs and ICCD images) of glow plasma according to bending angle of tungsten wire electrode: (<b>a</b>) 90 degrees, (<b>b</b>) 120 degrees, (<b>c</b>) 150 degrees, and (<b>d</b>) 180 degrees.</p>
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<p>Optical observation of glow plasma according to length of the bare part of the cruciform wire electrode: (<b>a</b>) 2 mm, (<b>b</b>) 15 mm, and (<b>c</b>) 30 mm.</p>
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<p>(<b>a</b>–<b>c</b>) Photographs of PTh films deposited onto glass disks with bare-wire lengths of (<b>a</b>) 2 mm, (<b>b</b>) 15 mm, and (<b>c</b>) 30 mm in an AP plasma reactor without substrate rotation; (<b>d</b>–<b>f</b>) Photographs of PTh films deposited onto glass disks with bare-wire lengths of (<b>d</b>) 2 mm, (<b>e</b>) 15 mm and (<b>f</b>) 30 mm with substrate rotating at 3 rpm; (<b>g</b>–<b>i</b>) Thickness profiles of the rotated nanostructured PTh films in (<b>d</b>–<b>f</b>).</p>
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<p>FE-SEM images of nanostructured PTh films deposited onto silicon substrates when the distances between the electrode and the substrate (<span class="html-italic">D</span>) were (<b>a</b>) 30 mm, (<b>b</b>) 40 mm, and (<b>c</b>) 50 mm and (<b>d</b>) comparison of thickness of PTh films.</p>
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<p>Comparison of ATR-FTIR spectra of deposited nanostructured PTh films when the distance between the electrode and the substrate of the plasma reactor was changed to 30 mm, 40 mm, and 50 mm.</p>
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<p>Transmission electron microscopy (TEM) images of PTh nanoparticles prepared via the proposed AP plasma reactor with (<b>a</b>) low magnification and (<b>b</b>) high magnification.</p>
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<p>FE-SEM images of nanostructured PTh films deposited onto silicon substrates as Ar flow for vaporized thiophene increased from 100 to 500 sccm.</p>
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<p>FE-SEM images of nanostructured PTh films as polymerization process time changed; (<b>a</b>) 10 min, (<b>b</b>) 20 min, and (<b>c</b>) 30 min.</p>
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<p>(<b>a</b>) XPS survey spectra of nanostructured PTh films synthesized under the plasma coupling and remote conditions. High-resolution XPS spectra of C 1s of PTh film prepared using the plasma (<b>b</b>) remote and (<b>c</b>) coupling modes. High-resolution XPS spectra of S 2p of PTh film prepared using the plasma (<b>d</b>) remote and (<b>e</b>) coupling modes.</p>
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<p>Comparison of FE-SEM images of plasma remote mode and coupling mode: (<b>a</b>) plasma remote mode, (<b>b</b>) plasma coupling mode, and (<b>c</b>) magnified side view FE-SEM images in the two different plasma modes.</p>
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<p>Changes in electrical resistance of iodine-doped PTh films on IDE substrates synthesized in plasma coupling and remote modes.</p>
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2 pages, 218 KiB  
Abstract
Effective Production of Bioactive Phenolic Compounds from Olive Stones
by Carmen Padilla-Rascón, Encarnación Ruiz, Eulogio Castro, Luisa B. Roseiro, Luis C. Duarte and Florbela Carvalheiro
Biol. Life Sci. Forum 2021, 6(1), 70; https://doi.org/10.3390/Foods2021-10940 - 13 Oct 2021
Viewed by 802
Abstract
Olive stones (OS) are a by-product generated in the olive oil production process. This residue is obtained in industries after the oil extraction process, and it is recognized as an interesting feedstock for the production of bioenergy and value-added products. Nevertheless, currently, it [...] Read more.
Olive stones (OS) are a by-product generated in the olive oil production process. This residue is obtained in industries after the oil extraction process, and it is recognized as an interesting feedstock for the production of bioenergy and value-added products. Nevertheless, currently, it is only used as a low-cost solid biofuel for combustion. An alternative valorization approach has been developed based on an acid-catalyzed process for the solubilization of hemicelluloses [1] and the production of furfural [2]. This process yields a solid cellulose and lignin-rich material, which can be further upgraded. In this work, an organosolv process for the delignification of the material and improvement of the enzymatic digestibility was applied and optimized. The organosolv stage was carried out with an ethanol:water ratio (50:50, w/w) in a Parr reactor, varying the temperature (140–190 °C) and the addition of the catalyst (0–100 mM H2SO4). The liquid fraction obtained was analyzed to evaluate the presence of value-added products, such as phenolic compounds with antioxidant activity. The total phenolic content was determined by the Folin–Ciocalteu method, obtaining a phenol concentration between 5 and 13 g GAE/L, corresponding to a phenol yield of 8 g GAE/100 g of processed material, which ranks in the range of those obtained from other plant sources, in other olive by-products such as exhausted olive pomace, up to 9 g GAE/100 g of extract have been reported [3]. The phenolic profile was obtained by capillary electrophoresis analysis, allowing the identification, among others, of vanillin and syringaldehyde as naturally occurring flavor components exhibiting antioxidant and antimicrobial properties. Therefore, with the present study, we were able to determine that the liquor obtained after the organosolv pretreatment of olive stones can also be valued as a bio-source of non-synthetic preservatives and additives for the food industry. Full article
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