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22 pages, 3747 KiB  
Article
Macroporous Poly(hydromethylsiloxane) Networks as Precursors to Hybrid Ceramics (Ceramers) for Deposition of Palladium Catalysts
by Jan Mrówka, Robert Kosydar, Kamil Kornaus, Janusz Partyka and Magdalena Hasik
Molecules 2024, 29(16), 3808; https://doi.org/10.3390/molecules29163808 (registering DOI) - 11 Aug 2024
Abstract
Poly(hydromethylsiloxane) (PHMS) was cross-linked with 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (D4Vi) in water-in-oil High Internal Phase Emulsions to form macroporous materials known as polyHIPEs. It was shown that in the process of pyrolysis under Ar atmosphere at 520 °C, the obtained polyHIPEs were converted [...] Read more.
Poly(hydromethylsiloxane) (PHMS) was cross-linked with 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (D4Vi) in water-in-oil High Internal Phase Emulsions to form macroporous materials known as polyHIPEs. It was shown that in the process of pyrolysis under Ar atmosphere at 520 °C, the obtained polyHIPEs were converted to ceramers with high yields (82.8–88.0 wt.%). Structurally, the obtained ceramers were hybrid ceramics, i.e., they consisted of Si-O framework and preserved organic moieties. Macropores present in the polyHIPE precursors remained in ceramers. Ceramers contained also micro- and mesopores which resulted from the precursor’s mass loss during pyrolysis. Total pore volume and BET specific surface area related to the existence of micro- and mesopores in ceramers depended on the PHMS: D4Vi ratio applied in polyHIPE synthesis. The highest total pore volume (0.143 cm3/g) and specific surface area (344 m2/g) were reached after pyrolysis of the precursor prepared with the lowest amount of D4Vi as compared to PHMS. The composite materials obtained after deposition of PdO nanoparticles onto ceramers followed by reduction of PdO by H2 were active and selective catalysts for phenylacetylene hydrogenation to styrene. Full article
(This article belongs to the Special Issue Porous Materials as Catalysts and Sorbents)
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<p>TG and DTG curves of the studied polyHIPEs. <span class="html-italic">Note:</span> for sample symbols please refer to <a href="#sec3dot2dot1-molecules-29-03808" class="html-sec">Section 3.2.1</a>.</p>
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<p>FTIR spectra of the studied polyHIPEs (P1–P3 samples) and ceramers (C1–C3 samples). <span class="html-italic">Note:</span> for sample symbols please refer to <a href="#sec3dot2dot1-molecules-29-03808" class="html-sec">Section 3.2.1</a> and <a href="#sec3dot2dot2-molecules-29-03808" class="html-sec">Section 3.2.2</a>.</p>
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<p>DRIFT spectra recorded in situ during heating of the P3 polyHIPE under Ar atmosphere.</p>
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<p>SEM images of the materials before (P1) and after (C1) pyrolysis.</p>
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<p>Void and window size distributions in the studied polyHIPEs and ceramers determined by analysis of SEM images. <span class="html-italic">Note:</span> for sample symbols please refer to <a href="#sec3dot2dot1-molecules-29-03808" class="html-sec">Section 3.2.1</a> and <a href="#sec3dot2dot2-molecules-29-03808" class="html-sec">Section 3.2.2</a>.</p>
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<p>N<sub>2</sub> adsorption/desorption isotherms of the studied ceramers. <span class="html-italic">Note:</span> for sample symbols please refer to <a href="#sec3dot2dot2-molecules-29-03808" class="html-sec">Section 3.2.2</a>.</p>
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<p>XRD diffraction patterns of the C3 ceramer and the C3_Pd material. <span class="html-italic">Note:</span> for sample symbols please refer to <a href="#sec3dot2dot2-molecules-29-03808" class="html-sec">Section 3.2.2</a>.</p>
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<p>TPR profiles of the prepared ceramer-PdO systems. <span class="html-italic">Note:</span> for sample symbols please refer to <a href="#sec3dot2dot2-molecules-29-03808" class="html-sec">Section 3.2.2</a>.</p>
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<p>Results of phenylacetylene hydrogenation catalyzed by C1_Pd, C2_Pd and C3_Pd materials treated with H<sub>2</sub> (<b>A</b>–<b>C</b>). <span class="html-italic">Note:</span> for sample symbols please refer to <a href="#sec3dot2dot2-molecules-29-03808" class="html-sec">Section 3.2.2</a>.</p>
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14 pages, 4295 KiB  
Article
Bio-Based Polyurethane–Urea with Self-Healing and Closed-Loop Recyclability Synthesized from Renewable Carbon Dioxide and Vanillin
by Tianyi Han, Tongshuai Tian, Shan Jiang and Bo Lu
Polymers 2024, 16(16), 2277; https://doi.org/10.3390/polym16162277 (registering DOI) - 10 Aug 2024
Viewed by 328
Abstract
Developing recyclable and self-healing non-isocyanate polyurethane (NIPU) from renewable resources to replace traditional petroleum-based polyurethane (PU) is crucial for advancing green chemistry and sustainable development. Herein, a series of innovative cross-linked Poly(hydroxyurethane-urea)s (PHUUs) were prepared using renewable carbon dioxide (CO2) and [...] Read more.
Developing recyclable and self-healing non-isocyanate polyurethane (NIPU) from renewable resources to replace traditional petroleum-based polyurethane (PU) is crucial for advancing green chemistry and sustainable development. Herein, a series of innovative cross-linked Poly(hydroxyurethane-urea)s (PHUUs) were prepared using renewable carbon dioxide (CO2) and vanillin, which displayed excellent thermal stability properties and solvent resistance. These PHUUs were constructed through the introduction of reversible hydrogen and imine bonds into cross-linked polymer networks, resulting in the cross-linked PHUUs exhibiting thermoplastic-like reprocessability, self healing, and closed-loop recyclability. Notably, the results indicated that the VL-TTD*-50 with remarkable hot-pressed remolding efficiency (nearly 98.0%) and self-healing efficiency (exceeding 95.0%) of tensile strength at 60 °C. Furthermore, they can be degraded in the 1M HCl and THF (v:v = 2:8) solution at room temperature, followed by regeneration without altering their original chemical structure and mechanical properties. This study presents a novel strategy for preparing cross-linked PHUUs with self-healing and closed-loop recyclability from renewable resources as sustainable alternatives for traditional petroleum-based PUs. Full article
(This article belongs to the Special Issue Preparation and Application of Biodegradable Polymeric Materials)
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<p>Schematic structure of VL-TTD* elastomers.</p>
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<p>(<b>a</b>) FTIR spectra of VL−C and VL−TTD*s; (<b>b</b>) FTIR spectra of VL−TTD*s; (<b>c</b>) swelling rates of the VL−TTD*s; (<b>d</b>) gel contents of the VL−TTD*s.</p>
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<p>Temperature-dependent <sup>1</sup>H NMR spectra of VL-TTD*-50 upon heating from 30 to 100 °C (<b>a</b>) and upon cooling from 100 to 30 °C (<b>b</b>).</p>
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<p>The rheology of VL-TTD*s: (<b>a</b>) Variation in the storage modulus as a function of the frequency and (<b>b</b>) variation in the loss modulus as a function of the frequency.</p>
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<p>(<b>a</b>) TGA and DTG curves of VL-TTD*s in N<sub>2</sub>; (<b>b</b>) DSC curves of VL-TTD*s; (<b>c</b>) stress–strain curves of VL-TTD*s; (<b>d</b>) mechanical properties of VL-TTD*s.</p>
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<p>(<b>a</b>) Photographs of the hot-pressing process. (<b>b</b>) FT-IR spectra of VL-TTD*-50 after two recycling processes; (<b>c</b>) stress–strain curves of VL-TTD*-50 after two recycling processes.</p>
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<p>(<b>a</b>) Polarizing optical microscopy images of the self-healing process of a crack on the VL-TTD*-50; (<b>b</b>) images of the self-healing of VL-TTD*-50: (i) original sample; (ii) cut segments; (iii) healed sample; (iv) the healed sample with the hanging weight of a 500 g bottle; (<b>c</b>) stress–strain curves of the VL-TTD*-50 after healing at different times.</p>
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<p>The self-healing mechanism of the VL-TTD*s.</p>
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<p>Closed-loop recycling of VL-TTD*s.</p>
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<p>(<b>a</b>) Degradation rate curves of VL-TTD*-50 in 1M HCl and THF (<span class="html-italic">v</span>:<span class="html-italic">v</span> = 2:8) and H<sub>2</sub>O/THF (<span class="html-italic">v</span>:<span class="html-italic">v</span> = 2:8); (<b>b</b>) FT-IR spectra of VL-TTD*-50, degraded products, and regenerated VL-TTD*-50; (<b>c</b>) stress–strain curves of original and regenerated VL-TTD*-50; (<b>d</b>) DSC curves of original and regenerated VL-TTD*-50.</p>
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<p>Synthetic routes of the VL-TTD*s.</p>
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21 pages, 5081 KiB  
Article
Radially and Axially Oriented Ammonium Alginate Aerogels Modified with Clay/Tannic Acid and Crosslinked with Glutaraldehyde
by Lucía G. De la Cruz, Tobias Abt, Noel León and Miguel Sánchez-Soto
Gels 2024, 10(8), 526; https://doi.org/10.3390/gels10080526 (registering DOI) - 10 Aug 2024
Viewed by 311
Abstract
Lightweight materials that combine high mechanical strength, insulation, and fire resistance are of great interest to many industries. This work explores the properties of environmentally friendly alginate aerogel composites as potential sustainable alternatives to petroleum-based materials. This study analyzes the effects of two [...] Read more.
Lightweight materials that combine high mechanical strength, insulation, and fire resistance are of great interest to many industries. This work explores the properties of environmentally friendly alginate aerogel composites as potential sustainable alternatives to petroleum-based materials. This study analyzes the effects of two additives (tannic acid and montmorillonite clay), the orientation that results during casting, and the crosslinking of the biopolymer with glutaraldehyde on the properties of the aerogel composites. The prepared aerogels exhibited high porosities between 90% and 97% and densities in the range of 0.059–0.191 g/cm3. Crosslinking increased the density and resulted in excellent performance under loading conditions. In combination with axial orientation, Young’s modulus and yield strength reached values as high as 305 MPa·cm3/g and 7 MPa·cm3/g, respectively. Moreover, the alginate-based aerogels exhibited very low thermal conductivities, ranging from 0.038 W/m·K to 0.053 W/m·K. Compared to pristine alginate, the aerogel composites’ thermal degradation rate decreased substantially, enhancing thermal stability. Although glutaraldehyde promoted combustion, the non-crosslinked aerogel composites demonstrated high fire resistance. No flame was observed in these samples under cone calorimeter radiation, and a minuscule peak of heat release of 21 kW/m2 was emitted as a result of their highly efficient graphitization and fire suppression. The combination of properties of these bio-based aerogels demonstrates their potential as substituents for their fossil-based counterparts. Full article
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<p>Aerogel preparation via the sol–gel method through radial and axial freeze casting (Created with Biorender.com Agrmt No. BG27599XKD).</p>
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<p>(<b>a</b>) FTIR spectra of pristine ammonium alginate (AA) aerogel before and after its modification with TA and MMT and crosslinking with GTA; (<b>b</b>) XPS spectra of non-crosslinked A5 and crosslinked A5* and A5C5T2* aerogels.</p>
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<p>(<b>a</b>) Comparison of bulk and relative density and porosity of ammonium alginate aerogel composites: N<sub>2</sub> adsorption/desorption isotherms and BET specific surface of (<b>b</b>) A5C5-R and (<b>c</b>) A5C5-X aerogels and (<b>d</b>) pore volume and pore size distribution of A5C5-R and A5C5-X aerogels.</p>
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<p>Virtual µ-CT image of pristine alginate aerogel frozen in the (<b>a</b>) radial (A5-R) and (<b>b</b>) axial (A5-X) directions and (<b>c</b>) GTA-crosslinked alginate axial aerogel composite (A5C5T2-X*).</p>
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<p>SEM images revealing the evolution of aerogel structures as the solid content increased: (<b>a</b>) A5-R, (<b>b</b>) A5C5-R, and (<b>c</b>) A5C5T2-R; pore alignment in the axial orientation: (<b>d</b>) A5-X, (<b>e</b>)A5C5-X, and (<b>f</b>) A5C5T2-X, and (<b>h</b>) after GTA crosslinking. (<b>g</b>) EDS of the dispersion of MMT clay on the A5C5T2-X* aerogel.</p>
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<p>(<b>a</b>) Stress–strain compressive plots of alginate–clay–tannic acid aerogels; (<b>b</b>) specific modulus and specific yield stress of the aerogels studied.</p>
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<p>(<b>a</b>) Correlation between the thermal conductivities and bulk densities of the AA aerogel composites, (<b>b</b>) Scheme of different contributions in thermal conductivity and thermography of A5C5-R and A5C5T1-X aerogels on a hot plate surface at 100 °C, and (<b>c</b>) Thermal conductivity and effusivity of AA composite aerogels.</p>
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<p>(<b>a</b>) TGA weight loss; (<b>b</b>) derivative thermogravimetric curves of alginate composite aerogels.</p>
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<p>Main representative (<b>a</b>) HRR, (<b>b</b>) THR, and (<b>c</b>) ARHE curves from ammonium alginate composites; (<b>d</b>) photograph and SEM photomicrograph and EDS elemental mapping of the char of A5C5T2 after cone calorimetry; (<b>e</b>) Raman spectra of A5, A5C5, and A5C5T2 aerogel ashes.</p>
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<p>(<b>a</b>) Comparison of the compositions and properties of the aerogels evaluated in this study; (<b>b</b>) comparison of our ammonium alginate aerogels with other aerogel composites reported in the literature [<a href="#B49-gels-10-00526" class="html-bibr">49</a>,<a href="#B50-gels-10-00526" class="html-bibr">50</a>,<a href="#B51-gels-10-00526" class="html-bibr">51</a>,<a href="#B52-gels-10-00526" class="html-bibr">52</a>,<a href="#B53-gels-10-00526" class="html-bibr">53</a>,<a href="#B54-gels-10-00526" class="html-bibr">54</a>].</p>
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14 pages, 1389 KiB  
Article
Vitronectin Levels in the Plasma of Neuroblastoma Patients and Culture Media of 3D Models: A Prognostic Circulating Biomarker?
by Amparo López-Carrasco, Isaac Vieco-Martí, Sofía Granados-Aparici, Delia Acevedo-León, Nuria Estañ-Capell, Raquel Portugal, Jorge Huerta-Aragonés, Adela Cañete, Samuel Navarro and Rosa Noguera
Int. J. Mol. Sci. 2024, 25(16), 8733; https://doi.org/10.3390/ijms25168733 (registering DOI) - 10 Aug 2024
Viewed by 177
Abstract
Vitronectin is a glycoprotein present in plasma and the extracellular matrix that is implicated in cell migration. The high amount of vitronectin found in neuroblastoma biopsies has been associated with poor prognosis. Moreover, increased vitronectin levels have been described in the plasma of [...] Read more.
Vitronectin is a glycoprotein present in plasma and the extracellular matrix that is implicated in cell migration. The high amount of vitronectin found in neuroblastoma biopsies has been associated with poor prognosis. Moreover, increased vitronectin levels have been described in the plasma of patients with different cancers. Our aim was to assess vitronectin as a potential circulating biomarker of neuroblastoma prognosis. Vitronectin concentration was quantified using ELISA in culture media of four neuroblastoma cell lines grown in a monolayer and in 3D models, and in the plasma of 114 neuroblastoma patients. Three of the neuroblastoma cell lines secreted vitronectin to culture media when cultured in a monolayer and 3D models. Vitronectin release was higher by neuroblastoma cells cultured in 3D models than in the monolayer and was still elevated when cells were grown in 3D scaffolds with cross-linked vitronectin. Vitronectin secretion occurred independently of cell numbers in cultures. Its concentration in the plasma of neuroblastoma patients ranged between 52.4 and 870 µg/mL (median, 218 µg/mL). A ROC curve was used to establish a cutoff of 361 µg/mL, above which patients over 18 months old had worse prognosis (p = 0.0018). Vitronectin could be considered a new plasma prognostic biomarker in neuroblastoma and warrants confirmation in collaborative studies. Drugs inhibiting vitronectin interactions with cells and/or the extracellular matrix could represent a significant improvement in survival for neuroblastoma patients. Full article
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<p>VN secretion by NB cells to culture media. (<b>A</b>) Origin and main clinical-molecular characteristics of the four NB cell lines. All presented aggressive features as derived from stage 4 patients, being <span class="html-italic">MYCN</span>-amplified or <span class="html-italic">ALK</span>-mutated and having SCAs. * For more details of PDX origin, see ref. [<a href="#B36-ijms-25-08733" class="html-bibr">36</a>]. (<b>B</b>) Comparison of VN levels secreted to culture media of 2D (monolayer) and 3D HG cultures by NB cell lines in which VN detection was positive by ELISA (<span class="html-italic">p</span>-value = 0.0052). (<b>C</b>) Concentration of VN secreted by the four NB cell lines to culture media of the 3D HGs in ng/mL per million cells (left Y-axis scale); blue and orange bars represent HGs without (NO-VN) and with cross-linked VN (VN), respectively; light colors refer to 2 weeks (2W) of culture and dark colors to 3W; number of cells calculated with digital analysis in two HGs from which we collected the culture media, measured in millions of cells, as shown on the right Y-axis scale (dots inside the bars).</p>
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<p>VN levels in plasma of NB patients. (<b>A</b>) Descriptive statistics of patient numbers and VN levels detected by ELISA in the plasma of all patients younger and older than 18 months of the patients who remained alive and of those who died. Median VN values are highlighted in bold format and the red font points out the lower levels of VN in alive than in dead patients older than 18 months. (<b>B</b>) Graphic representation of VN levels in the mentioned groups. VN concentration was significantly different between alive and dead patients older than 18 months (<span class="html-italic">p</span>-value = 0.0074). (<b>C</b>) The ROC curve obtained for patients older than 18 months was significant (<span class="html-italic">p</span>-value = 0.0026) and allowed us to establish a cutoff of 361 µL/mL (red arrow), over which patients showed a poor prognosis.</p>
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<p>Survival probabilities of NB patients older than 18 months according to VN levels. Kaplan–Meier curves for (<b>A</b>) overall survival (OS) and (<b>B</b>) event-free survival (EFS) reflected the significantly lower survival of NB patients with VN plasma levels over the cutoff (<span class="html-italic">p</span> = 0.0018 and <span class="html-italic">p</span> = 0.0027, respectively). Five-year OS for patients with VN levels under and over the cutoff was 53% and 7%, respectively, and EFS was 45% and 7%, respectively.</p>
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15 pages, 4640 KiB  
Article
Study of the Preparation and Properties of Chemically Modified Materials Based on Rapeseed Meal
by Sara Aquilia, Luca Rosi, Michele Pinna, Sabrina Bianchi, Walter Giurlani, Marco Bonechi, Francesco Ciardelli, Anna Maria Papini and Claudia Bello
Biomolecules 2024, 14(8), 982; https://doi.org/10.3390/biom14080982 (registering DOI) - 10 Aug 2024
Viewed by 167
Abstract
In recent years, there has been increasing interest in developing novel materials based on natural biopolymers as a renewable alternative to petroleum-based plastics. The availability of proteins derived from agricultural by-products, along with their favourable properties, has fostered a renewed interest in protein-based [...] Read more.
In recent years, there has been increasing interest in developing novel materials based on natural biopolymers as a renewable alternative to petroleum-based plastics. The availability of proteins derived from agricultural by-products, along with their favourable properties, has fostered a renewed interest in protein-based materials, promoting research in innovative technologies. In this study, we propose the use of rapeseed protein-rich meal as the main ingredient for the preparation of novel sustainable materials combining excellent environmental properties such as biodegradability and renewability. The application of sustainable products in the present high-tech society requires the modification of the basic native properties of these natural compounds. The original route proposed in this paper consists of preparation via the compression moulding of flexible biomaterials stabilized by crosslinkers/chain extenders. An investigation of the effects of different denaturing and disulfide bond reducing agents, crosslinkers, and preparation conditions on the material mechanical behaviour demonstrated that the novel materials have appreciable strength and stiffness. The results show the potential of utilizing full meal from vegetable by-products to prepare protein-based materials with guaranteed ecofriendly characteristics and mechanical properties adequate for specific structural applications. Full article
(This article belongs to the Collection Feature Papers in 'Biological and Bio- Materials' Section)
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<p>Histogram of tensile properties (<b>left</b>) and stress/strain diagram (<b>right</b>) of meal/casein/water/glycerol blends without or with the addition of Na<sub>2</sub>SO<sub>3</sub> and/or a denaturing agent (for specimens’ composition refers to <a href="#biomolecules-14-00982-t002" class="html-table">Table 2</a>).</p>
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<p>First-derivative curve of TGA of rapeseed meal protein-based materials RM-R0, RM, RM-R2, RM-D1, RM-D2, and RM-R2D2 14%.</p>
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<p>Overlapped full FT-IR spectra of rapeseed-meal-based materials.</p>
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<p>FT-IR spectra of amide I band of: (<b>A</b>) RM-R0, RM, RM-R2, RM-D1, RM-D2, and RM-R2D2 14% materials. (<b>B</b>) Rapeseed meal, RM-R0, RM, and RM-R2D2 14% materials (baseline corrected).</p>
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<p>Scanning electron microscopy images of surface (<b>left</b>) and cryofracture cross-section (<b>right</b>) of specimens RM-R0, RM-D2, and RM-R2D2 14%.</p>
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15 pages, 4626 KiB  
Article
Shape-Memory Effect of 4D-Printed Gamma-Irradiated Low-Density Polyethylene
by Yunke Huang, Yongxiang Tao and Yan Wang
Crystals 2024, 14(8), 717; https://doi.org/10.3390/cryst14080717 (registering DOI) - 10 Aug 2024
Viewed by 188
Abstract
Four-dimensional-printed smart materials have a wide range of applications in areas such as biomedicine, aerospace, and soft robotics. Among 3D printing technologies, fused deposition molding (FDM) is economical, simple, and apply to thermoplastics. Cross-linked polyethylene (XLPE) forms a stable chemical cross-linking structure and [...] Read more.
Four-dimensional-printed smart materials have a wide range of applications in areas such as biomedicine, aerospace, and soft robotics. Among 3D printing technologies, fused deposition molding (FDM) is economical, simple, and apply to thermoplastics. Cross-linked polyethylene (XLPE) forms a stable chemical cross-linking structure and shows good shape-memory properties, but the sample is not soluble or fusible, which makes it hard to be applied in FDM printing. Therefore, in this work, a new idea of printing followed by irradiation was developed to prepare 4D-printed XLPE. First, low-density polyethylene (LDPE) was used to print the products using FDM technology and then cross-linked by gamma irradiation was used. The printing parameters were optimized, and the gel content, mechanical properties, and shape-memory behaviors were characterized. After gamma irradiation, the samples showed no new peak in FTIR spectra. And the samples exhibited good shape-memory capabilities. Increasing the irradiation dose increased the cross-linking degree and tensile strength and improved the shape-memory properties. However, it also decreased the elongation at break, and it did not affect the crystallization or melting behaviors of LDPE. With 120 kGy of irradiation, the shape recovery and fixity ratios (Rr and Rf) of the samples were 97.69% and 98.65%, respectively. After eight cycles, Rr and Rf remained at 96.30% and 97.76%, respectively, indicating excellent shape-memory performance. Full article
(This article belongs to the Section Organic Crystalline Materials)
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<p>Preparation process of 4D printing shape-memory-cross-linked LDPE samples.</p>
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<p>Schematic diagram of printing orientations of FDM (<b>a</b>); deposition path of FDM filament (<b>b</b>).</p>
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<p>Digital photos of the LDPE dumbbell-shaped samples at different printing flows (<b>a</b>); SEM images of the cross-section of samples at 80% and 110% printing flows (<b>b</b>,<b>c</b>).</p>
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<p>Digital photos of the LDPE dumbbell-shaped samples at different printing speeds (<b>a</b>); SEM images of the cross-section of samples at 35 mm/s and 15 mm/s printing speeds (<b>b</b>,<b>c</b>).</p>
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<p>Digital photos of LDPE dumbbell-shaped samples at different printing temperatures (<b>a</b>); SEM images of the cross-section of samples at 140 °C and 200 °C printing temperatures (<b>b</b>,<b>c</b>).</p>
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<p>FTIR spectra of uncross-linked LDPE and 120 kGy cross-linked LDPE.</p>
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<p>The relationship between <span class="html-italic">R</span>(<span class="html-italic">s + s</span><sup>1/2</sup>) and <span class="html-italic">R</span><sup>1/2</sup> for the cross-linking printing samples.</p>
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<p>First cooling DSC curves and second heating DSC curves of the LDPE with different irradiation doses (<b>a</b>,<b>b</b>).</p>
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<p>Effect of irradiation doses on the mechanical properties of LDPE-printed samples.</p>
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<p>Shape-memory test results of samples with different irradiation doses.</p>
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<p>Effect of cycle times on shape-memory performance of LDPE-printed samples.</p>
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<p>Shape recovery process of the 4D-printed flower.</p>
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26 pages, 993 KiB  
Article
Tailoring the Structure and Physico-Chemical Features of Cellulose-Based Hydrogels Using Multi-Epoxy Crosslinking Agents
by Raluca Nicu, Gabriela Lisa, Raluca Nicoleta Darie-Nita, Mihaela Iuliana Avadanei, Alexandra Bargan, Daniela Rusu and Diana Elena Ciolacu
Gels 2024, 10(8), 523; https://doi.org/10.3390/gels10080523 (registering DOI) - 9 Aug 2024
Viewed by 123
Abstract
Hydrogel features can be designed and optimized using different crosslinking agents to meet specific requirements. In this regard, the present work investigates the physico-chemical features of cellulose-based hydrogels, designed by using different epoxy crosslinkers from the same glycidyl family, namely epichlorohydrin (ECH), 1,4-butanediol [...] Read more.
Hydrogel features can be designed and optimized using different crosslinking agents to meet specific requirements. In this regard, the present work investigates the physico-chemical features of cellulose-based hydrogels, designed by using different epoxy crosslinkers from the same glycidyl family, namely epichlorohydrin (ECH), 1,4-butanediol diglycidyl ether (BDDE), and trimethylolpropane triglycidyl ether (TMPTGE). The effect of the crosslinker’s structure (from simple to branched) and functionality (mono-, bi- and tri-epoxy groups) on the hydrogels’ features was studied. The performances of the hydrogels were investigated through the gel fraction, as well as by ATR-FTIR, DVS, SEM, DSC, and TG analyses. Also, the swelling and rheological behaviors of the hydrogels were examined. The advantages and limitations of each approach were discussed and a strong correlation between the crosslinker structure and the hydrogel properties was established. The formation of new ether bonds was evidenced by ATR-FTIR spectroscopy. It was emphasized that the pore size is directly influenced by the crosslinker type, namely, it decreases with the increasing number of epoxy groups from the crosslinker molecule, i.e., from 46 ± 11.1 µm (hydrogel CE, with ECH) to 12.3 ± 2.5 µm (hydrogel CB, with BDDE) and 6.7 ± 1.5 µm (hydrogel CT, with TMPTGE). The rheological behavior is consistent with the swelling data and hydrogel morphology, such as CE with the highest Qmax and the largest pore size being relatively more elastic than CB and CT. Instead, the denser matrices obtained by using crosslinkers with more complex structures have better thermal stability. The experimental results highlight the possibility of using a specific crosslinking agent, with a defined structure and functionality, in order to establish the main characteristics of hydrogels and, implicitly, to design them for a certain field of application. Full article
(This article belongs to the Special Issue Polysaccharide: Gelation Arts)
18 pages, 8835 KiB  
Article
Influence of Long-Term Moisture Exposure and Temperature on the Mechanical Properties of Hybrid FRP Composite Specimens
by Getahun Tefera, Glen Bright and Sarp Adali
J. Compos. Sci. 2024, 8(8), 312; https://doi.org/10.3390/jcs8080312 - 9 Aug 2024
Viewed by 194
Abstract
The present experimental study assesses the mechanical properties of glass/carbon/glass hybrid composite laminates after being exposed to moisture in a deep freezer and elevated temperatures for extended periods. The top and bottom layers of the hybrid laminates are reinforced with glass fibre, and [...] Read more.
The present experimental study assesses the mechanical properties of glass/carbon/glass hybrid composite laminates after being exposed to moisture in a deep freezer and elevated temperatures for extended periods. The top and bottom layers of the hybrid laminates are reinforced with glass fibre, and the middle layer is reinforced with carbon fibre using the epoxy matrix as a binder polymer material. The hybrid laminates were manufactured using the resin transfer moulding method, and their compressive and tensile properties were determined using a tensile testing machine. The storage modulus, loss modulus, and damping factors of all groups of laminates were identified using a dynamic mechanical analysis as a function of temperature and vibration frequency. The experimental results on compressive and tensile properties revealed slight variations when the hybrid laminates were kept at low temperatures in a deep freezer for extended periods. This might occur due to the increasing molecular crosslinking of the polymer network. As the testing temperature increased, compressive, tensile, storage modules, loss modulus, and damping factors decreased. This might occur due to the increasing mobility of the binder material. Particularly, the highest stiffness parameters were obtained at −80 °C/GCG (glass/carbon/glass) laminates due to the presence of a beta transition in the glassy region. The relationships between the glass transitions and the targeted frequencies were characterized. The values of the glass transition shift towards higher temperatures as the frequency increases. This might occur due to a reduction in the gaps between the crosslinking of the epoxy network when the frequency increases. The accuracy of the storage modulus results was compared with the empirical models. The model based on the Arrhenius law provided the closest correlation. Meanwhile, another model was observed that was not accurate enough to predict when gamma and beta relaxations occur in a glassy state. Full article
(This article belongs to the Section Fiber Composites)
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<p>The hybrid laminate preparation process includes (<b>a</b>) a fibre-cutting process, (<b>b</b>) a fibre orientation process, (<b>c</b>) setups for the infusion process, and (<b>d</b>) hybrid laminates after infusion.</p>
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<p>A flow chart for the construction and testing methods of GCG hybrid specimens.</p>
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<p>Mechanical properties and failure load of hybrid laminates at various temperatures, (<b>a</b>) compressive properties, and (<b>b</b>) tensile properties.</p>
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<p>Storage modulus properties of control GCG (<b>a</b>), 0 °C/GCG (<b>b</b>), −20 °C/GCG (<b>c</b>), and −80 °C/GCG (<b>d</b>) laminates at various temperatures and frequencies.</p>
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<p>Storage modulus properties of control GCG (<b>a</b>), 0 °C/GCG (<b>b</b>), −20 °C/GCG (<b>c</b>), and −80 °C/GCG (<b>d</b>) laminates at various temperatures and frequencies.</p>
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<p>The conversion degree of glass transition (<math display="inline"><semantics> <mrow> <msub> <mrow> <mi>α</mi> </mrow> <mrow> <mi>g</mi> </mrow> </msub> </mrow> </semantics></math>) for modelling the storage modulus of control GCG (<b>a</b>), 0 °C/GCG (<b>b</b>), −20 °C/GCG (<b>c</b>), and −80 °C/GCG (<b>d</b>) hybrid laminates.</p>
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<p>The conversion degree of glass transition (<math display="inline"><semantics> <mrow> <msub> <mrow> <mi>α</mi> </mrow> <mrow> <mi>g</mi> </mrow> </msub> </mrow> </semantics></math>) for modelling the storage modulus of control GCG (<b>a</b>), 0 °C/GCG (<b>b</b>), −20 °C/GCG (<b>c</b>), and −80 °C/GCG (<b>d</b>) hybrid laminates.</p>
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<p>Loss modulus and damping properties of control GCG (<b>a</b>), 0 °C/GCG (<b>b</b>), −20 °C/GCG (<b>c</b>), and −80 °C/GCG (<b>d</b>) laminates at various temperatures and frequencies.</p>
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<p>Loss modulus and damping properties of control GCG (<b>a</b>), 0 °C/GCG (<b>b</b>), −20 °C/GCG (<b>c</b>), and −80 °C/GCG (<b>d</b>) laminates at various temperatures and frequencies.</p>
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<p>The logarithmic frequencies versus the reciprocal of glass transition temperatures of the control GCG (<b>a</b>), 0 °C/GCG (<b>b</b>), −20 °C/GCG (<b>c</b>), and −80 °C/GCG (<b>d</b>) hybrid laminates.</p>
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<p>The logarithmic frequencies versus the reciprocal of glass transition temperatures of the control GCG (<b>a</b>), 0 °C/GCG (<b>b</b>), −20 °C/GCG (<b>c</b>), and −80 °C/GCG (<b>d</b>) hybrid laminates.</p>
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<p>Comparisons between the storage modulus data and empirical models for control GCG laminates at 1 Hz (<b>a</b>) and 100 Hz (<b>b</b>).</p>
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<p>Comparisons between the storage modulus data and empirical models for 0 °C/GCG laminates at 1 Hz (<b>a</b>) and 100 Hz (<b>b</b>).</p>
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<p>Comparisons between the storage modulus data and empirical models for −20 °C/GCG laminates at 1 Hz (<b>a</b>) and 100 Hz (<b>b</b>).</p>
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<p>Comparisons between the storage modulus data and empirical models for −80 °C/GCG laminates at 1 Hz (<b>a</b>) and 100 Hz (<b>b</b>).</p>
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12 pages, 3164 KiB  
Article
High-Temperature Water Electrolysis Properties of Membrane Electrode Assemblies with Nafion and Crosslinked Sulfonated Polyphenylsulfone Membranes by Using a Decal Method
by Je-Deok Kim
Membranes 2024, 14(8), 173; https://doi.org/10.3390/membranes14080173 - 8 Aug 2024
Viewed by 284
Abstract
To improve the stability of high-temperature water electrolysis, I prepared membrane electrode assemblies (MEAs) using a decal method and investigated their water electrolysis properties. Nafion 115 and crosslinked sulfonated polyphenylsulfone (CSPPSU) membranes were used. IrO2 was used as the oxygen evolution reaction [...] Read more.
To improve the stability of high-temperature water electrolysis, I prepared membrane electrode assemblies (MEAs) using a decal method and investigated their water electrolysis properties. Nafion 115 and crosslinked sulfonated polyphenylsulfone (CSPPSU) membranes were used. IrO2 was used as the oxygen evolution reaction (OER) catalyst, and Pt/C was used as the hydrogen evolution reaction (HER) catalyst. The conductivity of the CSPPSU membrane at 80 °C and 90% RH (relative humidity) is about four times lower than that of the Nafion 115 membrane. Single-cell water electrolysis was performed while measuring the current density and performing electrochemical impedance spectroscopy (EIS) at cell temperatures from 80 to 150 °C and the stability of the current density over time at 120 °C and 1.7 V. The current density of water electrolysis using Nafion 115 and CSPPSU membranes at 150 °C and 2 V was 1.2 A/cm2 for both. The current density of the water electrolysis using the CSPPSU membrane at 120 °C and 1.7 V was stable for 40 h. The decal method improved the contact between the CSPPSU membrane and the catalyst electrode, and a stable current density was obtained. Full article
(This article belongs to the Special Issue Membranes for Energy and the Environment)
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<p>Photographs of a single cell, the anode side, and the cathode side; (<b>a</b>) SUS316L end plate, (<b>b</b>) Pt/Ti separator plate, and (<b>c</b>) carbon separator plate.</p>
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<p>Polarization curves: (<b>a</b>) Nafion 115 and (<b>b</b>) CSPPSU membranes at different operation temperatures.</p>
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<p>Electrochemical performance analysis of Nafion 115 membrane (<a href="#membranes-14-00173-f002" class="html-fig">Figure 2</a>a): (<b>a</b>) Polarization curves of the HFR-free cell; (<b>b</b>) HFR vs. current density; (<b>c</b>) HFR-free polarization data at low current densities, plotted on a logarithmic scale and (<b>d</b>) at current densities between 800 and 1200 mA/cm<sup>2</sup>.</p>
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<p>Electrochemical performance analysis of CSPPSU membrane (<a href="#membranes-14-00173-f002" class="html-fig">Figure 2</a>b): (<b>a</b>) Polarization curves of HFR-free cell; (<b>b</b>) HFR over current density; (<b>c</b>) HFR-free polarization data at low current densities, plotted on a logarithmic scale and (<b>d</b>) at current densities between 500 and 1200 mA/cm<sup>2</sup>.</p>
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<p>Nyquist plots measured at different operation temperatures of cells with (<b>a</b>) Nafion 115 and (<b>b</b>) CSPPSU membranes; (<b>c</b>) equivalent circuit used to fit the EIS data.</p>
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<p>Time dependence of the single cell with (<b>a</b>) Nafion 115 and (<b>b</b>) CSPPSU membranes at 120 °C and 1.7 V.</p>
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<p>Comparison of the time dependence of a single cell of an MEA with a Nafion 115 or a CSPPSU membrane made using a decal method and a porous IrO<sub>2</sub> electrode at 120 °C and 1.7 V [<a href="#B18-membranes-14-00173" class="html-bibr">18</a>,<a href="#B19-membranes-14-00173" class="html-bibr">19</a>].</p>
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27 pages, 5757 KiB  
Article
Functionalised Sodium–Carboxymethylcellulose–Collagen Bioactive Bilayer as an Acellular Skin Substitute for Future Use in Diabetic Wound Management: The Evaluation of Physicochemical, Cell Viability, and Antibacterial Effects
by Maheswary Thambirajoo, Nur Izzah Md Fadilah, Manira Maarof, Yogeswaran Lokanathan, Mohd Ambri Mohamed, Sarani Zakaria, Ruszymah Bt Hj Idrus and Mh Busra Fauzi
Polymers 2024, 16(16), 2252; https://doi.org/10.3390/polym16162252 - 8 Aug 2024
Viewed by 252
Abstract
The wound healing mechanism is dynamic and well-orchestrated; yet, it is a complicated process. The hallmark of wound healing is to promote wound regeneration in less time without invading skin pathogens at the injury site. This study developed a sodium–carboxymethylcellulose (Na-CMC) bilayer scaffold [...] Read more.
The wound healing mechanism is dynamic and well-orchestrated; yet, it is a complicated process. The hallmark of wound healing is to promote wound regeneration in less time without invading skin pathogens at the injury site. This study developed a sodium–carboxymethylcellulose (Na-CMC) bilayer scaffold that was later integrated with silver nanoparticles/graphene quantum dot nanoparticles (AgNPs/GQDs) as an acellular skin substitute for future use in diabetic wounds. The bilayer scaffold was prepared by layering the Na-CMC gauze onto the ovine tendon collagen type 1 (OTC-1). The bilayer scaffold was post-crosslinked with 0.1% (w/v) genipin (GNP) as a natural crosslinking agent. The physical and chemical characteristics of the bilayer scaffold were evaluated. The results demonstrate that crosslinked (CL) groups exhibited a high-water absorption capacity (>1000%) and an ideal water vapour evaporation rate (2000 g/m2 h) with a lower biodegradation rate and good hydrophilicity, compression, resilience, and porosity than the non-crosslinked (NC) groups. The minimum inhibitory concentration (MIC) of AgNPs/GQDs presented some bactericidal effects against Gram-positive and Gram-negative bacteria. The cytotoxicity tests on bilayer scaffolds demonstrated good cell viability for human epidermal keratinocytes (HEKs) and human dermal fibroblasts (HDFs). Therefore, the Na-CMC bilayer scaffold could be a potential candidate for future diabetic wound care. Full article
(This article belongs to the Special Issue Advanced Biodegradable Polymer Scaffolds for Tissue Engineering II)
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<p>Fabrication of the bilayer scaffold (gauze–collagen bilayer).</p>
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<p>Gross appearance of the different scaffolds. (<b>A</b>) NCG. (<b>B</b>) CLG. (<b>C</b>) NCC. (<b>D</b>) CLC. (<b>E</b>) NCB. (<b>F</b>) CLB. (<b>G</b>) NCC scaffold. (<b>H</b>) CLC scaffold. (<b>I</b>) NCB bilayer scaffold. (<b>J</b>) CLB bilayer scaffold.</p>
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<p>FTIR spectrum analysis between non-crosslinked and crosslinked groups.</p>
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<p>TGA analysis between non-crosslinked and crosslinked groups.</p>
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<p>The morphological structures of the bilayer scaffolds. (<b>a</b>) Percentage of porosity. (<b>b</b>) Number of pores and SEM morphology of the bilayer scaffolds. (<b>c</b>) Gross appearance. Surface and cross-section of the bilayer scaffolds. (<b>d</b>) Bilayer scaffolds of non-crosslinked and crosslinked groups. Red lines denote the border line between gauze and collagen. (*) represents a significant difference (<span class="html-italic">p</span> &lt; 0.05) between non-crosslinked and crosslinked groups.</p>
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<p>(<b>a</b>) Degree of crosslinking. (<b>b</b>) Water absorption ability. (<b>c</b>) Water vapour transmission rate. (<b>d</b>) Contact angle. (*) represents a significant difference (<span class="html-italic">p</span> &lt; 0.05) between NC and CL groups.</p>
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<p>(<b>a</b>) Compression. (<b>b</b>) Resilience. (<b>c</b>) Biodegradation. (<b>d</b>) Ultimate tensile strength. (<b>e</b>) Young’s modulus. (<b>f</b>) Elongation at break. (*) represents a significant difference (<span class="html-italic">p</span> &lt; 0.05) between non-crosslinked and crosslinked groups.</p>
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<p>Live/dead cell viability assay. (<b>a</b>) The qualitative analysis of cell viability by using HEKs and HDF cells on bilayer scaffolds. (<b>b</b>,<b>c</b>) The quantitative analysis of HEKs and HDFs cells in 24 h of incubation based on the percentage of live/dead cells. (<b>d</b>,<b>e</b>) MTT assay based on the percentage of cell viability for HEKs and HDFs on Days 1, 3, and 7.</p>
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22 pages, 8826 KiB  
Article
Microbead-Encapsulated Luminescent Bioreporter Screening of P. aeruginosa via Its Secreted Quorum-Sensing Molecules
by Abraham Abbey Paul, Yael Schlichter Kadosh, Ariel Kushmaro and Robert S. Marks
Biosensors 2024, 14(8), 383; https://doi.org/10.3390/bios14080383 - 8 Aug 2024
Viewed by 432
Abstract
Pseudomonas aeruginosa is an opportunistic Gram-negative bacterium that remains a prevalent clinical and environmental challenge. Quorum-sensing (QS) molecules are effective biomarkers in pinpointing the presence of P. aeruginosa. This study aimed to develop a convenient-to-use, whole-cell biosensor using P. aeruginosa reporters individually [...] Read more.
Pseudomonas aeruginosa is an opportunistic Gram-negative bacterium that remains a prevalent clinical and environmental challenge. Quorum-sensing (QS) molecules are effective biomarkers in pinpointing the presence of P. aeruginosa. This study aimed to develop a convenient-to-use, whole-cell biosensor using P. aeruginosa reporters individually encapsulated within alginate-poly-L-lysine (alginate-PLL) microbeads to specifically detect the presence of bacterial autoinducers. The PLL-reinforced microbeads were prepared using a two-step method involving ionic cross-linking and subsequent coating with thin layers of PLL. The alginate-PLL beads showed good stability in the presence of a known cation scavenger (sodium citrate), which typically limits the widespread applications of calcium alginate. In media containing synthetic autoinducers—such as N-(3-oxo dodecanoyl) homoserine lactone (3-oxo-C12-HSL) and N-butanoyl-L-homoserine lactone (C4-HSL), or the cell-free supernatants of planktonic or the flow-cell biofilm effluent of wild P. aeruginosa (PAO1)—the encapsulated bacteria enabled a dose-dependent detection of the presence of these QS molecules. The prepared bioreporter beads remained stable during prolonged storage at 4 and −80 °C and were ready for on-the-spot sensing without the need for recovery. The proof-of-concept, optical fiber-based, and whole-cell biosensor developed here demonstrates the practicality of the encapsulated bioreporter for bacterial detection based on specific QS molecules. Full article
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<p>Schematic of the cellular events that result in the expression of a reporter protein. The cell can easily take up a bioavailable analyte, such as AHL, through its membrane. AHL (3-oxo-C<sub>12</sub>-HSL and C<sub>4</sub>-HSL) binds with a regulatory protein called LasR or RhlR, forming a protein–AHL complex. This complex binds to its corresponding promoter, <span class="html-italic">Plasl</span> or <span class="html-italic">Prhl</span>, which triggers activation of the transcription and translation of a reporter gene called luxCDABE. This results in the expression of the reporter protein, luciferase, inducing the bioluminescent reaction characterized by the emission of blue-green light (~490 nm). Created with BioRender.com, accessed on 13 June 2024.</p>
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<p>Schematics of the microcapsule synthesis. The size of the beads can be controlled by changing the flow rate of the feed solution (alginate + bioreporter) and the air pressure.</p>
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<p>The basic components of the whole-cell, fiber-optic biosensors. (<b>A</b>) Optical fiber with a bioreporter immobilized unto the core. (<b>B</b>) Light–tight portable black box encasing all the biosensor components. For the image of the black box, readers are directed to the <a href="#app1-biosensors-14-00383" class="html-app">Supplementary Materials section (Figure S19)</a>.</p>
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<p>The ATR-FTIR absorbance spectra of the outer dehydrated alginate-PPL microcapsules. (<b>a</b>) The 1700–900 cm<sup>−1</sup> region of the spectra that corresponds to the asymmetric and symmetric stretching vibrations characteristics of the carboxyl (COO<sup>−1</sup>) functional group. (<b>b</b>) The full spectra of ca-alginate, alginate-PLL, and the characteristic peaks are discussed in the text. A spectrum of the alginate/PLL interpenetrating network and sodium alginate can be found in the <a href="#app1-biosensors-14-00383" class="html-app">Supplementary Materials section (Figure S5)</a>.</p>
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<p>The deconvoluted XPS spectrum peaks of the lyophilized alginate-poly-lysine beads. The deconvoluted peaks were assigned to a chemical group based on the binding energy of the peaks (N<sub>1s</sub>, O<sub>1s</sub>, C<sub>1s</sub>, and Ca<sub>2p</sub>), as shown in <a href="#app1-biosensors-14-00383" class="html-app">Figure S6</a>.</p>
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<p>Scanning electron microscopy (SEM) images of the outer part of the alginate and alginate-poly-lysine microbeads at different magnifications. (<b>A</b>) Alginate microbeads prior to the poly-lysine (PLL) coating. (<b>B</b>) Alginate-PLL microbeads. (<b>C</b>) The alginate/PLL interpenetrating network (IPN) prior to the PLL outer coating. (<b>D</b>) PLL-coated alginate/PLL IPN.</p>
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<p>Stability of alginate-poly-lysine microbeads in the presence of cation scavengers. (<b>A</b>) The alginate microbeads (control) were rapidly degraded within 60 min when incubated in 5% <span class="html-italic">w</span>/<span class="html-italic">v</span> sodium citrate because of the Ca<sup>2+</sup> removal from the hydrogels. (<b>B</b>) Alginate-PLL. (<b>C</b>) The alginate-PLL IPN capsules remained stable in a 5% sodium citrate solution after 14 h.</p>
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<p>Swelling properties. (<b>A</b>) beads stored in refrigerators (pristine), air-dried, and rehydrated (wet). (<b>B</b>) beads stored at −80 °C (pristine), air-dried and rehydrated (wet). (<b>C</b>) The physical appearance of the beads during wet, dried, and swelled conditions.</p>
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<p>The bioluminescent response of the immobilized RhlR in different C<sub>4</sub>-HSL concentrations. The insert in (<b>A</b>) illustrates the induction factor calculated using the maximum relative luminescence unit (RLU) derived from the spectral data. The induction factor is the ratio of the test’s maximum RLU conducted in the presence of an inducer to the maximum RLU obtained in the absence of added inducers. (<b>B</b>) Confocal images of the live/dead stained bacteria within alginate-PLL beads. (<b>C</b>) Both the luminescence and cell density (absorbance at 600 nm) of the LasR bioreporter. (<b>D</b>) The luminescence and OD<sub>600</sub> readings of the RhlR bioreporter. The OD<sub>600</sub>-normalized luminescence reading (RLU/OD<sub>600</sub>) can be found in <a href="#app1-biosensors-14-00383" class="html-app">Figure S8</a>.</p>
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<p>The bioluminescent responses of the PLL- and PDL-coated alginate were similar. The PDL and PLL coatings were compared regarding the bacteria’s response to the added synthetic (C<sub>4</sub>-HSL) and secreted (by the PAO1 wild strain of <span class="html-italic">P. aeruginosa</span>) autoinducers.</p>
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<p>The effect of pre-incubation and shaking before testing. (<b>A</b>) Bioluminescent response of the LasR strain. (<b>B</b>) Bioluminescent response of the RhlR strain. The stored microspheres were analyzed with or without pre-incubation to determine the effect of pre-incubation on the biosensor performance of the reporter bacteria strains. Experiments were conducted with 0, 15, 30, 60, 90, and 120 min of incubation and shaking at 37 °C and 220 rpm. Each curve represents the mean of four replicate experiments.</p>
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<p>Calibration curve of the RlhR bioreporter beads at various concentrations of C<sub>4</sub>-HSL. The <b>left panel</b> shows the bioluminescence (expressed as an induction factor) produced by the encapsulated reporter in the presence of increasing concentrations of exogenously added C<sub>4</sub>-HSL. The <b>right panel</b> shows the dose–response relationships inferred from the data in the left panel. Linear regression lines (bold) were drawn on logarithmic and linear (upper insert) scales, and the 95% confidence interval limits were the black dotted lines parallel to the regression lines. The equation and the <span class="html-italic">R</span><sup>2</sup> value for each regression line are shown. Data are the mean ± SD of three independent experiments.</p>
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<p>The bioreporter specificity test. The RhlR (<b>A</b>) and LasR (<b>B</b>) response toward 5 µM each of synthetic QS molecules, respectively. The second experiment was conducted with either 20 µL of cell-free supernatants of each Gram-negative bacterium such as Escherichia coli (<span class="html-italic">E. coli</span>), <span class="html-italic">Pseudomonas aeruginosa</span> (PAO1), and Acinetobacter baumannii (<span class="html-italic">A. baumannii</span>) (72 h biofilm set up), or 5 µM of C<sub>4</sub>-HSL for the RhlR strain (<b>C</b>) or 5 µM of 3-oxo-C<sub>12</sub>-HSL for the LasR strain (<b>D</b>).</p>
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<p>The QS inhibitory effect of furanone C-30 in the presence of synthetic AHLs. (<b>A</b>) The inhibition of RhlR signaling in the presence of 5 µM of C<sub>4</sub>-HSL and (<b>B</b>) the inhibition of the LasR bioluminescence system in the presence of 5 µM of 3-OC<sub>12</sub>-HSL. Luminescent readings were taken for 10 h, and the maximum relative light unit (RLU) was plotted. The results are the mean ± SD of biological triplicates.</p>
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<p>Storability of the bioreporter beads in refrigerator conditions. (<b>A</b>) RhlR and (<b>B</b>) LasR 2 µM inducers. The RhlR strain experienced a significant (shown as ** at <span class="html-italic">p</span> &lt; 0.05) reduction in activities between Days 7 and 50 and remained fairly constant thereafter. Comparison of the effect of storage at 4 and −80 degrees (for 30 days) on the luminescence. The residual activity of RhlR (<b>C</b>) and LasR (<b>D</b>) was compared after storage in the refrigerator and freezer at −80 °C for a minimum of 30 days. Two concentrations of each AHL were tested, and the results are reported as the mean ± SD, n = 4. Statistical analysis revealed no significant differences in the readings at <span class="html-italic">p</span> &lt; 0.05.</p>
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<p>Storage at room temperature. (<b>A</b>) RhlR and (<b>B</b>) LasR results. The results are presented as the mean ± SD, (n = 4). RT: beads stored dried at room temperature.</p>
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18 pages, 4956 KiB  
Article
An Exosome-Laden Hydrogel Wound Dressing That Can Be Point-of-Need Manufactured in Austere and Operational Environments
by E. Cate Wisdom, Andrew Lamont, Hannah Martinez, Michael Rockovich, Woojin Lee, Kristin H. Gilchrist, Vincent B. Ho and George J. Klarmann
Bioengineering 2024, 11(8), 804; https://doi.org/10.3390/bioengineering11080804 - 8 Aug 2024
Viewed by 397
Abstract
Skin wounds often form scar tissue during healing. Early intervention with tissue-engineered materials and cell therapies may promote scar-free healing. Exosomes and extracellular vesicles (EV) secreted by mesenchymal stromal cells (MSC) are believed to have high regenerative capacity. EV bioactivity is preserved after [...] Read more.
Skin wounds often form scar tissue during healing. Early intervention with tissue-engineered materials and cell therapies may promote scar-free healing. Exosomes and extracellular vesicles (EV) secreted by mesenchymal stromal cells (MSC) are believed to have high regenerative capacity. EV bioactivity is preserved after lyophilization and storage to enable use in remote and typically resource-constrained environments. We developed a bioprinted bandage containing reconstituted EVs that can be fabricated at the point-of-need. An alginate/carboxymethyl cellulose (CMC) biomaterial ink was prepared, and printability and mechanical properties were assessed with rheology and compression testing. Three-dimensional printed constructs were evaluated for Young’s modulus relative to infill density and crosslinking to yield material with stiffness suitable for use as a wound dressing. We purified EVs from human MSC-conditioned media and characterized them with nanoparticle tracking analysis and mass spectroscopy, which gave a peak size of 118 nm and identification of known EV proteins. Fluorescently labeled EVs were mixed to form bio-ink and bioprinted to characterize EV release. EV bandages were bioprinted on both a commercial laboratory bioprinter and a custom ruggedized 3D printer with bioprinting capabilities, and lyophilized EVs, biomaterial ink, and thermoplastic filament were deployed to an austere Arctic environment and bioprinted. This work demonstrates that EVs can be bioprinted with an alginate/CMC hydrogel and released over time when in contact with a skin-like substitute. The technology is suitable for operational medical applications, notably in resource-limited locations, including large-scale natural disasters, humanitarian crises, and combat zones. Full article
(This article belongs to the Section Biomedical Engineering and Biomaterials)
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<p>Isolation and characterization of EVs from MSC-conditioned media. (<b>A</b>) Schematic of EV isolation using size exclusion chromatography followed by lyophilization and characterization using mass spectrometry, NTA, and TEM (<b>B</b>). NTA of EVs collected showed a particle size peak of 118 nm with a concentration of 6.67 × 10<sup>9</sup> +/− 1.69 × 10<sup>7</sup> EVs/mL. Fresh EVs (<b>C</b>) and EVs following lyophilization (<b>D</b>) were imaged with TEM. Red arrows are pointing to the fresh (<b>C</b>) and lyophilized EVs (<b>D</b>) imaged with TEM.</p>
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<p>Rheology of alginate/CMC dressing biomaterial ink. A 0.05–100% shear strain sweep was performed at 23 °C on a parallel plate rheometer with a 0.5 mm gap and 1 Hz frequency (<b>A</b>). Storage modulus, G′ (black squares) and loss modulus, G″ (black triangles) and plotted. The storage modulus value was independent of shear strain up to approximately 1%, and G′ is greater than G″ indicating the biomaterial ink is a viscoelastic solid. (<b>B</b>) Viscosity study where biomaterial ink was loaded on a parallel plate rheometer with a 0.5 mm gap, 1 Hz frequency, and a ramp logarithmic program for shear rate was used from 0.005 to 200 s<sup>−1</sup>. The shear rate is plotted versus shear stress at 10 °C (blue triangles), 23 °C (black triangles), and 37 °C (red triangles). Increasing temperature decreased the viscosity. The biomaterial ink is non-Newtonian and shear thinning at each temperature. (<b>C</b>) Biomaterial ink yield stress determination at 23 °C. Samples were loaded on a parallel plate rheometer with a 0.5 mm gap. Shear stress was varied from 1 to 300 Pa using a ramp linear program. The yield stress was calculated using rheometer software.</p>
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<p>Print fidelity of alginate/CMC biomaterial ink at two different infill percentages before and after crosslinking with CaCl<sub>2</sub>. The bio-ink was 3D printed into a 20 × 20 × 3 mm object using a commercial bioprinter (BioX, Cellink). Print parameters were 6 mm/sec and up to 100 kPa pressure using a 22-gauge conical tip (<b>top row</b>). Infill was either 20% or 10%. Following printing, the prints were incubated in CaCl<sub>2</sub> for 60 min to crosslink the alginate component (<b>bottom row</b>).</p>
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<p>Printed Alginate/CMC hydrogel dressings with varying crosslinking times. Hydrogel dressings were printed with 20% infill and crosslinked in CaCl<sub>2</sub> for 5, 15, or 60 min.</p>
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<p>Mechanical testing of the printed bandage dressing squares. (<b>A</b>) Linear portion of example stress–strain curves for samples with 20% infill crosslinked for 5 min, R = 0.99 (Black Diamonds), 15 min, R = 0.99 (Grey Squares) or 60 min, R = 0.99 (Black Circles). The data were fit to linear regression, and the slope of the curve fit is Young’s modulus. (<b>B</b>) Maximum force at 10% strain and Young’s modulus of printed alginate/CMC hydrogel dressings after 5, 15, and 60 min of crosslinking in CaCl<sub>2</sub>.</p>
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<p>Bioprinted alginate/CMC dressing with reconstituted, red fluorescently labeled EVs. The bioactive dressing was bioprinted with 20% infill and imaged before crosslinking (<b>A</b>) and after crosslinking (<b>B</b>). A confocal microscopy z-stack, tile scan at 20X magnification visualized as a 3D projection of the red-boxed region of the alginate/CMC/EV dressing (inset) (<b>C</b>). The labeled EVs are distributed throughout the hydrogel dressing material.</p>
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<p>Transfer of EVs from dressing bio-ink to collagen blocks. (<b>A</b>) A 3D-printed collagen block was used to simulate skin to test the transfer of EVs from the printed dressing to the skin. The alginate/CMC dressing was printed using 20% infill, crosslinked, and cut to 10 mm × 10 mm × 3 mm. It was placed on top of a similar-sized collagen block and incubated at 37 °C in a 6-well plate with 1 mL of PBS to keep the collagen hydrated. (<b>B</b>) Positive control: a solution of fluorescently labeled EVs pipetted on top of the collagen and left to absorb. The collagen block was removed at 24 h and imaged for the appearance of labeled EVs transferred from the dressings that were crosslinked for (<b>C</b>) 10 min or (<b>D</b>) 60 min. Microscopy images taken at 20X magnification.</p>
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<p>Three-dimensional printing and bioprinting of a wound dressing in a laboratory environment using a ruggedized 3D printer. The alginate/CMC dressing was bioprinted onto an FFF 3D printed PLA backing and crosslinked with CaCl<sub>2</sub> solution for 10 min.</p>
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<p>(<b>A</b>) CAD rendering and (<b>B</b>) bioprinted bandage with alginate/CMC EV-laden bio-ink dressing.</p>
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<p>Ruggedized 3D printer for point-of-need manufacturing of a bioactive wound dressing. The 3D printer contained three printheads. A fused filament fabrication (FFF) printhead was used to print the PLA thermoplastic backing. Two pneumatic printheads were used to print the alginate/EV bioactive bio-ink and a commercially available adhesive.</p>
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20 pages, 5733 KiB  
Article
Optimization of Preparation Process for Chitosan-Coated Pomelo Peel Flavonoid Microcapsules and Its Effect on Waterborne Paint Film Properties
by Jinzhe Deng, Tingting Ding and Xiaoxing Yan
Coatings 2024, 14(8), 1003; https://doi.org/10.3390/coatings14081003 - 8 Aug 2024
Viewed by 314
Abstract
In order to prepare chitosan-coated pomelo peel flavonoid microcapsules with antibacterial properties, chitosan was used as the wall material for the purpose of coating the core material, pomelo peel flavonoids. The pH of the microcapsule crosslinking reaction was 7.5, the mass ratio of [...] Read more.
In order to prepare chitosan-coated pomelo peel flavonoid microcapsules with antibacterial properties, chitosan was used as the wall material for the purpose of coating the core material, pomelo peel flavonoids. The pH of the microcapsule crosslinking reaction was 7.5, the mass ratio of the microcapsule core material to the wall material was 1:1, and the concentration of the emulsifier was 1%. The microcapsules obtained under these preparation conditions exhibited superior performance, morphology, and dispersion. Additionally, the yield and coating rates were recorded at 22% and 50%, respectively. To prepare the paint film, the microcapsules were added into the coatings at varying concentrations of 0%, 3.0%, 6.0%, 9.0%, 12.0%, and 15.0%. The antibacterial efficacy of the paint film for both bacteria was progressively enhanced with the incorporation of microcapsules. The antibacterial efficacy against Staphylococcus aureus was observed to be higher than that against Escherichia coli. As the content of microcapsules increased, the color difference in the paint film increased, the gloss loss rate increased, and the light transmission rate reduced. The tensile property and elongation at break reduced, and the roughness increased. At a microcapsule content of 6.0%, the paint film exhibited superior overall performance, with an antibacterial efficacy against Escherichia coli and Staphylococcus aureus of 46.3% and 56.7%, respectively. The color difference was 38.58. The gloss loss rate was 41.0%, the light transmission rate was 90.4%, and the paint film exhibited a large elastic region, with an elongation at break of 21.5% and a roughness of 1.46 μm. Full article
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<p>Macroscopic morphology: (<b>A</b>) pomelo peel flavonoids for core material, (<b>B</b>) chitosan for wall material, and (<b>C</b>) microcapsules (sample 7).</p>
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<p>OM images of the microcapsules: (<b>A</b>–<b>D</b>) samples 1–4.</p>
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<p>SEM images of one-factor microcapsules: (<b>A</b>–<b>E</b>) samples 5–9.</p>
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<p>Particle size distribution: (<b>A</b>–<b>D</b>) sample 6–9.</p>
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<p>FTIR images of chitosan, pomelo peel flavonoids, and microcapsule sample 7.</p>
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<p>Macroscopic morphology of the paint films with different contents of microcapsules: (<b>A</b>) without microcapsules, (<b>B</b>) with 3.0% microcapsules, (<b>C</b>) with 6.0% microcapsules, (<b>D</b>) with 9.0% microcapsules, (<b>E</b>) with 12.0% microcapsules, and (<b>F</b>) with 15.0% microcapsules.</p>
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<p>SEM images of paint films with different microcapsule contents: (<b>A</b>) with 3.0% microcapsules, (<b>B</b>) with 6.0% microcapsules, (<b>C</b>) with 9.0% microcapsules, and (<b>D</b>) with 12.0% microcapsules.</p>
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<p>FTIR image of the paint films with and without microcapsules.</p>
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<p>The antibacterial rate of paint films with different microcapsule contents.</p>
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<p>Visible light transmittance.</p>
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<p>The tensile properties.</p>
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16 pages, 8867 KiB  
Article
Structural, Thermal and Mechanical Assessment of Green Compounds with Natural Rubber
by Xavier Colom, Jordi Sans, Frederic de Bruijn, Fernando Carrillo and Javier Cañavate
Macromol 2024, 4(3), 566-581; https://doi.org/10.3390/macromol4030034 - 7 Aug 2024
Viewed by 196
Abstract
The inadequate disposal of tires poses a significant threat to human health and requires effective recycling solutions. The crosslinked structure of rubber, formed through sulfur bridges during vulcanization, presents a major challenge for recycling because it prevents the rubber scraps from being reshaped [...] Read more.
The inadequate disposal of tires poses a significant threat to human health and requires effective recycling solutions. The crosslinked structure of rubber, formed through sulfur bridges during vulcanization, presents a major challenge for recycling because it prevents the rubber scraps from being reshaped thermoplastically. Reclaiming or devulcanization aims to reverse this crosslinking, allowing waste rubber to be transformed into products that can be reprocessed and revulcanized, thereby saving costs and preserving resources. Microwave technology shows promise for devulcanization due to its ability to break sulfur crosslinks. In this study, we investigate the devulcanization of ground tire rubber (GTR) through a combined process applied to samples from both car and truck tires subjected to varying periods of microwave irradiation (0, 3, 5 and 10 min). The devulcanized GTR was then blended with natural rubber (NR) and underwent a new vulcanization process, simulating recycling for novel applications. The GTR was mixed with NR in proportions of 0, 10, 30 and 50 parts per hundred rubber (phr). This study also examines the differences between the GTR from car tires and GTR from truck tires. The results showed that the treatment effectively breaks the crosslinks in the GTR, creating double bonds (C=C) and improving the mechanical properties of the revulcanized samples. The crosslinking density and related properties of the samples increased with treatment time, reaching a maximum at 5 min of microwave treatment, followed by a decrease at 10 min. Additionally, the incorporation of GTR enhanced the thermal stability of the resulting materials. Full article
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<p>Stress–strain curves for NR vulcanizates with different amounts (0,10, 30 and 50 phr) of non-devulcanized GTRcar (GTRc).</p>
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<p>Stress–strain curves for NR vulcanizates with different amounts (0,10, 30 and 50 phr) of non-devulcanized GTRtruck (GTRt).</p>
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<p>Tensile properties of NR/GTRcar compounds.</p>
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<p>Tensile properties of NR/GTRtruck compounds.</p>
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<p>Hardness average values of different samples.</p>
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<p>(<b>a</b>) Apparent crosslink density of GTRcar vulcanizate samples (µmol/cm<sup>3</sup>); (<b>b</b>) percentage (%) of mono-, di- and polysulfidic bonds correlated with apparent CLD for non-treated (NT) and TMmW5 compounds.</p>
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<p>(<b>a</b>) Apparent crosslink density of GTRtruck vulcanizate samples (µmol/cm<sup>3</sup>); (<b>b</b>) percentage (%) of mono-, di- and polysulfidic bonds correlated apparent CLD for non-treated (NT) and TMmW5 compounds.</p>
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<p>Spectral area of 100NR with 50 phr GTRcar devulcanized by microwaves for different periods of time: (<b>a</b>) NR, (<b>b</b>) 50GTRc(NT)/NR, (<b>c</b>) 50GTRc(TMmW3)/NR, (<b>d</b>) 50GTRc(TMmW5)/NR and (<b>e</b>) 50GTRc(TMmW10)/NR.</p>
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<p>Spectral area of 100NR with 50 phr GTRtruck devulcanized by microwaves for different periods of time: (<b>a</b>) NR, (<b>b</b>) 50GTRt(NT)/NR, (<b>c</b>) 50GTRt(TMmW3)/NR, (<b>d</b>) 50GTRt(TMmW5)/NR and (<b>e</b>) 50GTRt(TMmW10)/NR.</p>
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<p>SEM pictures of crystal morphology of ZnSt<sub>2</sub> on 0GTRc(NT)/NR surface: (<b>a</b>) (×500) and (<b>b</b>) (×8000).</p>
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<p>TGA and DTG curves of 100NR, 100NR10GTRc, 100NR30GTRc and 100NR50GTRc. All the samples have been treated for 10′ with microwaves.</p>
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<p>TGA and DTG curves of 100NR, 100NR10GTRt, 100NR30GTRt and 100NR50GTRt. All the samples have been treated for 10′ with microwaves.</p>
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<p>SEM microphotographs of the tensile fracture surface of the composites: (<b>A1</b>) natural rubber (×500); (<b>A2</b>) natural rubber (×50); (<b>B</b>) NR50GTRc(NT); (<b>C</b>) NR50GTRc10; (<b>D</b>) NR50GTRt(NT); (<b>E</b>) NR50GTRc10.</p>
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13 pages, 537 KiB  
Article
The Influence of Arabinoxylan of Different Molar Masses on the Properties of Rye Bread Baked by the Postponed Baking Method
by Angelika Bieniek and Krzysztof Buksa
Foods 2024, 13(16), 2482; https://doi.org/10.3390/foods13162482 - 7 Aug 2024
Viewed by 266
Abstract
Rye grain is a good source of dietary fiber, phenolic compounds, vitamins, and mineral compounds. To prevent the staling process of bread, semi-finished bakery products are subjected to cooling or freezing, and this process is called the postponed baking method. The aim of [...] Read more.
Rye grain is a good source of dietary fiber, phenolic compounds, vitamins, and mineral compounds. To prevent the staling process of bread, semi-finished bakery products are subjected to cooling or freezing, and this process is called the postponed baking method. The aim of this study was to examine the influence of rye arabinoxylans differing in molar mass on the properties of rye bread baked using the postponed baking method. The breads were baked from rye flour types 720 and 1150, without and with a 1% share of unmodified or cross-linked rye arabinoxylans (AXs). The molar mass of the unmodified AXs was 432,160 g/mol, while that of the AXs after cross-linking was 1,158,980 g/mol. The results of this study show that the 1% share of AXs significantly increased the water addition to both types of rye flour and dough yield, and this increase was proportional to the molar mass of the AXs used. It is shown that a 1% share of both AX preparations positively increased the volume and crumb moisture of bread baked by the postponed baking method. Cross-linked AXs proved to be particularly effective in increasing the volume and bread crumb moisture. Both AX preparations had a positive effect on reducing the bread crumb hardness of rye breads baked by the postponed baking method. Full article
(This article belongs to the Section Grain)
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<p>Molecular mass distribution profiles of native LP_NM (-●-) and cross-linked LP_CR (-○-) water-soluble arabinoxylan.</p>
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