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Keywords = poly (vinyl alcohol)

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22 pages, 6407 KiB  
Article
(Ligno)Cellulose Nanofibrils and Tannic Acid as Green Fillers for the Production of Poly(vinyl alcohol) Biocomposite Films
by Urša Osolnik, Viljem Vek, Miha Humar, Primož Oven and Ida Poljanšek
Polymers 2025, 17(1), 16; https://doi.org/10.3390/polym17010016 - 25 Dec 2024
Viewed by 27
Abstract
This study compared the use of cellulose nanofibrils (CNF) and lignocellulose nanofibrils (LCNF) in different concentrations to reinforce the poly(vinyl alcohol) (PVA) matrix. Both nanofillers significantly improved the elastic modulus and tensile strength of PVA biocomposite films. The optimum concentration of CNF and [...] Read more.
This study compared the use of cellulose nanofibrils (CNF) and lignocellulose nanofibrils (LCNF) in different concentrations to reinforce the poly(vinyl alcohol) (PVA) matrix. Both nanofillers significantly improved the elastic modulus and tensile strength of PVA biocomposite films. The optimum concentration of CNF and LCNF was 6% relative to PVA, which improved the tensile strength of the final PVA biocomposite with CNF and LCNF by 53% and 39%, respectively, compared to the neat PVA film. The addition of LCNF resulted in more elastic films than the addition of CNF to the PVA matrix. The elongation at break of the PVA biocomposite with 2% of LCNF was more than 100% higher than that of the neat PVA film. The integration of tannic acid (TA) into the PVA-LCNF system resulted in antioxidant-active and more water-resistant PVA biocomposites. The three-component biocomposite films with 2 and 6% LCNF and 10% TA exhibited a more than 20° higher contact angle of the water droplet on the surfaces of the biocomposite films and absorbed more than 50% less water than the neat PVA film. New formulations of biocomposite films have been developed with the addition of LCNF and TA in a polymeric PVA matrix. Full article
(This article belongs to the Special Issue Functional Polymers and Their Composites for Sustainable Development)
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Graphical abstract

Graphical abstract
Full article ">Figure 1
<p>Thickness of PVA (black), PVA-CNF (blue), PVA-CNF-TA (red), PVA-LCNF (orange) and PVA-LCNF-TA (green) composite films (ANOVA, <span class="html-italic">p</span> &lt; 0.0001).</p>
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<p>FE-SEM images of LCNF film—(<b>a</b>,<b>b</b>) and of freeze-dried LCNFs—(<b>c</b>,<b>d</b>).</p>
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<p>FE-SEM images of P6LCNF before the tensile test—(<b>a</b>–<b>c</b>) and after the tensile test—(<b>d</b>–<b>f</b>).</p>
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<p>FE-SEM images of P2LCNF10T before the tensile test—(<b>a</b>–<b>c</b>) and after the tensile test—(<b>d</b>–<b>f</b>).</p>
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<p>FTIR spectra of CNFs and LCNFs.</p>
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<p>FTIR spectra of the PVA reference film (P) and PVA biocomposite films over the whole spectral range—(<b>a</b>) and in the spectral range from 1400 to 1050 cm<sup>−1</sup>—(<b>b</b>).</p>
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<p>Average stress–strain curves for the PVA reference film and two-component PVA-CNF films—(<b>a</b>) and two-component PVA-LCNF films—(<b>b</b>).</p>
Full article ">Figure 7 Cont.
<p>Average stress–strain curves for the PVA reference film and two-component PVA-CNF films—(<b>a</b>) and two-component PVA-LCNF films—(<b>b</b>).</p>
Full article ">Figure 8
<p>Average stress–strain curves for the PVA reference film and three-component PVA-LCNF-TA films—(<b>a</b>) and for the PVA reference film and PVA biocomposite films with CNF or LCNF and TA—(<b>b</b>).</p>
Full article ">Figure 8 Cont.
<p>Average stress–strain curves for the PVA reference film and three-component PVA-LCNF-TA films—(<b>a</b>) and for the PVA reference film and PVA biocomposite films with CNF or LCNF and TA—(<b>b</b>).</p>
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<p>Contact angle over time (0–60 s) for the PVA reference film (grey) and PVA biocomposite films with CNFs (blue) and with both CNFs and TA (red) (ANOVA, <span class="html-italic">p</span> &lt; 0.0001).</p>
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<p>Contact angle over time (0–60 s) for the PVA reference film (grey) and PVA biocomposite films with LCNFs (orange) and with both LCNFs and TA (green) (ANOVA, <span class="html-italic">p</span> &lt; 0.0001).</p>
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<p>Water uptake for the PVA reference film (grey) and PVA biocomposite films with LCNFs (orange) and with both LCNFs and TA (green) after 1 h of soaking films in water (ANOVA, <span class="html-italic">p</span> &lt; 0.0001).</p>
Full article ">
20 pages, 8056 KiB  
Article
Methyl Gallate and Amoxicillin-Loaded Electrospun Poly(vinyl alcohol)/Chitosan Mats: Impact of Acetic Acid on Their Anti-Staphylococcus aureus Activity
by Pimsumon Jiamboonsri, Weradesh Sangkhun and Sompit Wanwong
Polymers 2025, 17(1), 7; https://doi.org/10.3390/polym17010007 - 24 Dec 2024
Viewed by 18
Abstract
Methyl gallate (MG), a natural phenolic compound, exhibits in vitro synergistic activity with amoxicillin (Amox) against methicillin-resistant Staphylococcus aureus (MRSA), a global health concern. This study developed electrospun nanofibers incorporating MG and Amox into a poly(vinyl alcohol) (PVA)/chitosan (CS) blend to target both [...] Read more.
Methyl gallate (MG), a natural phenolic compound, exhibits in vitro synergistic activity with amoxicillin (Amox) against methicillin-resistant Staphylococcus aureus (MRSA), a global health concern. This study developed electrospun nanofibers incorporating MG and Amox into a poly(vinyl alcohol) (PVA)/chitosan (CS) blend to target both methicillin-susceptible S. aureus (MSSA) and MRSA. The formulation was optimized, and the impact of acetic acid on antibacterial activity was evaluated using agar disc diffusion. The final formulation was fabricated and characterized using SEM, FTIR, DSC, swelling, and release behavior analyses to understand its antibacterial efficacy. Results revealed that acetic acid eliminated antibacterial activity, but MG (64 mg/mL) and Amox (2.5 mg/mL) were successfully incorporated into a PVA/CS solution prepared with deionized water. The resulting nanofiber mats featured nanoscale fibers (126 ± 45 nm) with and micron-oval beads. Despite the in vitro synergism, the MG/Amox/PVA/CS mats showed no significant improvement over MG or Amox alone against MRSA, likely due to their physicochemical properties. FTIR and DSC results confirmed molecular interactions between the active compounds and the polymer matrix, which may cause a minimal swelling and low drug release at 24 h. This study offers insights into the potential of MG/Amox-loaded nanofibers for anti-MRSA material development. Full article
(This article belongs to the Special Issue Preparation of Polymer Materials via Electrospinning Technology)
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Figure 1

Figure 1
<p>Schematic illustrations showing the electrospinning method to fabricate MG/Amox/PVA/CS nanofibers.</p>
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<p>(<b>a</b>) Images of the electrospun nanofiber mat fabricated under optimization conditions with acetic acid conditions (formulation set A) and (<b>b</b>) their antibacterial activities compared with neat PVA and PVA/CS against <span class="html-italic">S. aureus</span> ATCC 25923 (MSSA) and 43300 (MRSA). Each symbol indicates the mean ± S.D. (<span class="html-italic">n</span> = 3). # The inhibition zone could not be determined. * Denotes a significant difference between the mean inhibition zones of the two bacterial strains (<span class="html-italic">p</span> &lt; 0.05).</p>
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<p>(<b>a</b>) Images of the electrospun nanofiber mat fabricated under optimization conditions without acetic acid conditions (formulation set B) and (<b>b</b>) their antibacterial activities compared with neat PVA/CS against <span class="html-italic">S. aureus</span> ATCC 25923 (MSSA) and 43300 (MRSA). Each symbol indicates the mean ± S.D. (<span class="html-italic">n</span> = 3). # The inhibition zone could not be determined. ## A large and overlapping inhibition zone was observed.</p>
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<p>(<b>a</b>) Images of the electrospun nanofiber mat and (<b>b</b>) the antibacterial activities of the formulation set C; 64 mg MG/PVA/CS, 25 mg Amox/PVA/CS, and 64 mg MG/25 mg Amox/PVA/CS nanofiber mats, compared with neat PVA and PVA/CS against <span class="html-italic">S. aureus</span> ATCC 25923 (MSSA) and 43300 (MRSA). Each symbol indicates the mean ± S.D. (<span class="html-italic">n</span> = 3). # The inhibition zone could not be determined. * Significant difference between the mean inhibition zones of the two bacterial strains, <span class="html-italic">p</span> &lt; 0.05.</p>
Full article ">Figure 5
<p>SEM images of fabricated mats from formulation set C: (<b>a</b>) PVA, (<b>b</b>) PVA/CS, (<b>c</b>) MG/PVA/CS, (<b>d</b>) Amox/PVA/CS, and (<b>e</b>) MG/Amox/PVA/CS.</p>
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<p>FTIR spectra of PVA, PVA/CS, MG/PVA/CS, Amox/PVA/CS, and MG/Amox/PVA/CS nanofibers from formulation set C.</p>
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<p>DSC thermograms of PVA, PVA/CS, MG/PVA/CS Amox/PVA/CS, and MG/Amox/PVA/CS nanofibers from formulation set C (heating rate 5 °C/min).</p>
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<p>Percentage of swelling degree, weight loss, and water retention of PVA, PVA/CS, MG/PVA/CS, Amox/PVA/CS, and MG/Amox/PVA/CS nanofiber from formulation set C. Data shown as mean ± S.D. (<span class="html-italic">n</span> = 3).</p>
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<p>The 24 h percentage release of MG and Amox from PVA/CS electrospun (formulation set C). Data shown as mean ± S.D. (<span class="html-italic">n</span> = 3). # The concentration of MG and Amox could not be determined.</p>
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11 pages, 4314 KiB  
Article
Microwave-Assisted Extraction of Cellulose from Aloe Vera Plant Residue and Preparation of Cellulose Nanocrystal–Poly(vinyl alcohol) Hydrogels
by Eleni Triantafyllou, Andreas Karydis-Messinis, Dimitrios Moschovas, Christina Kyriakaki, Konstantinos C. Vasilopoulos, Aris E. Giannakas, Michael A. Karakassides, Apostolos Avgeropoulos, Nikolaos E. Zafeiropoulos and Constantinos E. Salmas
Molecules 2024, 29(24), 6012; https://doi.org/10.3390/molecules29246012 - 20 Dec 2024
Viewed by 312
Abstract
Biomass valorization and bio-based material development are of major research interest following the spirit of the circular economy. Aloe vera cultivation is a widespread agricultural activity oriented toward supplement production because of its well-known antioxidant and antimicrobial properties. Aloe vera juice production also [...] Read more.
Biomass valorization and bio-based material development are of major research interest following the spirit of the circular economy. Aloe vera cultivation is a widespread agricultural activity oriented toward supplement production because of its well-known antioxidant and antimicrobial properties. Aloe vera juice production also produces a large amount of biomass byproducts that are usually landfilled. On the other hand, cellulose nanocrystals are widely used in several applications, such as biomaterials, bio-compatible polymers, nanocomposites, food packaging, medicines, cosmetics, and sensors, due to their unique physical, mechanical, optical, electrical, and healing properties as well as their compatibility with biological tissues. This study introduces a novel approach combining the microwave-assisted extraction (MAE) of cellulose from this residue with the subsequent isolation of cellulose nanocrystals (CNCs). The MAE process, which exhibits a rapid heating and penetrating ability, was optimized to maximize the cellulose yield under various conditions (microwave power, solvent ratio, and time). Analysis using FTIR, XRD, SEM, and DMA indicated that isolated pure cellulose nanocrystals and a stable PVA–CNC porous hydrogel network were produced. The PVA–CNC hydrogel was synthesized to enable the formation of a semi-crystalline network that imparts the material with enhanced mechanical properties. Both final products of this study could potentially be used for various applications. Full article
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Figure 1

Figure 1
<p>FTIR spectra of (<b>a</b>) pure aloe vera leaves and extracted cellulose and (<b>b</b>) pure PVA powder and (<b>c</b>) CNC–PVA hydrogel.</p>
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<p>XRD diffractograms of (<b>a</b>) pure aloe vera leaves and extracted cellulose, (<b>b</b>) CNCs, and (<b>c</b>) the CNC–PVA hydrogel.</p>
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<p>SEM images of (<b>a</b>) pure aloe vera leaves, (<b>b</b>) extracted cellulose, and (<b>c</b>) isolated CNCs.</p>
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<p>SEM images of the CNC–PVA hydrogel, (<b>a</b>) sponge morphology and (<b>b</b>) interconnected porous system.</p>
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<p>Dynamic mechanical analysis of the CNC–PVA hydrogel, (<b>a</b>) Storage and Loss Modulus and (<b>b</b>) Tan delta are plotted as function of Frequency.</p>
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<p>Schematic illustration of cellulose extraction.</p>
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<p>Schematic illustration of cellulose nanocrystal isolation.</p>
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<p>Schematic illustration of CNC–PVA hydrogel preparation.</p>
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15 pages, 4107 KiB  
Article
A Spectral Method for Rapidly Determining the Linear Birefringence of Thin Polymer Films
by Dana Ortansa Dorohoi and Dan Gheorghe Dimitriu
Molecules 2024, 29(24), 6007; https://doi.org/10.3390/molecules29246007 - 20 Dec 2024
Viewed by 297
Abstract
A rapid and simple spectral method for determining the linear birefringence of thin anisotropic films, using the channeled spectra, is proposed in this article. Two channeled spectra must be recorded for a transparent system containing a thick anisotropic layer and a thin stretched [...] Read more.
A rapid and simple spectral method for determining the linear birefringence of thin anisotropic films, using the channeled spectra, is proposed in this article. Two channeled spectra must be recorded for a transparent system containing a thick anisotropic layer and a thin stretched polymer film, when the two anisotropic uniaxial layers have parallel and perpendicular optical axes, respectively. The sum and difference of the two channeled spectra indicate (by the positions of the maxima and minima in the resulting channeled spectra) the phase difference introduced by the thin polymer film. One must measure with precision only the thickness of the polymer film in order to compute the linear birefringence of the thin polymer film, using the position of the maxima and minima of the sum and difference. The experimental data obtained for poly (vinyl alcohol)—PVA—and poly (ethylene terephthalate)—PET—films attest to the applicability of the proposed method to the uniaxial transparent polymeric thin films. Full article
(This article belongs to the Special Issue Macromolecular Chemistry in Europe)
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Figure 1

Figure 1
<p>Device D for channeled spectra recording. P and A, identical polarizing filters with crossed transmission directions; C, thick crystalline layer; AL, anisotropic thin layer. The arrows drawn on the polarizers P and A represent their transmission directions, while the arrow drawn on the anisotropic layer AL represents its optical axis.</p>
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<p>Relative orientation of the transmission directions of polarizers P and A and the main axes O<span class="html-italic">a</span> and O<span class="html-italic">c</span> of the anisotropic layers. Light propagates along O<span class="html-italic">b</span>.</p>
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<p>Channeled spectrum of crystalline layer C (<span class="html-italic">L</span><sub>1</sub> = 1 mm = 10<sup>−3</sup> m, Δ<span class="html-italic">n</span> = 0.0092).</p>
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<p>Channeled spectrum of PVA film (<span class="html-italic">L</span><sub>2</sub> = 10<sup>−1</sup> mm = 10<sup>−4</sup> m).</p>
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<p>Channeled spectrum for crystalline layer C and PVA polymer film when their optical axes are parallel.</p>
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<p>Channeled spectrum for crystalline layer C and PVA polymer film when their optical axes are perpendicular.</p>
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<p>Sum <span class="html-italic">T</span><sub>+</sub> of the channeled spectra from <a href="#molecules-29-06007-f005" class="html-fig">Figure 5</a> and <a href="#molecules-29-06007-f006" class="html-fig">Figure 6</a>.</p>
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<p>Difference <span class="html-italic">T</span><sub>−</sub> of the channeled spectra from <a href="#molecules-29-06007-f005" class="html-fig">Figure 5</a> and <a href="#molecules-29-06007-f006" class="html-fig">Figure 6</a>.</p>
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<p>Channeled spectrum of PET film (<span class="html-italic">L</span><sub>2</sub> = 17.2 μm; <span class="html-italic">γ</span> = 2.4).</p>
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<p>Sum of the channeled spectra <span class="html-italic">T<sub>o</sub></span> and <span class="html-italic">T<sub>p</sub></span> recorded for PET thin film.</p>
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<p>Difference of the channeled spectra <span class="html-italic">T<sub>p</sub></span> and <span class="html-italic">T<sub>o</sub></span> recorded for PET thin film.</p>
Full article ">
17 pages, 2503 KiB  
Article
Preparation and Characterization of Poly(vinyl-alcohol)/Chitosan Polymer Blend Films Chemically Crosslinked with Glutaraldehyde: Mechanical and Thermal Investigations
by Daniel Pugar, Tatjana Haramina, Mirela Leskovac and Lidija Ćurković
Molecules 2024, 29(24), 5914; https://doi.org/10.3390/molecules29245914 - 14 Dec 2024
Viewed by 490
Abstract
In this study, poly(vinyl-alcohol) (PVA)/chitosan (CS) polymer blend films with different amounts of CS (0, 5, 20 and 35 wt. %) crosslinked by glutaraldehyde (GA) were prepared. The structure and properties of the prepared polymer films were studied by means of dynamic mechanical [...] Read more.
In this study, poly(vinyl-alcohol) (PVA)/chitosan (CS) polymer blend films with different amounts of CS (0, 5, 20 and 35 wt. %) crosslinked by glutaraldehyde (GA) were prepared. The structure and properties of the prepared polymer films were studied by means of dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and the time-lag permeation technique. The DMA analysis showed that CS reduces the crystallinity degree of PVA, leading to a higher amount of the amorphous phase contributing to the α relaxation that corresponds to the glass-to-rubber transition. However, the mobility of the amorphous phase can be restricted with crosslinking with 1 wt. % GA. Interaction between the PVA and the CS was confirmed by DCS analysis. Additionally, the influence of the CS and crosslinking on the permeation of nitrogen molecules was investigated. The permeation was examined by the time-lag method. It was found that the addition of CS and GA to PVA improves barrier properties. Full article
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Figure 1

Figure 1
<p>Temperature dependence of tan <span class="html-italic">δ</span> for PVA films with 0 wt. % (PVA), wt. % (CS1), 20 wt. % (CS2), and 35 wt. % (CS3) of CS.</p>
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<p>Storage modulus <span class="html-italic">E</span>′ vs. temperature for PVA films with 0 wt. % (PVA), wt. % (CS1), 20 wt. % (CS2), and 35 wt. % (CS3) of CS.</p>
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<p>Damping factor tan <span class="html-italic">δ</span> as a function of temperature for crosslinked and non-crosslinked PVA films with the following mass fractions of CS: (<b>a</b>) 0 wt. %, (<b>b</b>) 5 wt. %, (<b>c</b>) 20 wt. %, (<b>d</b>) 35 wt. %.</p>
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<p>Storage modulus <span class="html-italic">E</span>′ as a function of temperature of crosslinked and non-crosslinked PVA films with different amounts of CS: (<b>a</b>) 0 wt. %, (<b>b</b>) 5 wt. %, (<b>c</b>) 20 wt. %, (<b>d</b>) 35 wt. %.</p>
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<p>DMA spectra of pure PVA, PVA with 20 wt. % of CS (CS2) and crosslinked PVA with 20 wt. % of CS (CS2/GA); (<b>a</b>) damping factor tan <span class="html-italic">δ</span> and (<b>b</b>) storage modulus <span class="html-italic">E</span>′ depending on temperature.</p>
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<p>DSC thermograms of PVA/CS blends crosslinked with glutaraldehyde and with different amounts of CS: 0 wt. % (PVA), 5 wt. % (CS1), 20 wt. % (CS2), and 35 wt. % (CS3).</p>
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<p>Melting enthalpy of PVA/CS blends.</p>
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<p>Results of permeability measurements for PVA films with different amounts of CS: 0 wt. % (PVA), 5 wt. % (CS1), 20 wt. % (CS2), and 35 wt. % (CS3).</p>
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<p>Influence of CS on the permeability of PVA films; data are representative of the results of repeated experiments (n = 3) and expressed as the mean value.</p>
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<p>Influence of crosslinking on the permeability of PVA films with 0, 5, 20, and 35 wt. % amount of CS; data are representative of the results of repeated experiments (n = 3) and expressed as the mean value.</p>
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16 pages, 3434 KiB  
Article
Dynamic Double-Networked Hydrogels by Hybridizing PVA and Herbal Polysaccharides: Improved Mechanical Properties and Selective Antibacterial Activity
by Weidong Liu, Chuying Yao, Daohang Wang, Guangyan Du, Yutian Ji and Quan Li
Gels 2024, 10(12), 821; https://doi.org/10.3390/gels10120821 - 13 Dec 2024
Viewed by 364
Abstract
Chinese herbal medicine has offered an enormous source for developing novel bio-soft materials. In this research, the natural polysaccharide isolated from the Chinese herbal medicine Dendrobium was employed as the secondary building block to fabricate a “hybrid” hydrogel with synthetic poly (vinyl alcohol) [...] Read more.
Chinese herbal medicine has offered an enormous source for developing novel bio-soft materials. In this research, the natural polysaccharide isolated from the Chinese herbal medicine Dendrobium was employed as the secondary building block to fabricate a “hybrid” hydrogel with synthetic poly (vinyl alcohol) (PVA) polymers. Thanks to the presence of mannose units that contain cis-diol motifs on the chain of the Dendrobium polysaccharides, efficient crosslinking with the borax is allowed and reversible covalent borate ester bonds are formed. Eventually, highly dynamic and double-networked hydrogels were successfully prepared by the integration of Dendrobium polysaccharides and PVA. Interestingly, the introduction of polysaccharides has given rise to more robust and dynamic hydrogel networks, leading to enhanced thermal stability, mechanical strength, and tensile capacity (>1000%) as well as the rapid self-healing ability (<5 s) of the “hybrid” hydrogels compared with the PVA/borax single networked hydrogel. Moreover, the polysaccharides/PVA double network hydrogel showed selective antibacterial activity towards S. aureus. The reported polysaccharides/PVA double networked hydrogel would provide a scaffold to hybridize bioactive natural polysaccharides and synthetic polymers for developing robust but dynamic multiple networked hydrogels that are tailorable for biomedical applications. Full article
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Graphical abstract

Graphical abstract
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<p>(<b>a</b>) FT−IR spectra, (<b>b</b>) XRD patterns, (<b>c</b>) TG, (<b>d</b>) DTG curves of P<sub>30</sub>B<sub>50</sub>, P<sub>30</sub>B<sub>50</sub>D<sub>1</sub>, and P<sub>30</sub>B<sub>50</sub>D<sub>5</sub> hydrogels and their compositions. All the samples were freeze-dried before the measurement.</p>
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<p>(<b>a</b>–<b>c</b>) SEM images of P<sub>30</sub>B<sub>50</sub>, P<sub>30</sub>B<sub>50</sub>D<sub>1</sub>, and P<sub>30</sub>B<sub>50</sub>D<sub>5</sub> hydrogels. (<b>d</b>–<b>f</b>) Pore size of P<sub>30</sub>B<sub>50</sub>, P<sub>30</sub>B<sub>50</sub>D<sub>1</sub>, and P<sub>30</sub>B<sub>50</sub>D<sub>5</sub> hydrogels.</p>
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<p>(<b>a</b>) Strain dependence of G′ and G″ of hydrogel P<sub>30</sub>B<sub>50</sub>, P<sub>30</sub>B<sub>50</sub>D<sub>1</sub>, and P<sub>30</sub>B<sub>50</sub>D<sub>5</sub>. (<b>b</b>) Shear rate−dependent viscosity of hydrogel P<sub>30</sub>B<sub>50</sub>, P<sub>30</sub>B<sub>50</sub>D<sub>1</sub>, and P<sub>30</sub>B<sub>50</sub>D<sub>5</sub>.</p>
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<p>(<b>a</b>) Injectable properties of P<sub>30</sub>B<sub>50</sub>, P<sub>30</sub>B<sub>50</sub>D<sub>1</sub>, and P<sub>30</sub>B<sub>50</sub>D<sub>5</sub> hydrogels. (<b>b</b>) Self-healing properties of P<sub>30</sub>B<sub>50</sub>, P<sub>30</sub>B<sub>50</sub>D<sub>1,</sub> and P<sub>30</sub>B<sub>50</sub>D<sub>5</sub> hydrogels. (<b>c</b>) Self-healing Mechanism Diagram of P<sub>30</sub>B<sub>50</sub>D<sub>5</sub> hydrogels.</p>
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<p>Tensile properties of (<b>a</b>) P<sub>30</sub>B<sub>50</sub>, (<b>b</b>) P<sub>30</sub>B<sub>50</sub>D<sub>1</sub>, and (<b>c</b>) P<sub>30</sub>B<sub>50</sub>D<sub>5</sub> hydrogels. The arrow denotes the stretching direction. (<b>d</b>) Swelling ratio of P<sub>30</sub>B<sub>50</sub>, P<sub>30</sub>B<sub>50</sub>D<sub>1</sub>, and P<sub>30</sub>B<sub>50</sub>D<sub>5</sub> hydrogels in PBS. Data are reported as means ± SD, <span class="html-italic">n</span> = 3 (** <span class="html-italic">p</span> &lt; 0.01, *** <span class="html-italic">p</span> &lt; 0.001).</p>
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<p>(<b>a</b>) Water retention properties of hydrogel P<sub>30</sub>B<sub>50</sub>, P<sub>30</sub>B<sub>50</sub>D<sub>1</sub>, and P<sub>30</sub>B<sub>50</sub>D<sub>5</sub>. (<b>b</b>) In vitro degradation behavior of hydrogel P<sub>30</sub>B<sub>50</sub>, P<sub>30</sub>B<sub>50</sub>D<sub>1</sub>, and P<sub>30</sub>B<sub>50</sub>D<sub>5</sub>. Data are reported as means ± SD, <span class="html-italic">n</span> = 3.</p>
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<p>Antibacterial activity of the P<sub>30</sub>B<sub>50</sub>, P<sub>30</sub>B<sub>50</sub>D<sub>1</sub>, and P<sub>30</sub>B<sub>50</sub>D<sub>5</sub> hydrogels. (<b>a</b>–<b>c</b>) Quantitative statistics of the bacterial killing ratio of the hydrogels against <span class="html-italic">E. coli</span> and <span class="html-italic">S. aureus</span> in the surface antibacterial activity test. Data are reported as means ± SD, <span class="html-italic">n</span> = 3 (*** <span class="html-italic">p</span> &lt; 0.001).</p>
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<p>Schematic illustration of the composition, preparation, and properties of double networked PVA/DP hydrogels.</p>
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17 pages, 3450 KiB  
Article
Enhancing the Performance of Biodegradable Lignin Nanoparticle/PVA Composite Films via Phenolation Pretreatment of Lignin Using a Novel Ternary Deep Eutectic Solvent
by Xiansheng Cao, Xueping Li, Ruchun Wu, Bao Liu and Wenfei Lin
Coatings 2024, 14(12), 1544; https://doi.org/10.3390/coatings14121544 - 11 Dec 2024
Viewed by 520
Abstract
As an environment-friendly biodegradable material, poly (vinyl alcohol) (PVA) has been focused on improving performance and expanding its applications. In this study, improved performance lignin nanoparticle/PVA composite film was prepared by phenolation of bagasse lignin (BL) using a novel ternary deep eutectic solvent [...] Read more.
As an environment-friendly biodegradable material, poly (vinyl alcohol) (PVA) has been focused on improving performance and expanding its applications. In this study, improved performance lignin nanoparticle/PVA composite film was prepared by phenolation of bagasse lignin (BL) using a novel ternary deep eutectic solvent (DES). The effects of introduction of DES-phenolated lignin (DL) nanoparticles with different additions (1, 3, 5, 10 wt%) on the properties of DL/PVA composite film were comprehensively studied by mechanical performance test, UV-shielding performance test, contact angle measurement, thermogravimetric analyses and DPPH free radical scavenging activity. The experimental results indicated that lignin nanoparticles (LNPs) were homogeneously distributed in a biodegradable PVA matrix due to hydrogen bonds between the PVA matrix and lignin nanoparticles. With the introduction of DES pretreatment on native bagasse lignin, the various performances of DL/PVA composite films, such as tensile strength, surface hydrophobicity, UV-shielding and thermal stability, were enhanced in comparison with both pure PVA film and BL/PVA composite film incorporated with DES-untreated BL. The tensile strength of DL/PVA composite film with 3 wt% addition increased to 97.79 MPa from 69.41 MPa for pure PVA film, and the water contact angle increased from 43.7° to 84.2°. DL/PVA composite film with 10 wt% addition shielded 95.8% of the UV spectrum (400–200 nm). Moreover, after incorporating the DL nanoparticles into the PVA matrix, the as-obtained DL/PVA composite films displayed good antioxidant activity by eliminating most of the DPPH free radicals. With 10 wt% addition of DL nanoparticles, the DPPH radical scavenging activity of DL/PVA composite film increased by about 76% compared with pure PVA film. These enhanced properties were attributed to the more phenolic hydroxyl groups of DL nanoparticles than of BL and the hydrogen-bonding interactions. In conclusion, the DES-phenolation pretreatment of lignin clearly improved the properties of PVA composite films. Furthermore, as both lignin and PVA are biodegradable, the lignin nanoparticle/PVA composite film may be a promising candidate for fully biodegradable robust coating materials with vital potential applications, such as UV-shielding and food packaging, etc. Full article
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<p>Schematic representation of preparation of lignin nanoparticle/PVA composite films.</p>
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<p>(<b>a</b>) Particle size distribution and (<b>b</b>) Tyndall effect for two types of LNP.</p>
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<p>FT–IR spectra of pure PVA and lignin nanoparticle/PVA composite films.</p>
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<p>FE–SEM images of pure PVA and lignin nanoparticle/PVA composite films. The red circles represent irregular nanoscale agglomerations.</p>
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<p>Tensile strength and elongation at break of pure PVA and lignin nanoparticle/PVA composite films.</p>
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<p>UV–vis transmittance curves of pure PVA and lignin nanoparticle/PVA composite films.</p>
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<p>Digital photographs of pure PVA and lignin nanoparticle/PVA composite films. (<b>a</b>) PVA, (<b>b</b>) 1% DL/PVA, (<b>c</b>) 3% DL/PVA, (<b>d</b>) 5% DL/PVA, (<b>e</b>) 10% DL/PVA, (<b>f</b>) 5% BL/PVA.</p>
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<p>Thermal analysis of pure PVA and lignin nanoparticle/PVA composite films: (<b>a</b>) TG curves and (<b>b</b>) DTG curves.</p>
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<p>Water contact angle of pure PVA and lignin nanoparticle/PVA composite films.</p>
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<p>DPPH radical scavenging activity of pure PVA and DL/PVA composite films with various contents of DLNP.</p>
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13 pages, 2842 KiB  
Article
Fast-Swelling Tamarind Xyloglucan/PVA Hydrogels with Interconnected Macroporous Structures for Biomedical Applications
by Umpornpan Ninjumrat, Piyachat Chuysinuan, Thitirat Inprasit, Sarute Ummartyotin, Kittipong Chainok and Penwisa Pisitsak
Polymers 2024, 16(24), 3457; https://doi.org/10.3390/polym16243457 - 10 Dec 2024
Viewed by 483
Abstract
This work demonstrates the preparation of fast-swelling hydrogels based on poly(vinyl alcohol) (PVA) and tamarind xyloglucan (XG), utilizing freeze-drying to achieve an interconnected macroporous structure. Although XG is non-toxic and abundant, it has poor mechanical properties. Therefore, XG was mixed with PVA and [...] Read more.
This work demonstrates the preparation of fast-swelling hydrogels based on poly(vinyl alcohol) (PVA) and tamarind xyloglucan (XG), utilizing freeze-drying to achieve an interconnected macroporous structure. Although XG is non-toxic and abundant, it has poor mechanical properties. Therefore, XG was mixed with PVA and crosslinked with citric acid (CA). Without XG, the crosslinked PVA sample contained partially aligned channels several hundred microns wide. The addition of XG (25% w/w) reduced the structural order of the hydrogels. However, the addition of XG improved the swelling ratio from 308 ± 19% in crosslinked PVA to 533.33% in crosslinked PVA/XG. XG also increased the porosity, as the porosity of the crosslinked PVA, XG, and PVA/XG samples was 56.09 ± 2.79%, 68.99 ± 2.06%, and 66.49 ± 1.62%, respectively. Resistance to compression was decreased by the incorporation of XG but was increased by CA crosslinking. The determination of the gel fraction revealed that CA crosslinking was more effective for the PVA component than the XG component. The swelling of all hydrogels was very rapid, reaching equilibrium within 10 s, due to the interconnected macroporous structure that allowed for capillary action. In conclusion, the prepared hydrogels are non-cytotoxic and well suited for biomedical applications such as drug delivery, wound dressings, and hygienic products. Full article
(This article belongs to the Special Issue Polymer-Based Materials for Drug Delivery and Biomedical Applications)
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<p>Structural representations of (<b>a</b>) tamarind XG [<a href="#B2-polymers-16-03457" class="html-bibr">2</a>,<a href="#B5-polymers-16-03457" class="html-bibr">5</a>,<a href="#B6-polymers-16-03457" class="html-bibr">6</a>], (<b>b</b>) partially hydrolyzed PVA [<a href="#B20-polymers-16-03457" class="html-bibr">20</a>], (<b>c</b>) CA, and (<b>d</b>) the crosslinking reaction between PVA and XG with CA as the crosslinker.</p>
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<p>FTIR spectra of the samples before and after crosslinking.</p>
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<p>SEM images of the crosslinked samples taken at 100× and 1000× magnifications: (<b>a</b>,<b>b</b>) PVA/CA, (<b>c</b>,<b>d</b>) XG/CA, and (<b>e</b>,<b>f</b>) PVA/XG/CA.</p>
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<p>DSC thermograms of the prepared hydrogels.</p>
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<p>Swelling ratio of the prepared hydrogels.</p>
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<p>Textural analysis results.</p>
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<p>MTT assay results showing cell viability at various extraction medium concentrations.</p>
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22 pages, 9704 KiB  
Article
Spinnability and Morphological Stability of Carboxymethyl Cellulose and Poly(Vinyl Alcohol) Blends by Electrospinning
by Javier M. Anaya-Mancipe, Vanessa F. da Silva, Angela Y. Becerra-Lovera, Marcos L. Dias and Rossana M. S. M. Thiré
Processes 2024, 12(12), 2759; https://doi.org/10.3390/pr12122759 - 4 Dec 2024
Viewed by 430
Abstract
Carboxymethyl cellulose (CMC) is a plant-derived polymer known for its excellent anti-adhesive properties, making it suitable for dressings for highly exudative lesions. However, CMC alone is considered an un-spinnable biopolymer due to its complex intermolecular interactions. This study explored the spinnability of CMC [...] Read more.
Carboxymethyl cellulose (CMC) is a plant-derived polymer known for its excellent anti-adhesive properties, making it suitable for dressings for highly exudative lesions. However, CMC alone is considered an un-spinnable biopolymer due to its complex intermolecular interactions. This study explored the spinnability of CMC through electrospinning by blending it with poly(vinyl alcohol) (PVA) at an 8:2 (PVA/CMC) ratio. Two types of PVA with varying molecular weights and degrees of hydrolysis were used at different concentrations. Solutions were prepared with Milli-Q water at 90 °C for about 2 h, followed by electrospinning under different voltages and flow rates. Scanning electron microscopy (SEM) was used to assess spinning ability, while Fourier-transform infrared spectroscopy (FTIR-ATR) characterized the mats’ chemical composition. Thermal behavior was analyzed using thermogravimetry analysis (TGA) and differential scanning calorimetry (DSC). Results showed that the neat PVA.1 solution produced smaller nanofibers (~217.9 nm), while the PVA.1/CMC blend resulted in a smaller fiber diameter (129.9 nm) but with more defects due to higher surface tension. In contrast, PVA.2 and PVA.2/CMC exhibited larger diameters (448.6 nm and 270.1 nm, respectively) and better thermal and morphological stability, indicating their potential for anti-adhesive chronic wound dressings. Full article
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<p>Viscosities and surface tensions of PVA and PVA/CMC solutions. For solution from PVA.1 and PVA.1/CMC solutions: (<b>A</b>) viscosity and (<b>B</b>) surface tension. From PVA.2 and PVA.2/CMC solutions: (<b>C</b>) viscosity and (<b>D</b>) surface tension.</p>
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<p>SEM images of (4.0 wt. %) PVA.1 nanofiber with rate flow variation. (<b>A</b>) 0.1 mL/h, (<b>B</b>) 0.5 mL/h. PVA.1/CMC: (<b>C</b>) 0.5 mL/h. (<b>D</b>) Histogram of PVA.1 nanofibers.</p>
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<p>SEM images of electrospun nanofibers with 6 wt. % PVA.1 and CMC (8:2 mass ratio). Operating conditions: voltage 17 kV, distance tip needle—collector: 11 cm. Flow rate 0.5 mL/h: (<b>A</b>) Pure PVA.1 and (<b>B</b>) PVA.1/CMC; flow rate 0.6 mL/h: (<b>C</b>) Pure PVA.1, (<b>D</b>) PVA.1/CMC.</p>
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<p>SEM images and their histograms for PVA.1/CMC samples with 6% <span class="html-italic">w</span>/<span class="html-italic">v</span> (PVA mass ratio). Varying the applied voltage. Operating conditions: 1.0 mL/h, needle tip–collector distance: 11 cm. (<b>A</b>) 15 kV; (<b>B</b>) 17 kV; (<b>C</b>) 20 kV, and (<b>D</b>) histogram comparative.</p>
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<p>SEM images of PVA (8 wt. %) for two magnifications with voltage variation. PVA.1: (<b>A</b>) 15 kV; (<b>B</b>) 20 kV. For PVA.1/CMC solution: (<b>C</b>) 15 kV; (<b>D</b>) 20 kV.</p>
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<p>SEM images of PVA.1/CMC samples with varying flow rates and different magnifications (voltage: 20 kV; distance: 11 cm) in 5k (<b>left</b>) and 20k (<b>right</b>). Flow rate: (<b>A</b>) 0.6 mL/h and (<b>B</b>) 0.5 mL/h.</p>
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<p>SEM images and histograms of PVA.2 (6 wt.%) and PVA.1/CMC (8:2) nanofibers. (<b>A</b>) 15 kV; (<b>B</b>) 17 kV; (<b>C</b>) 20 kV.</p>
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<p>SEM images of electrospun nanofibers of 8 wt. % PVA.2 (Mn: 80,000 g/mol), varying the applied voltage at 15 kV (<b>left</b>), 17 kV (<b>center</b>), and 20 kV (<b>right</b>), with two magnifications of 2k (<b>A</b>,<b>C</b>,<b>E</b>) and 10k (<b>B</b>,<b>D</b>,<b>F</b>). (<b>G</b>) Comparative histogram of PVA.2 fibers; (<b>H</b>) PVA.2/CMC fibers and its histogram.</p>
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<p>SEM micrographs and their histograms for electrospun samples of PVA.2, 10 wt.% (Mn: 80,000 g/mol) with a voltage of 20 kV at two magnifications of 2k (<b>A</b>) and 10k (<b>B</b>), and of PVA.2/CMC (<b>C</b>,<b>D</b>).</p>
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<p>Comparative FTIR-ATR spectrograms of PVAs, CMC, and blend electrospun mats. Evaluating for 4000–500 cm<sup>−1</sup>: (<b>A</b>) PVA.1 and PVA.1/CMC mats, (<b>B</b>) PVA.2, and PVA.2/CMC. Zoom of spectrogram in range of 2000 to 500 cm<sup>−1</sup>: (<b>C</b>) for PVA.1 and blend mats and (<b>D</b>) for PVA.2 and blend mats.</p>
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<p>TGA and DSC thermograms for different PVAs and PVA/CMC electrospun mats produced by TGA: (<b>A</b>) PVA.1; (<b>B</b>) PVA.2; DSC: PVA.1; (<b>C</b>) first heat cycle; (<b>E</b>) second heat cycle; and PVA.2: (<b>D</b>) first heat cycle; (<b>F</b>) second heat cycle (DSC analysis: Exo up).</p>
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28 pages, 7445 KiB  
Article
Study on Fabrication and Properties of Polyvinyl Alcohol/Chitosan Nanofibers Created from Aqueous Solution with Acetic Acid and Ethanol by the Electrospinning Method
by Thi Hong Nhung Vu, Svetlana N. Morozkina, Roman O. Olekhnovich, Aleksandr V. Podshivalov and Mayya V. Uspenskaya
Polymers 2024, 16(23), 3393; https://doi.org/10.3390/polym16233393 - 30 Nov 2024
Viewed by 681
Abstract
The development of nanofibers with incorporated biologically active molecules with a targeted mode of action is a current research trend. Potential materials for the development of such systems include poly(vinyl alcohol) (PVA) and chitosan (CS) nanofibers, which are traditionally fabricated by the electrospinning [...] Read more.
The development of nanofibers with incorporated biologically active molecules with a targeted mode of action is a current research trend. Potential materials for the development of such systems include poly(vinyl alcohol) (PVA) and chitosan (CS) nanofibers, which are traditionally fabricated by the electrospinning of aqueous solutions of these polymers with acetic acid. To improve drug integration, ethanol was added to the binary-solvent system. This results in several important data: noticeable shifts in the solvent system’s solubility parameter, the interaction of the various component forces, and optical and rheological properties of the PVA-CS solution. The use of ethanol in the electrospun solution also contributes to adjusting the solubility parameters of the solution in the Teas graph, maintaining the “fh − fd” in the optimal region for the fabrication of PVA-CS nanofibers. Increasing the efficiency of PVA-CS nanofiber fabrication by electrospinning is quite difficult due to the requirements of solution parameters, technological parameters, and environmental parameters; however, this efficiency was increased in this work by 2 to 3 times with a more optimal PVA-CS nanofiber morphology. These results demonstrate that aqueous solution containing 4% PVA, 3% CS, 15% ethanol, and 45% acetic acid is optimal for increasing the nanofiber fabrication productivity, improving the morphology and diameter of PVA-CS nanofibers without changing in chemical bonds. The XRD spectrum revealed that the alterations in the crystal lattice and diameter of the PVA-CS nanofibers led to the variation in their thermal and tensile properties. Full article
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<p>Effect of the ethanol-acetic acid ratio on the optical density and turbidity of the PVA-CS solution.</p>
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<p>Graphs of the dependence of shear rates on the dynamic viscosity of PVA-CS solutions at the different ratios of ethanol-acetic acid.</p>
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<p>Graphs of the dependence of the rheological properties of the PVA-CS solution on the ethanol-acetic acid ratios.</p>
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<p>The Teas plot for PVA-CS electrospinning solutions with CH<sub>3</sub>COOH-H<sub>2</sub>O and CH<sub>3</sub>COOH-C<sub>2</sub>H<sub>5</sub>OH-H<sub>2</sub>O as the co-solvent system.</p>
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<p>The values of polar interactions <span class="html-italic">f<sub>h</sub></span>, <span class="html-italic">f<sub>p</sub></span>, and <span class="html-italic">f<sub>d</sub></span> for a mixture of solvents, CH<sub>3</sub>COOH-C<sub>2</sub>H<sub>5</sub>OH-H<sub>2</sub>O, in the solution of 4% PVA–3% CS.</p>
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<p>Microscopic images at 100× and 1000× and the diameter distributions of PVA-CS nanofibers obtained from solutions of 4% PVA, 3% CS, and different concentration of acetic acid and ethanol (electrospinning parameters fixed at a collector—needle distance of 140 mm, a feed rate of 0.2 mL/h, and a voltage of 28 kV).</p>
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<p>Microscopic images at 100× and 1000× and the diameter distributions of PVA-CS nanofibers obtained from the solution of PVA-CS (the ratio being 4–3) with an ethanol-acetic acid solvent ratio of 15–45 at a feed rate of 0.2 mL/h, a voltage of 28 kV, and with variation of the needle-collector distance.</p>
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<p>Microscopic images at 100× and 1000× and diameter distributions of PVA-CS nanofibers obtained from the solution of PVA-CS (the ratio 4–3) with an ethanol-acetic acid solvent ratio of 15–45 at a needle-collector distance of 140 mm, a voltage of 28 kV, and a variation of the feed rate from 0.1 to 0.4 mL/h.</p>
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<p>Microscopic images at 100× and 1000× and diameter distributions of PVA-CS nanofibers obtained from the solution of PVA-CS (the ratio 4–3) with an ethanol-acetic acid solvent ratio of 15–45 at a needle-collector distance of 140 mm, a feed rate of 0.3 mL/h, and a variation in voltage from 25 to 30 kV.</p>
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<p>Infrared spectra of PVA powder, chitosan powder, and PVA-CS nanofibers.</p>
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<p>X-ray diffraction data of PVA powder, CS powder, and PVA nanofibers from an aqueous solution and PVA-CS nanofibers from an aqueous solution with C<sub>2</sub>H<sub>5</sub>OH and CH<sub>3</sub>COOH.</p>
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<p>DSC heating curve of PVA-CS nanofibers at different ethanol-acetic acid ratios.</p>
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<p>TGA thermogram of PVA powder, CS powder, and PVA-CS nanofibers at different ethanol-acetic acid ratios in initial electrospun solution.</p>
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<p>The deformation of PVA-CS nanofibers according to the ethanol-acetic acid ratios in the electrospun solutions.</p>
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<p>Changes in tensile properties of PVA-CS nanofibers according to ethanol-acetic acid ratios in the electrospun solutions.</p>
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17 pages, 3258 KiB  
Article
Bioconversion of Agro-Industrial Byproducts Using Bacillus sp. CL18: Production of Feather Hydrolysates for Development of Bioactive Polymeric Nanofibers
by Naiara Jacinta Clerici, Daniel Joner Daroit, Aline Aniele Vencato and Adriano Brandelli
Fermentation 2024, 10(12), 615; https://doi.org/10.3390/fermentation10120615 - 30 Nov 2024
Viewed by 806
Abstract
Microbial fermentation represents an interesting strategy for the management and valorization of agro-industrial byproducts. In this study, the proteolytic strain Bacillus sp. CL18 was used to produce bioactive hydrolysates during submerged cultivation with various protein-containing substrates, including byproducts from the poultry (feathers), cheese [...] Read more.
Microbial fermentation represents an interesting strategy for the management and valorization of agro-industrial byproducts. In this study, the proteolytic strain Bacillus sp. CL18 was used to produce bioactive hydrolysates during submerged cultivation with various protein-containing substrates, including byproducts from the poultry (feathers), cheese (whey), fish (scales), and vegetable oil (soybean meal) industries. The bioactive feather hydrolysates (BFHs) showing high antioxidant activity were incorporated in poly(vinyl alcohol) (PVA) and poly-ε-caprolactone (PCL) nanofibers by the electrospinning technique. The PVA nanofibers containing 5% BFH reached antioxidant activities of 38.7% and 76.3% for DPPH and ABTS assays, respectively. Otherwise, the PCL nanofibers showed 49.6% and 55.0% scavenging activity for DPPH and ABTS radicals, respectively. Scanning electron microscopy analysis revealed that PVA and PCL nanofibers containing BFH had an average diameter of 282 and 960 nm, respectively. Moreover, the results from thermal analysis and infrared spectroscopy showed that the incorporation of BFH caused no significant modification in the properties of the polymeric matrix. The bioconversion of feathers represents an interesting strategy for the management and valorization of this byproduct. Furthermore, the effective incorporation of BFH in polymeric nanofibers and validation of the biological activity suggest the application of these materials as antioxidant coatings and packaging. Full article
(This article belongs to the Special Issue Waste as Feedstock for Fermentation)
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<p>Soluble protein contents (<b>A</b>) and ABTS radical-scavenging activity (<b>B</b>) during submerged cultivations with <span class="html-italic">Bacillus</span> sp. CL18 in media containing whole feathers (●), milled feathers (○), fish scales (▼), soybean meal (SBM, △), soy protein isolate (SPI, ■), casein (□), whey protein isolate (WPI, ◆), and lyophilized sweet whey (LSW, ◇).</p>
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<p>Feather degradation by <span class="html-italic">Bacillus</span> sp. CL18. Bottom views of Erlenmeyer flasks containing mineral medium and feathers (10 g/L), incubated with <span class="html-italic">Bacillus</span> sp. CL18 for (<b>A</b>) 0 h and (<b>B</b>) 120 h (5 days).</p>
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<p>Scanning electron microscopy (upper panels) and histograms of diameter distribution (lower panels) of PVA nanofibers. Control 10% PVA (<b>a</b>), 10% PVA + 5% BFH (<b>b</b>), control 15% PVA (<b>c</b>), and 15% PVA + 5% BFH (<b>d</b>).</p>
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<p>Scanning electron microscopy (upper panels) and histograms of diameter distribution (lower panels) of PCL nanofibers. Control 10% PCL (<b>a</b>), 10% PCL + 5% BFH, (<b>b</b>), control 15% PCL (<b>c</b>), and 15% PCL + 5% BFH (<b>d</b>).</p>
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<p>Thermogravimetric analysis of nanofibers. (<b>a</b>) TGA 10% PVA, (<b>b</b>) DTG 10% PVA, (<b>c</b>) TGA 10% PCL, and (<b>d</b>) DTG 10% PCL. The evaluation was performed in nanofibers functionalized with bioactive feather hydrolysate (5% BFH) and control nanofibers (without BFH).</p>
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<p>Differential scanning calorimetry (DSC) analysis of nanofibers composed of 10% PCL (<b>a</b>) and 10% PVA (<b>b</b>). The evaluation was performed in nanofibers functionalized with bioactive feather hydrolysate (5% BFH) and control nanofibers (without BFH).</p>
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<p>FTIR spectra of nanofibers composed of 10% PVA (<b>a</b>) and 10% PCL (<b>b</b>). The evaluation was performed in nanofibers functionalized with bioactive feather hydrolysate (5% BFH) and control nanofibers (without BFH).</p>
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<p>Mechanical properties of poly-ε-caprolactone (PCL) and poly(vinyl alcohol) (PVA) nanofibers. Values of Young’s modulus (<b>a</b>), tensile strength (<b>b</b>), and elongation at break (<b>c</b>) were determined for control (blue bars) and functionalized nanofibers with 5% BFH (red bars). Data represent mean ± standard deviation of three independent experiments. Distinct letters indicate significant differences (<span class="html-italic">p</span> &lt; 0.05).</p>
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23 pages, 10821 KiB  
Article
Poly(Vinyl Alcohol) Drug and PVA–Drug–Surfactant Complex Organogel with Dimethyl Sulfoxide as a Drug Delivery System
by Sabina Otarbayeva and Dmitriy Berillo
Gels 2024, 10(11), 753; https://doi.org/10.3390/gels10110753 - 20 Nov 2024
Viewed by 919
Abstract
The relevance of active research lies in the need to develop new technologies to improve drug delivery methods for the effective treatment of wound healing. Additionally, the potential application of organogels in other areas of biomedicine, such as creating medical patches with controlled [...] Read more.
The relevance of active research lies in the need to develop new technologies to improve drug delivery methods for the effective treatment of wound healing. Additionally, the potential application of organogels in other areas of biomedicine, such as creating medical patches with controlled drug delivery, indicates a wide range of possibilities for using this technology. This study focuses on developing controlled drug delivery systems using organogels as carriers for ceftriaxone and ofloxacin. By selecting optimal formulations, organogels were created to immobilize the drugs, facilitating their effective and sustained release. The swelling behavior of the hydrogels was studied, showing a swelling coefficient between 16 and 32%, indicating their ability to absorb liquid relative to their weight. Drug release studies demonstrated that ceftriaxone was released 1.8 times slower than ofloxacin, ensuring a more controlled delivery. Microbiological tests confirmed that the organogels containing ofloxacin exhibited antimicrobial activity against Escherichia coli, Bacillus subtilis, and Staphylococcus aureus. However, it was a challenge to estimate activity for the model antibiotic ceftriaxone due to bacterial resistance to it. Organogel poly(vinyl alcohol) (PVA)-DMSO–alginate modifications with surfactant cetylpyridinium bromide led to the formation of a polyelectrolyte complex on the interphase, allowing further enhanced the prolonged release of the drugs. The research identified that the optimal compositions for sustained drug release were organogels with compositions PVA (10%)-PVP (1%) DMSO (50%) and PVA (10%)-DMSO (50%) formulations, illustrating the transparent nature of these organogels making them suitable for ophthalmological application. Various organogels compositions (PVA-DMSO, PVA-poly(vinylpyrrolidone)-DMSO, PVA-DMSO–alginate, PVA-DMSO-PLGA, PVA-DMSO–drug–surfactant) loaded with ceftriaxone, ofloxacin, and surfactant were prepared and characterized, highlighting their potential use in antibiotic patches for wound healing. These organogels illustrate promising results for localized treatment of infections in wounds, cuts, burns, and other skin lesions. Full article
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<p>PVA solution 10 wt % in (<b>a</b>) water (sol.); (<b>b</b>) pure DMSO (sol.); (<b>c</b>) PVA 10% organogel from 60/40% DMSO/H<sub>2</sub>O; (<b>d</b>,<b>e</b>) PVA-PLGA10 and 4% organogel from 60/40% DMSO/H<sub>2</sub>O, respectively.</p>
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<p>PVA 10% organogel from 60/40% DMSO/H<sub>2</sub>O: (<b>a</b>) diameter of freshly prepared gel d = 20 mm; (<b>b</b>) diameter of the gel after 24 h. at 25 °C diameter 15 mm, scale bar 2 mm.</p>
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<p>Swelling curve of PVA organogels in carbonate buffer pH 7.4.</p>
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<p>Desorption rate of ofloxacin from the PVA (10 wt.%)-DMSO gel in carbonate buffer at pH 7.4.</p>
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<p>Kinetic of drug release from various PVA organogels in carbonate buffer at pH 7.4 relatively initially loaded concentration.</p>
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<p>Korsmeyer–Peppas models for the ofloxacin cumulative release from organogel, orange line theoretical model; blue line experimental data: (<b>a</b>) 10% PVA-DMSO; (<b>b</b>) 10% PVA-DMSO-Alg (<b>c</b>) 10% PVA-DMSO-PVP; (<b>d</b>) 10% PVA-DMSO-PLGA.</p>
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<p>Korsmeyer–Peppas models of ceftriaxone cumulative release from organogels orange line theoretical model; blue line experimental data.: (<b>a</b>) PVA-DMSO; (<b>b</b>) PVA-DMSO-Alg; (<b>c</b>) PVA-DMSO-PVP (<b>d</b>) PVA-DMSO-PLGA.</p>
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<p>Kinetic release of Oflox and ceftriaxone from PVA-DMSO-Alg-CPBr-Oflox and PVA-DMSO-Alg-CPBr-CEF, PVA-DMSO-Alg-Oflox, PVA-DMSO-Alg-CEF.</p>
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<p>Zones of inhibition of antibacterial activity (ofloxacin).</p>
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<p>Antibacterial activity of organogels via method diffusion to agar gel: (<b>a</b>) 10%PVA-DMSO-Oflox; (<b>b</b>) 10%PVA-DMSO-Oflox; (<b>c</b>) control samples paper disk with ofloxacin and cetylpyridinium bromide; (<b>d</b>) 10%PVA-DMSO-AlgoOflox-CPBr; (<b>e</b>) 10%PVA-DMSO-Alg-Oflox-CPBr, (control sample) disk with Ofloxacin, (control sample) disk with Ceftriaxone against <span class="html-italic">B. subtilis</span>.</p>
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<p>Antibacterial activity of drug delivery system based on organogel against <span class="html-italic">S. Aureus</span>: (<b>A</b>) 10%PVA-DMSO-Oflox, 10%PVA-DMSO-Ceftriaxone, 10%PVA-DMSO-Alg-CPBr-Ceftriaxone; and (<b>B</b>) control samples paper disk with ceftriaxone, 10%PVA-DMSO-Alg-Oflox-CPBr.</p>
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<p>Zones of inhibition of antibacterial activity (ceftriaxone).</p>
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16 pages, 3540 KiB  
Article
Cryostructuring of Polymeric Systems: 68. Evaluation of Poly(vinyl alcohol) Composite Cryogels Filled with Poly(3-hydroxybutyric acid)-Based Microspheres of Different Porous Morphology as Potential Delivery Systems for Drugs of Various Water-Solubility
by Dmitrii A. Michurov, Gagik A. Andreasyan and Vladimir I. Lozinsky
Gels 2024, 10(11), 734; https://doi.org/10.3390/gels10110734 - 13 Nov 2024
Viewed by 719
Abstract
Poly(3-hydroxybutyric acid)-based microspheres of two types, with and without macropores, were prepared; their morphology and particle size were evaluated. These microspheres were entrapped as disperse fillers into the bulk of macroporous cryogels based on poly(vinyl alcohol) (PVA). It was found that the rigidity [...] Read more.
Poly(3-hydroxybutyric acid)-based microspheres of two types, with and without macropores, were prepared; their morphology and particle size were evaluated. These microspheres were entrapped as disperse fillers into the bulk of macroporous cryogels based on poly(vinyl alcohol) (PVA). It was found that the rigidity of the resultant composite cryogels increased markedly as compared to that of unfilled cryogels of the same PVA concentration. The resulting composites were further tested for their potential to act as drug carriers. With that, simvastatin was included into the filler particles directly in the course of their preparation, followed by entrapment of such drug-loaded microspheres into the PVA cryogel. In turn, ibuprofen sodium salt was introduced into the preliminary prepared cryogels filled with the drug-free microspheres. The experimental study of drug release kinetics showed that due to the non-covalent interactions of both simvastatin and ibuprofen sodium salt with the particles of discrete phase, prolongation of the release processes was observed. Full article
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<p>Images (optical stereomicroscope) of wet PHB microspheres: MS-1 (<b>a</b>) and MS-2 (<b>b</b>).</p>
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<p>SEM images of dry PHB microspheres: MS-1 (<b>a</b>) and MS-2 (<b>b</b>).</p>
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<p>PHB particle size distribution. Curve 1 corresponds to MS-1, curve 2 corresponds to MS-2.</p>
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<p>Values of the Young’s modulus of the PVA cryogel samples prepared from the feed compositions indicated in <a href="#gels-10-00734-t002" class="html-table">Table 2</a>.</p>
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<p>Chemical structure of ibuprofen sodium salt [<a href="#B53-gels-10-00734" class="html-bibr">53</a>].</p>
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<p>Chemical structure of simvastatin [<a href="#B54-gels-10-00734" class="html-bibr">54</a>].</p>
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<p>Change in the amount of ibuprofen sodium salt in solution during saturation of samples. Curve 1—cryogel sample without filler; curve 2—cryogel sample with additions of porous PHB microspheres; curve 3—cryogel sample with additions of non-porous PHB microspheres. The mass content of PHB particles in cryogels is equal to ~27 mg/cm<sup>3</sup> in all cases.</p>
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<p>Ibuprofen sodium salt release. Curve 1—cryogel sample without filler; curve 2—cryogel sample with the addition of porous PHB microspheres; curve 3—cryogel sample with the addition of non-porous PHB microspheres.</p>
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<p>Weibull model plot for the release of ibuprofen sodium salt. Curve 1—cryogel sample without filler; curve 2—cryogel sample with the addition of porous PHB microspheres; curve 3—cryogel sample with the addition of non-porous PHB microspheres.</p>
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<p>Simvastatin release. Curve 1—cryogel sample without filler; curve 2—cryogel sample with added porous PHB microspheres; curve 3—cryogel sample with added non-porous PHB microspheres.</p>
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19 pages, 8091 KiB  
Article
The Role of Freeze-Drying as a Multifunctional Process in Improving the Properties of Hydrogels for Medical Use
by Kacper Odziomek, Anna K. Drabczyk, Paulina Kościelniak, Patryk Konieczny, Mateusz Barczewski and Katarzyna Bialik-Wąs
Pharmaceuticals 2024, 17(11), 1512; https://doi.org/10.3390/ph17111512 - 10 Nov 2024
Viewed by 1269
Abstract
Background/Objectives: Freeze-drying is a dehydration method that extends the shelf life and stability of drugs, vaccines, and biologics. Recently, its role has expanded beyond preservation to improve novel pharmaceuticals and their carriers, such as hydrogels, which are widely studied for both drug delivery [...] Read more.
Background/Objectives: Freeze-drying is a dehydration method that extends the shelf life and stability of drugs, vaccines, and biologics. Recently, its role has expanded beyond preservation to improve novel pharmaceuticals and their carriers, such as hydrogels, which are widely studied for both drug delivery and wound healing. The main aim of this study was to explore the multifunctional role of freeze-drying in improving the physicochemical properties of sodium alginate/poly(vinyl alcohol)-based hydrogels for medical applications. Methods: The base matrix and hydrogels containing a nanocarrier-drug system, were prepared by chemical cross-linking and then freeze-dried for 24 h at −53 °C under 0.2 mBa. Key analyses included determination of gel fraction, swelling ratio, FT-IR, SEM, TG/DTG, in vitro drug release and kinetics, and cytotoxicity assessment. Results: Freeze-drying caused an increase in the gel fraction of the hydrogel with the dual drug delivery system from 55 ± 1.6% to 72 ± 0.5%. Swelling ability was pH-dependent and remained in the same range (175–282%). Thermogravimetric analysis showed that freeze-dried hydrogels exhibited higher thermal stability than their non-freeze-dried equivalents. The temperature at 10% weight loss increased from 194.0 °C to 198.9 °C for the freeze-dried drug-loaded matrix, and from 188.4 °C to 203.1 °C for the freeze-dried drug-free matrix. The average pore size of the freeze-dried hydrogels was in the range of 1.07 µm ± 0.54 to 1.74 µm ± 0.92. In vitro drug release revealed that active substances were released in a controlled and prolonged way, according to the Korsmeyer–Peppas model. The cumulative amount of salicylic acid released at pH = 9.0 after 96 h was 63%, while that of fluocinolone acetonide reached 73%. Both hydrogels were non-toxic to human fibroblast cells, maintaining over 90% cell viability after 48 h of incubation. Conclusions: The results show a high potential for commercialisation of the obtained hydrogels as medical dressings. Full article
(This article belongs to the Special Issue Progress of Hydrogel Applications in Novel Drug Delivery Platforms)
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<p>Swelling ratio (%) of the freeze-dried base matrix (F-D-M) and freeze-dried matrix containing a dual drug delivery system based on a thermosensitive nanocarrier (F-D-M-SA + FA) at 37 °C after tests in buffer solutions of pH: (<b>a</b>) 4.0; (<b>b</b>) 7.4; (<b>c</b>) 9.0. The results are presented as mean values (<span class="html-italic">n</span> = 3), while the bars represent ±SD.</p>
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<p>FT-IR spectra of the: (<b>a</b>) freeze-dried matrix containing a dual drug delivery system based on a thermosensitive nanocarrier (F-D-M-SA + FA); (<b>b</b>) freeze-dried base matrix (F-D-M). The arrow represents an additional band at the wavenumber of ~1600 cm<sup>−1</sup>, which can be related to benzene ring vibration.</p>
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<p>The cross-section SEM images of the freeze-dried base matrix (F-D-M) at magnifications: (<b>a</b>) 150×; (<b>b</b>) 500×; (<b>c</b>) 10,000×; (<b>d</b>) 20,000×, the cross-section SEM images of the freeze-dried matrix containing a dual drug delivery system based on a thermosensitive nanocarrier (F-D-M-SA + FA) at magnifications: (<b>e</b>) 150×; (<b>f</b>) 500×; (<b>g</b>) 10,000×; (<b>h</b>) 20,000×, and pore size distributions of samples: (<b>i</b>) F-D-M; (<b>j</b>) F-D-M-SA + FA.</p>
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<p>TG and DTG curves of the: (<b>a</b>) non-freeze-dried matrix containing a dual drug delivery system based on a thermosensitive nanocarrier (M-SA + FA); (<b>b</b>) freeze-dried matrix containing a dual drug delivery system based on a thermosensitive nanocarrier (F-D-M-SA + FA); (<b>c</b>) freeze-dried base matrix (F-D-M).</p>
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<p>Release profile of: (<b>a</b>) salicylic acid; (<b>b</b>) fluocinolone acetonide from the freeze-dried matrix containing a dual drug delivery system based on a thermosensitive nanocarrier (F-D-M-SA + FA). The bars represent ±SD. The dotted squares represent the first phase of drugs release, which is magnified in the graphs on the right.</p>
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<p>Kinetics of the salicylic acid release from freeze-dried matrix containing a dual drug delivery system based on a thermosensitive nanocarrier (F-D-M-SA + FA) according to: (<b>a</b>) zero-order model; (<b>b</b>) first-order model; (<b>c</b>) Higuchi model; (<b>d</b>) Korsmeyer–Peppas model.</p>
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<p>Fluocinolone acetonide release kinetics according to: (<b>a</b>) zero-order model; (<b>b</b>) first-order model; (<b>c</b>) Higuchi model; (<b>d</b>) Korsmeyer–Peppas model.</p>
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<p>The cell viability in the presence of freeze-dried matrix containing a dual drug delivery system based on a thermosensitive nanocarrier (F-D-M-SA + FA) and freeze-dried base matrix (F-D-M). The results are presented as mean values (<span class="html-italic">n</span> = 3), while the bars represent ±SD.</p>
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<p>The preparation scheme of the freeze-dried hydrogels.</p>
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12 pages, 3604 KiB  
Article
Development of Polymer Composite Membrane Electrolytes in Alkaline Zn/MnO2, Al/MnO2, Zinc/Air, and Al/Air Electrochemical Cells
by Sheng-Jen Lin, Juin-Yih Su, Dave W. Chen and Gwomei Wu
Polymers 2024, 16(21), 3068; https://doi.org/10.3390/polym16213068 - 31 Oct 2024
Viewed by 719
Abstract
This paper reports on the novel composite membrane electrolytes used in Zn/MnO2, Al/MnO2, Al/air, and zinc/air electrochemical devices. The composite membranes were made using poly(vinyl alcohol), poly(acrylic acid), and a sulfonated polypropylene/polyethylene separator to enhance the electrochemical characteristics and [...] Read more.
This paper reports on the novel composite membrane electrolytes used in Zn/MnO2, Al/MnO2, Al/air, and zinc/air electrochemical devices. The composite membranes were made using poly(vinyl alcohol), poly(acrylic acid), and a sulfonated polypropylene/polyethylene separator to enhance the electrochemical characteristics and dimensional stability of the solid electrolyte membranes. The ionic conductivity was improved significantly by the amount of acrylic acid incorporated into the polymer systems. In general, the ionic conductivity was also enhanced gradually as the testing temperature increased from 20 to 80 °C. Porous zinc gel electrodes and pure aluminum plates were used as the anodes, while porous carbon air electrodes or porous MnO2 electrodes were used as the cathodes. The cyclic voltammetry properties and electrochemical impedance characteristics were investigated to evaluate the cell behavior and electrochemical properties of these prototype cells. The results showed that these prototype cells had a low bulk resistance, a high cell power density, and a unique device stability. The Al/MnO2 cell achieved a density of 110 mW cm−2 at the designated current density for the discharge tests, while the other cells also exhibited good values in the range of 70–100 mW cm−2. Furthermore, the Zn/air cell consisting of the PVA/PAA = 10:5 composite membrane revealed an excellent discharge capacity of 1507 mAh. This represented a very high anode utilization of 95.7% at the C/10 rate. Full article
(This article belongs to the Special Issue Advanced Polymer Nanocomposites III)
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<p>SEM micrographs of (<b>a</b>) the un-sulfonated and (<b>b</b>) sulfonated PP/PE membrane, and (<b>c</b>) the top surface of s-PP/PE/PVA/PAA.</p>
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<p>IR spectra of the membrane samples.</p>
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<p>Mechanical testing curves for the membrane specimens.</p>
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<p>Nyquist plots for the polymer composite samples at room temperature.</p>
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<p>Cyclic voltammetry spectra for alkaline s-PP/PE/PVA/PAA composite membrane using PVA/PAA = 10:5 in Zn|membrane|Zn cell at 25 °C. (<b>a</b>) Different sweeping cycles, and (<b>b</b>) different PVA/PAA compositions at the 100th sweeping cycle.</p>
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<p>Cyclic voltammetry for the s-PP/PE/PVA/PAA composite membranes in the Al|membrane|Al cell at 25 °C with different sweeping cycles.</p>
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<p>Discharge curves for Zn/air cells using different s-PP/PE/PVA/PAA composite membrane electrolytes at a C/10 rate.</p>
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<p>AC impedance spectra for the alkaline Zn/air cells at 25 °C (<b>a</b>) before and (<b>b</b>) after the C/10 discharge tests.</p>
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<p>Current–potential and power–current curves for the (<b>a</b>) Zn/air cells and (<b>b</b>) Al/air cells.</p>
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<p>Current–potential and power–current curves for (<b>a</b>) Zn/MnO<sub>2</sub> cells and (<b>b</b>) Al/MnO<sub>2</sub> cells.</p>
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