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Keywords = nanocomposite hydrogels

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18 pages, 9596 KiB  
Article
Poly(Acrylic Acid)/TiO2 Nanocomposite Hydrogels for Paper Artwork Cleaning and Protection
by Sabina Botti, Francesca Bonfigli, Rosaria D’Amato, Jasmine Rodesi and Maria Gabriella Santonicola
Molecules 2025, 30(1), 75; https://doi.org/10.3390/molecules30010075 - 28 Dec 2024
Viewed by 349
Abstract
Paper-based artworks are prone to natural aging processes driven by chemical and biological processes. Numerous treatments have been developed to mitigate deterioration and prevent irreversible damage. In this study, we investigated the use of poly(acrylic acid)/TiO2 composite hydrogels, combining their cleaning and [...] Read more.
Paper-based artworks are prone to natural aging processes driven by chemical and biological processes. Numerous treatments have been developed to mitigate deterioration and prevent irreversible damage. In this study, we investigated the use of poly(acrylic acid)/TiO2 composite hydrogels, combining their cleaning and protective functions in a minimally invasive treatment. Hydrogels allow for controlled water flow and photocatalytic TiO2 nanoparticles enhance the hydrogel’s efficacy by enabling the removal of oxidation products and inactivating biological contaminants. Furthermore, this innovative material can act as a protective coating against UV-induced aging, preserving both color and stability of the paper. Raman spectroscopy and confocal laser scanning microscopy imaging techniques were employed to evaluate the treatments, allowing for us to differentiate between hydrolytic and oxidative aging processes. Our findings demonstrate that papers coated with poly(acrylic acid)/TiO2 composite hydrogels exhibit significant reductions in oxidative markers, an enhanced color stability, and an overall improved resistance to degradation compared to uncoated samples. Full article
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<p>Optical images in bright field of XIX paper. The green rectangle indicates the area of 200 µm × 200 µm scanned with a step size of 5 µm in Raman spectral imaging mode using green excitation (λ = 532 nm) and 10X objective (<b>a</b>) before the cleaning treatment; (<b>b</b>) after the cleaning treatment; (<b>c</b>) examples Raman spectra acquired before and after the cleaning treatment.</p>
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<p>Optical images of XIX paper (<b>upper</b> panels) and <span class="html-italic">O</span><sub>T</sub> marker value colocalized maps. (<b>a</b>) Before and (<b>b</b>) after 1 h CBP cleaning treatment. The color code is blue, green, red, yellow for increasing value of <span class="html-italic">O</span><sub>T</sub> marker.</p>
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<p>(<b>a</b>) Ageing marker variation in percentage for the XIX century paper, (<b>b</b>) the same for the XXI century paper. This laser printer 2021 paper was exposed to ambient light for three years.</p>
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<p>CLSM images (objective 4×) of a selected spot on Brehm paper. (<b>a</b>) Before cleaning treatment; (<b>b</b>) after cleaning treatment with CBP/TiO<sub>2</sub>. The figures show red and the green fluorescence channels and their overlay in yellow color (<b>c</b>) Graph of the red fluorescence signal intensity profiles detected along the yellow arrows of the spot before and after CBP/TiO<sub>2</sub> treatment.</p>
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<p>(<b>a</b>) Raman spectra of CBP/TiO<sub>2</sub> coated XIX century paper (red curve), XIX century paper sample after gel removal (light green curve), XIX century paper (green curve), and CBP/TiO<sub>2</sub> gel (brown curve); (<b>b</b>) score plot related to map of CBP/TiO<sub>2</sub> coated XIX century paper (red diamonds); CBP/TiO<sub>2</sub> coated XIX century paper after a first run of gel removal (orange dots) and a second run of gel removal (green squares). Ellipses are only a guide for the eyes.</p>
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<p>Optical images of 2024 modern paper: (<b>a</b>) uncoated and non-irradiated; (<b>b</b>) coated with a thin layer of CBP/TiO<sub>2</sub>; (<b>c</b>) uncoated and UVA irradiated; (<b>d</b>) coated with a thin layer of CBP/TiO<sub>2</sub> and UVA irradiated.</p>
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<p>Red–green–blue value distributions of 2024 modern paper comparing (<b>a</b>) uncoated (solid lines) and CBP/TiO<sub>2</sub> coated paper (dashed line); (<b>b</b>) uncoated paper (solid lines) and uncoated paper UVA-irradiated (dotted lines); (<b>c</b>) uncoated paper (solid lines), uncoated UVA-irradiated paper (dotted lines), CBP/TiO<sub>2</sub> coated UVA-irradiated paper (brown, light green, and cyan solid lines). (<b>d</b>) Magnification of red value distribution of uncoated paper (solid line), uncoated UVA-irradiated paper (dotted line), uncoated UVA irradiated paper (brown solid line).</p>
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<p>(<b>a</b>) Raman spectra acquired from 2024 paper before and after 31 h of UVA irradiation. (<b>b</b>,<b>c</b>) <span class="html-italic">C</span><sub>I</sub> marker value maps of uncoated 2024 paper non-irradiated and UVA-irradiated, respectively. (<b>d</b>) Raman spectra acquired from 2024 paper CBP/TiO<sub>2</sub> coated before and after 31 h of UVA irradiation. (<b>e</b>,<b>f</b>) <span class="html-italic">C</span><sub>I</sub> marker value maps of CBP/TiO<sub>2</sub> coated 2024 paper, non-irradiated and UVA-irradiated, respectively.</p>
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<p>(<b>a</b>,<b>b</b>) O<sub>T</sub> marker value maps of uncoated 2024 paper before and after 31 h of UVA irradiation, respectively. (<b>c</b>,<b>d</b>) O<sub>T</sub> marker value maps of CBP/TiO<sub>2</sub> coated 2024 paper before and after 31 h of UVA irradiation, respectively.</p>
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<p>(<b>a</b>) Marker variation in percentage after 31 h of UVA irradiation for the uncoated and coated 2024 paper. (<b>b</b>) Score plots of coated paper before (blue points) and after irradiation (fuchsia points). The PC1 component is the CBP/TiO<sub>2</sub> gel Raman spectrum, while PC2 component is the paper one.</p>
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<p>Optical images of 2021 paper naturally aged in laboratory: (<b>a</b>) uncoated; (<b>b</b>) coated with a thin layer of CBP/TiO<sub>2</sub>. (<b>c</b>) Red value distributions of 2021 paper naturally aged in laboratory: uncoated paper (solid line), CBP/TiO<sub>2</sub> coated paper (dashed line), uncoated UVA-irradiated paper (dotted line), CBP/TiO<sub>2</sub> coated UVA-irradiated paper.</p>
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<p>O<sub>T</sub> marker value maps for (<b>a</b>) uncoated paper, (<b>b</b>) UVA-irradiated uncoated paper, (<b>c</b>) coated paper, (<b>d</b>) UVA-irradiated coated paper. (<b>e</b>) Marker variation in percentage after 31 h of UVA irradiation for the uncoated and CBP/TiO<sub>2</sub> coated 2021 paper exposed to ambient light of laboratory for three years.</p>
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<p>CLSM images obtained in reflection mode of the 2021 paper: (<b>a</b>) uncoated; (<b>b</b>) CBP/TiO<sub>2</sub>-coated; (<b>c</b>) the intensity profiles measured along the yellow arrow; (<b>d</b>) marker variation percentage after 30 and 60 min of outdoor sun irradiation.</p>
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<p>Photo of hydrogel. On the left CBP gel (1–2–3) on the right CBP/TiO<sub>2</sub> gel (4–5–6).</p>
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16 pages, 11348 KiB  
Article
Thermal Degradation Study of Hydrogel Nanocomposites Based on Polyacrylamide and Nanosilica Used for Conformance Control and Water Shutoff
by Aleksey Telin, Farit Safarov, Ravil Yakubov, Ekaterina Gusarova, Artem Pavlik, Lyubov Lenchenkova and Vladimir Dokichev
Gels 2024, 10(12), 846; https://doi.org/10.3390/gels10120846 - 22 Dec 2024
Viewed by 405
Abstract
The application of nanocomposites based on polyacrylamide hydrogels as well as silica nanoparticles in various tasks related to the petroleum industry has been rapidly developing in the last 10–15 years. Analysis of the literature has shown that the introduction of nanoparticles into hydrogels [...] Read more.
The application of nanocomposites based on polyacrylamide hydrogels as well as silica nanoparticles in various tasks related to the petroleum industry has been rapidly developing in the last 10–15 years. Analysis of the literature has shown that the introduction of nanoparticles into hydrogels significantly increases their structural and mechanical characteristics and improves their thermal stability. Nanocomposites based on hydrogels are used in different technological processes of oil production: for conformance control, water shutoff in production wells, and well killing with loss circulation control. In all these processes, hydrogels crosslinked with different crosslinkers are used, with the addition of different amounts of nanoparticles. The highest nanoparticle content, from 5 to 9 wt%, was observed in hydrogels for well killing. This is explained by the fact that the volumes of injection of block packs are counted only in tens of cubic meters, and for the sake of trouble-free workover, it is very important to preserve the structural and mechanical properties of block packs during the entire repair of the well. For water shutoff, the volumes of nanocomposite injection, depending on the well design, are from 50 to 150 m3. For conformance control, it is required to inject from one to several thousand cubic meters of hydrogel with nanoparticles. Naturally, for such operations, service companies try to select compositions with the minimum required nanoparticle content, which would ensure injection efficiency but at the same time would not lose economic attractiveness. The aim of the present work is to develop formulations of nanocomposites with increased structural and mechanical characteristics based on hydrogels made of partially hydrolyzed polyacrylamide crosslinked with resorcinol and paraform, with the addition of commercially available nanosilica, as well as to study their thermal degradation, which is necessary to predict the lifetime of gel shields in reservoir conditions. Hydrogels with additives of pyrogenic (HCSIL200, HCSIL300, RX380) and hydrated (white carbon black grades: ‘BS-50’, ‘BS-120 NU’, ‘BS-120 U’) nanosilica have been studied. The best samples in terms of their structural and mechanical properties have been established: nanocomposites with HCSIL200, HCSIL300, and BS-120 NU. The addition of hydrophilic nanosilica HCSIL200 in the amount of 0.4 wt% to a hydrogel consisting of partially hydrolyzed polyacrylamide (1%), resorcinol (0.04%), and paraform (0.09%) increased its elastic modulus by almost two times and its USS by almost three times. The thermal degradation of hydrogels was studied at 140 °C, and the experimental time was converted to the exposure time at 80 °C using Van’t Hoff’s rule. It was found that the nanocomposite with HCSIL200 retains its properties at a satisfactory level for 19 months. Filtration studies on water-saturated fractured reservoir models showed that the residual resistance factor and selectivity of the effect of nanocomposites with HCSIL200 on fractures are very high (226.4 and 91.6 for fracture with an opening of 0.05 cm and 11.0 for porous medium with a permeability of 332.3 mD). The selectivity of the isolating action on fractured intervals of the porous formation was noted. Full article
(This article belongs to the Special Issue Chemical and Gels for Oil Drilling and Enhanced Recovery)
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<p>Schematic of the crosslinking reaction of polyacrylamide with paraform and resorcinol.</p>
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<p>Dynamics of pressure drop variation from injection volume.</p>
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<p>Dynamics of pressure drop variation from pore volume injection.</p>
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<p>Plate-to-plate measuring system.</p>
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<p>Sketch of finger-type autoclave.</p>
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<p>Schematic diagram of experimental unit SMP-FES-2R.</p>
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<p>Photo of the ideal fracture model. (<b>a</b>) photo of the sawn core; (<b>b</b>) photo of the sawn halves of the core with glued foil strips; (<b>c</b>) scheme of an ideal fracture [<a href="#B32-gels-10-00846" class="html-bibr">32</a>].</p>
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<p>Photo of the ideal fracture model. (<b>a</b>) photo of the sawn core; (<b>b</b>) photo of the sawn halves of the core with glued foil strips; (<b>c</b>) scheme of an ideal fracture [<a href="#B32-gels-10-00846" class="html-bibr">32</a>].</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 460
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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<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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22 pages, 3287 KiB  
Article
The Use of AgNP-Containing Nanocomposites Based on Galactomannan and κ-Carrageenan for the Creation of Hydrogels with Antiradical Activity
by Marina Zvereva
Gels 2024, 10(12), 800; https://doi.org/10.3390/gels10120800 - 6 Dec 2024
Viewed by 511
Abstract
Series of composites containing 2.5–17.0% Ag and consisting of spherical silver nanoparticles with sizes ranging from 5.1 to 18.3 nm and from 6.4 to 21.8 nm for GM- and κ-CG-based composites, respectively, were prepared using the reducing and stabilizing ability of the natural [...] Read more.
Series of composites containing 2.5–17.0% Ag and consisting of spherical silver nanoparticles with sizes ranging from 5.1 to 18.3 nm and from 6.4 to 21.8 nm for GM- and κ-CG-based composites, respectively, were prepared using the reducing and stabilizing ability of the natural polysaccharides galactomannan (GM) and κ-carrageenan (κ-CG). The antiradical activity of the obtained composites was evaluated using the decolorization of ABTS+· solution. It was found that the IC50 value of a composite’s aqueous solution depends on the type of stabilizing ligand, the amount of inorganic phases, and the average size of AgNPs, and varies in the range of 0.015–0.08 mg·mL−1 and 0.03–0.59 mg·mL−1 for GM-AgNPs − κ-CG-AgNPs composites, respectively. GM-AgNPs − κ-CG-AgNPs hydrogels were successfully prepared and characterized on the basis of composites containing 2.5% Ag (demonstrating the most pronounced antiradical activity in terms of IC50 values per mole amount of Ag). It was found that the optimal ratio of composites that provided the best water-holding capacity and prolonged complete release of AgNPs from the hydrogel composition was 1:1. The influence of Ca2+ cations on the co-gel formation of the GM-AgNPs − κ-CG-AgNPs system, as well as the expression of their water-holding capacity and the rate of AgNPs release from the hydrogel carrier, was evaluated. Full article
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<p>XRD diffractograms of AgNP composites based on GM (<b>a</b>–<b>c</b>) and κ-CG (<b>d</b>–<b>f</b>) with different percentages of silver nanoparticles.</p>
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<p>Microphotographs (TEM) of AgNP composites based on GM (<b>a</b>–<b>c</b>) and κ-CG (<b>d</b>–<b>f</b>) with different percentages of silver.</p>
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<p>Absorption spectra of 0.05% aqueous solutions of AgNP composites based on GM (<b>a</b>) and κ-CG (<b>b</b>) with different silver contents.</p>
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<p>Intensity distribution of Rh particles in 0.1% aqueous solutions of κ-CG (<b>a</b>) and κ-CG-AgNPs composites with 2.5% and 7.0% Ag (<b>b</b>,<b>c</b>), respectively.</p>
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<p>Radical-binding ability of GM-AgNPs (<b>a</b>) and κ-CG-AgNPs (<b>b</b>) composites against ABTS<sup>+</sup>·; dependence of the IC<sub>50</sub> parameter on the silver concentration in the GM and κ-CG-based nanocomposites (<b>c</b>). Error bars are hidden in the bar when not visible; data are mean ± SD, <span class="html-italic">n</span> ≥ 3.</p>
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<p>Water-holding capacity of AgNP-containing hydrogels based on the GM-κ-CG system in the absence (<b>a</b>) and presence (<b>b</b>) of Ca<sup>2+</sup> ions. Error bars are hidden in the bar when not visible; data are mean ± SD, <span class="html-italic">n</span> ≥ 3.</p>
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<p>Effect of GM-AgNPs-κ-CG-AgNPs ratio on the stress–strain dependence of hydrogels (<b>a</b>) and their elastic modulus (<b>b</b>).</p>
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<p>AgNPs release dynamics from hydrogels based on the GM-AgNPs/κ-CG-AgNPs system with different composite ratios in the absence (<b>a</b>) and presence of Ca<sup>2+</sup> ions (<b>b</b>); Ag+ concentration dynamics in aqueous medium within the dissolution of hydrogels based on the GM-AgNPs/κ-CG-AgNPs system in the presence of Ca<sup>2+</sup> ions with different composite ratios (<b>c</b>). Error bars are hidden in the bar when not visible; data are mean ± SD, <span class="html-italic">n</span> ≥ 3.</p>
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21 pages, 3538 KiB  
Article
Hemostatic Antimicrobial Hydrogels Based on Silicon, Iron, Zinc, and Boron Glycerolates for Wound Healing Applications
by Tat’yana Khonina, Semyon Alekseenko, Elena Shadrina, Il’ya Ganebnykh, Alexander Mekhaev, Leonid Larionov, Maria Dobrinskaya, Nadezhda Izmozherova, Irina Antropova, Maxim Karabanalov, Muza Kokhan, Natali’ya Evstigneeva and Oleg Chupakhin
Gels 2024, 10(12), 795; https://doi.org/10.3390/gels10120795 - 5 Dec 2024
Viewed by 723
Abstract
The use of glycerolates of biogenic elements as biocompatible precursors in sol–gel synthesis is an innovative direction and opens up new scientific and practical prospects in chemistry and technology of producing practically important biomedical materials, including hemostatic, antimicrobial, and wound healing materials. Using [...] Read more.
The use of glycerolates of biogenic elements as biocompatible precursors in sol–gel synthesis is an innovative direction and opens up new scientific and practical prospects in chemistry and technology of producing practically important biomedical materials, including hemostatic, antimicrobial, and wound healing materials. Using biocompatible precursors, silicon, zinc, boron, and iron glycerolates, new bioactive nanocomposite hydrogels were obtained by the sol–gel method. The composition and structural features of the hydrogels were studied using a complex of modern analytical techniques, including TEM, XRD, AES, and ESI MS. Hemostatic activity of the hydrogels was studied in the in vivo experiments; using the example of silicon-iron-zinc-boron glycerolates hydrogel, primary toxicological studies were carried out. Antimicrobial properties of hydrogels were studied using the agar diffusion method. The structural features of hydrogels and their relationship to medical and biological properties were revealed. It was shown that glycerolates hydrogels are non-toxic, and exhibit pronounced hemostatic activity, generally comparable to the commercial hemostatic drug Capramine. Antimicrobial activity is more pronounced for silicon-iron-zinc-boron and silicon-iron-boron glycerolates gel. The results obtained indicate that these glycerolates hydrogels are potential hemostatic and antibiotic-independent antimicrobial agents for topical wound healing applications in medical and veterinary practice. Full article
(This article belongs to the Special Issue Designing Gels for Antibacterial and Antiviral Agents)
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Graphical abstract

Graphical abstract
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<p>The biocompatible precursors used in the sol–gel synthesis of the glycerolates hydrogels: (<b>a</b>) silicon tetraglycerolate, (<b>b</b>) boron bisglycerolates, (<b>c</b>) zinc monoglycerolate, and (<b>d</b>) iron(III) monoglycerolate.</p>
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<p>IR spectra of (<b>a</b>) Si-Fe– (for comparison), (<b>b</b>) Si-Fe-Zn–, (<b>c</b>) Si-Fe-B–, and (<b>d</b>) Si-Fe-Zn-B–gel.</p>
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<p>TEM micrographs of dried suspension: (<b>a</b>) Si-Fe–(for comparison), (<b>b</b>) Si-Fe-Zn–, (<b>c</b>) Si-Fe-B–, (<b>d</b>) Si-Fe-Zn-B–gel in ethanol. (<b>a</b>–<b>d</b>) High-resolution TEM image, inserts show electron diffraction area.</p>
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<p>Thermal analysis data for (<b>a</b>) Si-Fe–, (<b>b</b>) Si-Fe-Zn–, (<b>c</b>) Si-Fe-B–, (<b>d</b>) Si-Fe-Zn-B–gel.</p>
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<p>ESI mass spectrum in negative mode of Si-Fe-Zn-B–gel liquid medium (* averaged for scan number from 60 to 80).</p>
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<p>XRD patterns of extracted solid phase of (<b>a</b>) Si-Fe– (for comparison), (<b>b</b>) Si-Fe-Zn–gel, (<b>c</b>) Si-Fe-B–gel, and (<b>d</b>) Si-Fe-Zn-B–gel.</p>
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<p>Histological analysis of Si-Fe-Zn-B–gel treated group 14 days after administration, hematoxylin-eosin, magnification ×100.</p>
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<p>Comparative assessment of bleeding time in mice with incised liver wounds.</p>
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<p>Strain growth inhibition zones: (<b>1</b>) <span class="html-italic">E. coli</span> ATCC 8739; (<b>2</b>) <span class="html-italic">P. aeruginosa</span> ATCC 9027; (<b>3</b>) clinical strain <span class="html-italic">S. aureus</span> (MRSA); (<b>4</b>) <span class="html-italic">S. pyogenes</span> ATCC 19615. (<b>5</b>) <span class="html-italic">C. albicans</span> RCPF <sub>Y</sub>-401/NCTC-885-653: (<b>a</b>) Si-Fe-Zn-B-gel; (<b>b</b>) positive control; (<b>c</b>) silicon glycerolates gel (negative control).</p>
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21 pages, 7677 KiB  
Article
Thermo-Responsive and Electroconductive Nano Au-PNiPAAm Hydrogel Nanocomposites: Influence of Synthesis Method and Nanoparticle Shape on Physicochemical Properties
by Nikolina Radojković, Jelena Spasojević, Zorica Kačarević-Popović, Una Stamenović, Vesna Vodnik, Goran Roglić and Aleksandra Radosavljević
Polymers 2024, 16(23), 3416; https://doi.org/10.3390/polym16233416 - 5 Dec 2024
Viewed by 772
Abstract
Hydrogel nanocomposites that respond to external stimuli and possess switchable electrical properties are considered as emerging materials with potential uses in electrical, electrochemical, and biological devices. This work reports the synthesis and characterization of thermo-responsive and electroconductive hydrogel nanocomposites based on poly(N [...] Read more.
Hydrogel nanocomposites that respond to external stimuli and possess switchable electrical properties are considered as emerging materials with potential uses in electrical, electrochemical, and biological devices. This work reports the synthesis and characterization of thermo-responsive and electroconductive hydrogel nanocomposites based on poly(N-isopropylacrylamide) (PNiPAAm) and gold nanoparticles (nanospheres—AuNPs and nanorods—AuNRs) using two different synthetic techniques. Method I involved γ-irradiation-induced crosslinking of a polymer matrix (hydrogel), followed by radiolytic in situ formation of gold nanoparticles, while Method II included the chemical synthesis of nanoparticles, followed by radiolytic formation of a polymer matrix around the gold nanoparticles. UV–Vis spectral studies revealed the presence of local surface plasmon resonance (LSPR) bands characteristic of nanoparticles of different shapes, confirming their formation and stability inside the polymer matrix. Morphological, structural, and physicochemical analyses indicated the existence of a stable porous polymer matrix, the formation of nanoparticles with a face-centered cubic structure, increased swelling capacity, and a slightly higher volume phase transition temperature (VPTT) for the hydrogel nanocomposites. Comparative electrochemical impedance spectroscopy (EIS) showed an increase in conductivity for the nano Au-PNiPAAm hydrogel nanocomposites compared to the PNiPAAm hydrogel, with a considerable rise detected above the VPTT. By reverting to room temperature, the conductivity decreased, indicating that the investigated hydrogel nanocomposites exhibited a remarkable reversible “on–off” thermo-switchable mechanism. The highest conductivity was observed for the sample with rod-shaped gold nanoparticles. The research findings, which include optical, structural, morphological, and physicochemical characterization, evaluation of the efficiency of the chosen synthesis methods, and conductivity testing, provide a starting point for future research on the given nanocomposite materials with integrated multifunctionality. Full article
(This article belongs to the Special Issue Polymer Hydrogels: Synthesis, Properties and Applications)
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<p>Schematic representation of synthesis: Method I (<b>a</b>), Method II (<b>b</b>), and photographs of nano Au-PNiPAAm hydrogel nanocomposites obtained by Method II (<b>c</b>).</p>
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<p>UV–Vis absorption spectra of AuNPs-PNiPAAm (<b>a</b>) and AuNRs-PNiPAAm (<b>b</b>) hydrogel nanocomposites obtained by Method I.</p>
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<p>UV–Vis absorption spectra of chemically synthesized colloidal dispersion of AuNPs and AuNRs (<b>a</b>), AuNPs-PNiPAAm (<b>b</b>), and AuNRs-PNiPAAm (<b>c</b>) hydrogel nanocomposites obtained by Method II.</p>
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<p>TEM micrographs of chemically synthesized AuNPs (<b>a</b>) and AuNRs (<b>b</b>), with corresponding particle size distribution (PSD, (<b>a</b>,<b>b</b>) upper-left insets), HRTEM images ((<b>a</b>,<b>b</b>) upper-right insets), and SAED ((<b>a</b>,<b>b</b>) lower-right insets), and FE-SEM micrographs of the AuNPs-PNiPAAm hydrogel nanocomposites obtained by the Method I (<b>c</b>) and AuNRs-PNiPAAm hydrogel nanocomposites obtained by the Method II (<b>d</b>).</p>
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<p>The swelling behavior (<b>a</b>–<b>c</b>), temperature dependence of <span class="html-italic">SD<sub>eq</sub></span> (<b>d</b>–<b>f</b>), and deswelling curves (<b>g</b>–<b>i</b>) of AuNPs-PNiPAAm and AuNRs-PNiPAAm hydrogel nanocomposites.</p>
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<p>XRD patterns (<b>a</b>) and FTIR spectra (<b>b</b>) of nano Au-PNiPAAm hydrogel nanocomposites.</p>
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<p>Bode plots of the impedance magnitude (<b>a</b>–<b>c</b>) and Nyquist plots for the real and the imaginary impedances (<b>d</b>–<b>f</b>) for PNiPAAm hydrogel and AuNPs-PNiPAAm and AuNRs-PNiPAAm hydrogel nanocomposites (c(NPs) = 2.5 × 10<sup>−4</sup> mol/dm<sup>3</sup>) obtained by Method II (<span style="color:red">•</span> Initial T = 25 °C, <span style="color:#5BDF41">•</span> T = 40 °C, <span style="color:#0C2DF4">•</span> Final T = 25 °C).</p>
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<p>An equivalent electrical circuit used for the impedance plot fitting of the hydrogel nanocomposites.</p>
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<p>The electrical conductivity (<b>a</b>) and resistance (<b>b</b>) of PNiPAAm hydrogel and nano Au-PNiPAAm hydrogel nanocomposites.</p>
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19 pages, 6572 KiB  
Article
Calcium Alginate/Laponite Nanocomposite Hydrogels: Synthesis, Swelling, and Sorption Properties
by Yurii Samchenko, Konrad Terpilowski, Kateryna Samchenko, Lyudmila Golovkova, Olena Oranska and Olena Goncharuk
Coatings 2024, 14(12), 1519; https://doi.org/10.3390/coatings14121519 - 2 Dec 2024
Viewed by 757
Abstract
This study presents the synthesis, characterization, and evaluation of hybrid hydrogels based on calcium alginate (Ca-Alg) and synthetic nanoclay LaponiteRD (Lap), with an emphasis on their swelling and sorption properties. The motivation behind the development of these hybrid hydrogels stems from the need [...] Read more.
This study presents the synthesis, characterization, and evaluation of hybrid hydrogels based on calcium alginate (Ca-Alg) and synthetic nanoclay LaponiteRD (Lap), with an emphasis on their swelling and sorption properties. The motivation behind the development of these hybrid hydrogels stems from the need for sustainable materials with enhanced mechanical strength, swelling properties, and sorption capacity for environmental remediation and controlled-release applications. Synthesis methods for the ionotropically cross-linked Ca-Alg hydrogel and Alg–Lap composite hydrogels, based on Alg and Lap in the form of granules and fibres, have been developed. The Fourier-transform infrared spectroscopy (FTIR), Energy-dispersive X-ray spectroscopy (EDX), and X-ray diffraction (XRD) analyses of composite hydrogels confirmed the successful incorporation of Lap into the Ca-Alg matrix, indicating strong interactions between the polymer and clay, which enhanced the structural integrity of the hydrogels. The morphology of the surface and pore structure of nanocomposites were studied using Scanning Electron Microscopy (SEM). The swelling behaviour of the nanocomposites was largely dependent on the concentrations of Lap and the cross-linking agent (CaCl2), with higher concentrations leading to more rigid, less swellable structures due to the increased cross-linking density. The sorption studies, specifically with Fe(II) ions, demonstrated that the hybrid hydrogels possess a large sorption capacity, with Lap contributing to selective sorption at lower Fe(II) ion concentrations and Alg enhancing overall capacity at higher concentrations. This suggests that the synergistic interaction between Alg and Lap not only improves mechanical stability but also tailors the sorption properties of the hydrogels. These findings position the Alg-Lap hydrogels as promising materials for a range of environmental applications, including wastewater treatment, heavy metal ion removal, and the design of advanced filtration systems. The study’s insights into the tunability of these hydrogels pave the way for further research into their use in diverse fields such as biomedicine, agriculture, and industrial water management. Full article
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<p>FTIR spectra of Na- (curve 1) and Ca-Alg (curve 2), Lap (curve 3), and Alg-Lap composite based on them (curve 4).</p>
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<p>XRD patterns for the LaponiteRD and the Alg-Lap composite hydrogels with different component ratios: (<b>a</b>) full 2θ° range and (<b>b</b>) the first peak from 5 to 20 of 2θ°.</p>
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<p>SEM micrographs of alginate gel (C<sub>Alg</sub> = 2 wt% in reaction solution) (<b>a</b>) and Alg-Lap composite hydrogel (<b>b</b>) (C<sub>Alg</sub> = 2 wt%, C<sub>Lap</sub> = 1.25 wt%, C<sub>CaCl2</sub> = 0.5 wt% in reaction solution) (zoom 37× (<b>a</b>) and 39× (<b>b</b>)).</p>
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<p>Cross-section of Alg-Lap (C<sub>Alg</sub> = 2 wt%, C<sub>Lap</sub> = 1.25 wt%, C<sub>CaCl2</sub> = 0.5 wt% in reaction solution) composite (zoom 126× (<b>a</b>), 379× (<b>b</b>), 1260× (<b>c</b>), and 12,600× (<b>d</b>)).</p>
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<p>Surface of alginate gel (<b>a</b>) and Alg-Lap (C<sub>Alg</sub> = 2 wt%, C<sub>Lap</sub> = 1.25 wt%, C<sub>CaCl2</sub> = 0.5 wt% in reaction solution) composite (<b>b</b>). Zoom 1260×.</p>
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<p>Comparison of cross-section of alginate gel (<b>a</b>) and Alg-Lap (C<sub>Alg</sub> = 2 wt%, C<sub>Lap</sub> = 1.25 wt%, C<sub>CaCl2</sub> = 0.5 wt% in reaction solution) composite (<b>b</b>). Zoom 379×.</p>
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<p>Area of Ca-Alg (<b>a</b>) and Alg-Lap composite (<b>b</b>) selected for EDX analysis and comparison of EDX-spectra of Ca-Alg (<b>c</b>) and Alg-Lap composite (<b>d</b>).</p>
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<p>Swelling kinetics of nanocomposites based on Ca-Alg and Lap at low and high CaCl<sub>2</sub> concentrations (C<sub>Alg</sub> = 2 wt%; C<sub>Lap</sub> = 1 wt% in reaction solution).</p>
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<p>Changes in the size of hydrogel beads based on Ca-Alg and Lap (C<sub>Alg</sub> = 2 wt%, C<sub>Lap</sub> = 0.5 wt%, C<sub>CaCl2</sub> = 0.5 wt% in the reaction solution) during processing: (<b>a</b>) after synthesis; (<b>b</b>) after swelling; (<b>c</b>) after drying.</p>
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<p>Visualization of dry Alg-Lap bead (C<sub>Lap</sub> = 1 wt%; C<sub>Alg</sub> = 2 wt%; C<sub>CaCl2</sub> = 0.25 wt% in the reaction solution) swelling during the first three hours.</p>
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<p>Dependencies according to the Peppas and Ritger equation for determining the type of diffusion in the Alg gel and the Alg-Lap composites: (<b>a</b>) C<sub>Alg</sub> = 2 wt%, C<sub>CaCl2</sub>= 0.5 wt%; (<b>b</b>) C<sub>Alg</sub> = 2 wt%, C<sub>Lap</sub> = 2 wt%, in reaction solution.</p>
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<p>Adsorption isotherms of Fe(II) on the Alg-based composites filled with Lap (<b>a</b>) and the effect of Fe(II) sorption on the degree of swelling (<b>b</b>) of hybrid hydrogels.</p>
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23 pages, 8866 KiB  
Article
New Carrageenan/2-Dimethyl Aminoethyl Methacrylate/Gelatin/ZnO Nanocomposite as a Localized Drug Delivery System with Synergistic Biomedical Applications
by Abeer A. Ageeli and Sahera F. Mohamed
Processes 2024, 12(12), 2702; https://doi.org/10.3390/pr12122702 - 30 Nov 2024
Viewed by 875
Abstract
In recent years, the development of multifunctional hydrogels has gained significant attention due to their potential in various biomedical applications, including antimicrobial, antioxidant, and anticancer therapies. By integrating biocompatible polymers and nanoparticles, these hydrogels can achieve enhanced activity and targeted therapeutic effects. In [...] Read more.
In recent years, the development of multifunctional hydrogels has gained significant attention due to their potential in various biomedical applications, including antimicrobial, antioxidant, and anticancer therapies. By integrating biocompatible polymers and nanoparticles, these hydrogels can achieve enhanced activity and targeted therapeutic effects. In this study, carrageenan/2-dimethyl aminoethyl methacrylate/gelatin (CAR/DEMA/Gelt) composite hydrogel was synthesized using microwave radiation specifically for its efficiency in enhancing cross-linking and promoting uniform nanoparticle dispersion within the matrix. Zinc oxide (ZnO) nanoparticles were incorporated into the hydrogel to form the (CAR/DEMA/Gelt/ZnO) nanocomposite. The hydrogels were characterized using FT-IR, FE-SEM, XRD, TGA, and EDX, confirming successful cross-linking and structural integrity. The nanocomposite hydrogel exhibited more enhanced antimicrobial activity than the composite hydrogel against Gram-positive Staphylococcus aureus (S. aureus) and Bacillus subtilis (B. subtilis), with inhibition zones of 15 mm and 16 mm, respectively, while in case of the Gram-negative bacteria, Klebsiella pneumoniae (K. pneumoniae) and Escherichia coli (E. coli), the inhibition zones were 29 mm and 19 mm, respectively. In addition to the unicellular fungi, Candida albicans (C. albicans), the inhibition zone was 19 mm. Moreover, the nanocomposite showed anti-inflammatory activity comparable to those of Indomethacin and antioxidant activity, with an impressive IC50 value of 33.3 ± 0.05 µg/mL. In vitro cytotoxicity assays revealed significant anticancer activity. Against the MCF-7 breast cancer cell line, the CAR/DEMA/Gelt/ZnO nanocomposite showed 72.5 ± 0.02% cell viability, which decreased to 30.8 ± 0.01% after loading doxorubicin (DOX). Similarly, against the HepG2 liver cancer cell line, the free nanocomposite displayed 59.9 ± 0.006% cell viability, which depleted to 29.9 ± 0.005% when DOX was uploaded. This CAR/DEMA/Gelt/ZnO nanocomposite hydrogel demonstrates strong potential as a multifunctional platform for targeted biomedical applications, particularly in cancer therapy. Full article
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<p>FTIR analysis of (<b>a</b>) ZnO nanoparticles, (<b>b</b>) DOX powder, and (<b>c</b>) CAR/DEMA/Gelt hydrogel, CAR/DEMA/Gelt/ZnO nanocomposite, and CAR/DEMA/Gelt/ZnO/DOX.</p>
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<p>FTIR analysis of (<b>a</b>) ZnO nanoparticles, (<b>b</b>) DOX powder, and (<b>c</b>) CAR/DEMA/Gelt hydrogel, CAR/DEMA/Gelt/ZnO nanocomposite, and CAR/DEMA/Gelt/ZnO/DOX.</p>
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<p>XRD patterns of (<b>a</b>) ZnO nanoparticles and (<b>b</b>) CAR/DEMA/Gelt hydrogel and CAR/DEMA/Gelt/ZnO nanocomposite.</p>
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<p>TGA (<b>a</b>) and DTA (<b>b</b>) analysis of CAR/DEMA/Gelt hydrogel and CAR/DEMA/Gelt/ZnO nanocomposite.</p>
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<p>FE-SEM of CAR/DEMA/Gelt hydrogel, CAR/DEMA/Gelt/ZnO nanocomposite, and CAR/DEMA/Gelt/ZnO/DOX nanocomposite.</p>
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<p>(<b>a</b>) EDX elemental analysis and mapping of the CAR/DEMA/Gelt hydrogel. (<b>b</b>) EDX elemental analysis and mapping of the CAR/DEMA/Gelt/ZnO nanocomposite hydrogel.</p>
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<p>(<b>a</b>) EDX elemental analysis and mapping of the CAR/DEMA/Gelt hydrogel. (<b>b</b>) EDX elemental analysis and mapping of the CAR/DEMA/Gelt/ZnO nanocomposite hydrogel.</p>
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<p>Antimicrobial activity of the CAR/DEMA/Gelt hydrogel (i) and the CAR/DEMA/Gelt/ZnO nanocomposite (ii).</p>
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<p>Antimicrobial activity of the CAR/DEMA/Gelt hydrogel (i) and the CAR/DEMA/Gelt/ZnO nanocomposite (ii).</p>
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<p>Anti-inflammatory activity of the CAR/DEMA/Gelt/ZnO nanocomposite using Indomethacin as a control.</p>
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<p>Antioxidant activity of the CAR/DEMA/Gelt/ZnO nanocomposite using ascorbic acid as a control.</p>
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<p>(<b>a</b>) The cell viability and cytotoxicity (%) data for CAR/DEMA/Gelt/ZnO and CAR/DEMA/Gelt/ZnO/DOX against MCF-7. (<b>b</b>) Effects of CAR/DEMA/Gelt/ZnO and CAR/DEMA/Gelt/ZnO/DOX on MCF-7 cells.</p>
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<p>(<b>a</b>) The cell viability and cytotoxicity (%) data for CAR/DEMA/Gelt/ZnO and CAR/DEMA/Gelt/ZnO/DOX against MCF-7. (<b>b</b>) Effects of CAR/DEMA/Gelt/ZnO and CAR/DEMA/Gelt/ZnO/DOX on MCF-7 cells.</p>
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<p>(<b>a</b>) The cell viability and cytotoxicity (%) data for CAR/DEMA/Gelt/ZnO and CAR/DEMA/Gelt/ZnO/DOX against the HepG2 cell line. (<b>b</b>) Effects of CAR/DEMA/Gelt/ZnO and CAR/DEMA/Gelt/ZnO/DOX on HepG2 cells.</p>
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<p>(<b>a</b>) The cell viability and cytotoxicity (%) data for CAR/DEMA/Gelt/ZnO and CAR/DEMA/Gelt/ZnO/DOX against the HepG2 cell line. (<b>b</b>) Effects of CAR/DEMA/Gelt/ZnO and CAR/DEMA/Gelt/ZnO/DOX on HepG2 cells.</p>
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23 pages, 3053 KiB  
Review
Carbon Based Polymeric Nanocomposite Hydrogel Bioink: A Review
by Alle Madhusudhan, Tejaskumar A. Suhagia, Chhavi Sharma, Saravana Kumar Jaganathan and Shiv Dutt Purohit
Polymers 2024, 16(23), 3318; https://doi.org/10.3390/polym16233318 - 27 Nov 2024
Viewed by 721
Abstract
Carbon-based polymeric nanocomposite hydrogels (NCHs) represent a groundbreaking advancement in biomedical materials by integrating nanoparticles such as graphene, carbon nanotubes (CNTs), carbon dots (CDs), and activated charcoal (AC) into polymeric matrices. These nanocomposites significantly enhance the mechanical strength, electrical conductivity, and bioactivity of [...] Read more.
Carbon-based polymeric nanocomposite hydrogels (NCHs) represent a groundbreaking advancement in biomedical materials by integrating nanoparticles such as graphene, carbon nanotubes (CNTs), carbon dots (CDs), and activated charcoal (AC) into polymeric matrices. These nanocomposites significantly enhance the mechanical strength, electrical conductivity, and bioactivity of hydrogels, making them highly effective for drug delivery, tissue engineering (TE), bioinks for 3D Bioprinting, and wound healing applications. Graphene improves the mechanical and electrical properties of hydrogels, facilitating advanced tissue scaffolding and drug delivery systems. CNTs, with their exceptional mechanical strength and conductivity, enhance rheological properties, facilitating their use as bioinks in supporting complex 3D bioprinting tasks for neural, bone, and cardiac tissues by mimicking the natural structure of tissues. CDs offer fluorescence capabilities for theranostic applications, integrating imaging and therapeutic functions. AC enhances mechanical strength, biocompatibility, and antibacterial effectiveness, making it suitable for wound healing and electroactive scaffolds. Despite these promising features, challenges remain, such as optimizing nanoparticle concentrations, ensuring biocompatibility, achieving uniform dispersion, scaling up production, and integrating multiple functionalities. Addressing these challenges through continued research and development is crucial for advancing the clinical and industrial applications of these innovative hydrogels. Full article
(This article belongs to the Special Issue Polymeric Nanocomposites: Synthesis and Applications)
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<p>A recyclable composite formation with self-assembly of carbon dots during digital—processing 3D printing of vanillin Schiff-base resin.</p>
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<p>(a) The illustration of cell-laden pNHG hydrogel preparation. (b) The white pNHG solid powder is dissolved in cell solution (around 20 °C) first, and the cell-loaded solution is transferred to a Petri plate, then the Petri plate is put in a cell incubator with 95% air and 5% CO<sub>2</sub> at 37 °C. Once the cell-laden hydrogel is formed, more cell medium is added for further cell growth. (c) Fluorescent images of hBMSCs encapsulated in pNHG2 hydrogels over days; the cells are stained with DAPI (blue) and Phalloidin-FITC (green). (d) The illustration of hBMSCs-laden pNHG2 hydrogel injected in the neck of SD rat. (e) Optical micrographs of H&amp;E, Masson, and Safranin staining slices of surrounding tissues after injection of hBMSCs-laden pNHG2 hydrogel subcutaneously over days. Adapted with permission from [<a href="#B17-polymers-16-03318" class="html-bibr">17</a>]. Copyright Elsevier 2022.</p>
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<p>Morphological comparison between polymeric and CNT containing polymeric 3D printed vessel scaffolds. (<b>A</b>,<b>B</b>) Radial and axial views of printed vessel scaffolds, with an average diameter of 3.5 mm and wall thickness of 0.5 mm. (<b>C</b>) Multi-sized tubes with outer diameters of 3, 4, and 5 mm. (<b>D</b>,<b>E</b>) Macroscopic comparison between scaffolds incorporating carbon nanotubes (CNT) and blank (non-CNT) scaffolds. (<b>F</b>) Vessel scaffold structures produced using rotation-axis versus vertical-stacking methods. (<b>G</b>,<b>H</b>) Polarizing microscope images (10× magnification) comparing Gel-SA-1%C and Gel-SA-0.5%C scaffold groups. Adapted with permission from [<a href="#B25-polymers-16-03318" class="html-bibr">25</a>].</p>
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<p>Schematic of a three-layer liquid sensor: (<b>a</b>) The sensor includes a non-conductive (SI500) layer, a PEGDA hydrogel layer, and a PEGDA/MWCNT hydrogel layer. (<b>b</b>) In wet conditions, the PEGDA layer’s resistivity decreases due to water-facilitated electron transport, while the PEGDA/MWCNT layer’s resistivity increases as MWCNT spacing expands. (<b>c</b>) the conductivity of PEGDA/MWCNT composite hydrogel by swelling behavior in wetting and drying state. Adapted from [<a href="#B80-polymers-16-03318" class="html-bibr">80</a>].</p>
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30 pages, 3826 KiB  
Review
Exosome-Integrated Hydrogels for Bone Tissue Engineering
by Hee Sook Hwang and Chung-Sung Lee
Gels 2024, 10(12), 762; https://doi.org/10.3390/gels10120762 - 23 Nov 2024
Viewed by 659
Abstract
Exosome-integrated hydrogels represent a promising frontier in bone tissue engineering, leveraging the unique biological properties of exosomes to enhance the regenerative capabilities of hydrogels. Exosomes, as naturally occurring extracellular vesicles, carry a diverse array of bioactive molecules that play critical roles in intercellular [...] Read more.
Exosome-integrated hydrogels represent a promising frontier in bone tissue engineering, leveraging the unique biological properties of exosomes to enhance the regenerative capabilities of hydrogels. Exosomes, as naturally occurring extracellular vesicles, carry a diverse array of bioactive molecules that play critical roles in intercellular communication and tissue regeneration. When combined with hydrogels, these exosomes can be spatiotemporally delivered to target sites, offering a controlled and sustained release of therapeutic agents. This review aims to provide a comprehensive overview of the recent advancements in the development, engineering, and application of exosome-integrated hydrogels for bone tissue engineering, highlighting their potential to overcome current challenges in tissue regeneration. Furthermore, the review explores the mechanistic pathways by which exosomes embedded within hydrogels facilitate bone repair, encompassing the regulation of inflammatory pathways, enhancement of angiogenic processes, and induction of osteogenic differentiation. Finally, the review addresses the existing challenges, such as scalability, reproducibility, and regulatory considerations, while also suggesting future directions for research in this rapidly evolving field. Thus, we hope this review contributes to advancing the development of next-generation biomaterials that synergistically integrate exosome and hydrogel technologies, thereby enhancing the efficacy of bone tissue regeneration. Full article
(This article belongs to the Special Issue Recent Advances in Hydrogels for Biomedical Application (2nd Edition))
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<p>Exosome-integrated hydrogels for bone tissue engineering. Exosomes, which develop from the endosomal system within cells, are packed with proteins, lipids, and nucleic acids that facilitate robust intercellular communication. Exosomes, typically around 40–100 nm in size, belong to a diverse group of extracellular vesicles, set apart by their phospholipid membrane and specific formation pathway. They are released by a variety of cell types and circulate in bodily fluids, with their molecular composition reflecting the origin and condition of the parent cell. Exosomes can be isolated and fabricated through differential centrifugation, density gradient centrifugation, ultrafiltration, size exclusion chromatography, affinity nanoparticle-based isolation, polymer precipitation, microfluidic technologies, etc. Exosomes contain diverse bioactive molecules such as proteins, nucleic acids, and lipids, with two main types of proteins: general markers (like CD9, CD63, and CD81) and proteins unique to their parent cell. Exosomes can be modified with drug loading, active targeting, and stimuli-responsiveness. Hydrogels have become valuable tools in biomedical applications for exosome delivery. Hydrogels, as water-retentive polymer networks, encapsulate exosomes, improving their retention at target sites and providing controlled release to enhance localized effects. These exosome–hydrogel composites show promise in areas such as bone tissue engineering and treatment. (Created with <a href="https://biorender.com" target="_blank">https://biorender.com</a>).</p>
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<p>Human umbilical cord mesenchymal stem cell-derived exosomes with hydroxyapatite-embedded hyaluronic acid-alginate hydrogel for bone regeneration. (<b>A</b>) Schematic illustration of human umbilical cord mesenchymal stem cell-derived exosomes with hydroxyapatite-embedded hyaluronic acid-alginate hydrogel. (<b>B</b>) Transmission electron microscopy image of exosomes. (<b>C</b>) Size distribution of exosomes. (<b>D</b>) Western blot analysis of the exosome surface markers. (<b>E</b>) Release profiles of exosomes from the hydrogels with or without hydroxyapatite. * <span class="html-italic">p</span> &lt; 0.05 compared to the control group; <sup>#</sup> <span class="html-italic">p</span> &lt; 0.05 compared to the hydrogel group. (<b>F</b>) Confocal microscopy images of hydrogel with or without red fluorescence DiI-labeled exosomes. (<b>G</b>) Reconstructed 3D micro-CT images of the exosome-integrated hydrogels. Red circles indicate the defect area. (<b>H</b>) Quantitative analysis of bone regeneration using bone volume/tissue volume (BV/TV). Reproduced with permission from Yang et al. [<a href="#B164-gels-10-00762" class="html-bibr">164</a>].</p>
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<p>Exosome (Exo)-encapsulated stem cell-recruitment hydrogel microcarriers for osteoarthritis (OA) treatment. (<b>A</b>) Schematic illustration of Exo-encapsulated stem cell recruitment particles for OA treatment. (<b>a</b>) Hyaluronic acid (HA) and gelatin-based polymer matrix and bioactive components of hydrogel microcarriers. (<b>b</b>) Fabrication process of hydrogel microcarriers. (<b>c</b>) Application of microcarriers for OA treatment. (<b>B</b>–<b>D</b>) Characterization of particles and Exo. (<b>B</b>) Microscopic image of the particles. (<b>C</b>) The enlarged view of (<b>B</b>). (<b>D</b>) The size distribution of the particles. (<b>E</b>,<b>F</b>) H&amp;E and Safranin O-fast green staining results. (<b>E</b>) H&amp;E results after different particle treatments. (<b>F</b>) Safranin O-fast green staining results after the particle treatment. Par = microfluidic electrospray-generated hydrogel particles; Par@Pep = Par modified by SKPPGTSS peptides; Par@Exo = Par loaded with Exo; Par@Pep&amp;Exo = Par@Pep loaded with Exo. Reproduced with permission from Yang et al. [<a href="#B173-gels-10-00762" class="html-bibr">173</a>].</p>
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31 pages, 8437 KiB  
Article
Multifunctional Ag-Poly(N-isopropylacrylamide/itaconic Acid) Hydrogel Nanocomposites Prepared by Gamma Irradiation for Potential Application as Topical Treatment Dressings
by Jelena Spasojević, Milica Milošević, Sašenka Vidičević-Novaković, Jelena Tasić, Petar Milovanović, Marija Djurić, Dragan Ranković, Zorica Kačarević-Popović and Aleksandra Radosavljević
Polymers 2024, 16(22), 3211; https://doi.org/10.3390/polym16223211 - 19 Nov 2024
Cited by 1 | Viewed by 781
Abstract
Today, hydrogel dressings that can protect injury sites and effectively promote healing have become highly desirable in wound management. Therefore, multifunctional silver-poli(N-isopropylacrylamide/itaconic acid) (Ag-P(NiPAAm/IA)) hydrogel nanocomposites were developed for potential application as topical treatment dressings. The radiolytic method, used for the [...] Read more.
Today, hydrogel dressings that can protect injury sites and effectively promote healing have become highly desirable in wound management. Therefore, multifunctional silver-poli(N-isopropylacrylamide/itaconic acid) (Ag-P(NiPAAm/IA)) hydrogel nanocomposites were developed for potential application as topical treatment dressings. The radiolytic method, used for the crosslinking of the polymer matrix as well as for the in situ incorporation of silver nanoparticles (AgNPs) into the polymer matrix, enables the preparation of hydrogel nanocomposites without introducing harmful and toxic agents. Moreover, materials produced using γ-irradiation are simultaneously sterilized, thus fulfilling one of the basic requirements regarding their potential biomedical applications. The NiPAAm/IA ratio and the presence of AgNPs influenced the microstructural parameters of the investigated systems. Increasing the IA content leads to the formation of a more porous polymer matrix with larger pores, while the incorporated AgNPs act as additional junction points, decreasing the porosity and pore size of the resulting nanocomposite hydrogels. Swelling studies showed that most investigated systems uptake the fluids from their surroundings by non-Fick diffusion. Further, the Ag+ ion release, antibacterial activity, and cytotoxicity of Ag-P(NiPAAm/IA) hydrogel nanocomposites were examined to evaluate their biomedical potential. All hydrogel nanocomposites showed an initial burst release of Ag+ ions (useful in preventing bacteria adherence and biofilm formation), followed by a slower release of the same (ensuring sterility for longer use). An antibacterial activity test against Escherichia coli and Staphylococcus aureus showed that Ag-P(NiPAAm/IA) hydrogel nanocomposites, with silver concentrations around 10 ± 1 ppm, successfully prevent bacterial growth. Finally, it was shown that the investigated hydrogel nanocomposites do not exhibit a cytotoxic effect on human keratinocyte HaCaT cells. Therefore, these multifunctional hydrogel nanocomposites may promote wound repair and show promising potential for application as functional wound dressing. Full article
(This article belongs to the Special Issue Polymer Hydrogels: Synthesis, Properties and Applications)
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<p>FE-SEM micrographs of (<b>a</b>) P(NiPAAm/IA) 95.5/4.5 and (<b>b</b>) Ag-P(NiPAAm/IA) 95.5/4.5.</p>
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<p>Representative micro-CT images of P(NiPAAm/IA) 100.0/0.0 hydrogel: (<b>a</b>) 2D cross-section and (<b>b</b>) 3D reconstruction.</p>
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<p>Pore size distribution and wall thickness distribution (insets) for P(NiPAAm/IA) hydrogels (<b>a1</b>–<b>a4</b>) and Ag-P(NiPAAm/IA) hydrogel nanocomposites (<b>b1</b>–<b>b4</b>) obtained by micro-CT analysis.</p>
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<p>Extinction spectra of Ag-P(NiPAAm/IA) hydrogel nanocomposites: comparison of normalized extinction spectra obtained by experiment and by MiePlot simulation (<b>a1</b>–<b>a4</b>) and normalized efficiency of MiePlot simulated extinction spectra for AgNPs (<b>b1</b>–<b>b4</b>): <span class="html-italic">Q<sub>ext</sub></span>—extinction efficiency, <span class="html-italic">Q<sub>abs</sub></span>—absorption efficiency, <span class="html-italic">Q<sub>sca</sub></span>—scattering efficiency.</p>
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<p>XRD patterns of Ag-P(NiPAAm/IA) xerogel nanocomposites.</p>
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<p>SEM micrograph of AgNPs (sample Ag-P(NiPAAm/IA) 97.0/3.0) (<b>a</b>) and AgNP size distribution (<b>b</b>). The red line represents the Gaussian fit function of experimental data for particle size distribution.</p>
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<p>Swelling curves of P(NiPAAm/IA) hydrogels (<b>a1</b>,<b>b1</b>) and Ag-P(NiPAAm/IA) hydrogel nanocomposites (<b>a2</b>,<b>b2</b>) in distilled water (<b>up</b>) and SBF (<b>down</b>) at 37 °C.</p>
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<p>Cumulative silver release profiles (<b>a</b>), mathematical modeling (<b>b</b>–<b>g</b>), and diffusion coefficients (<b>h</b>) for Ag-P(NiPAAm/IA) hydrogel nanocomposites.</p>
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<p>Antibacterial activity of P(NiPAAm/IA) hydrogels (<b>a</b>,<b>b</b>) and Ag-P(NiPAAm/IA) hydrogel nanocomposites (<b>c</b>–<b>f</b>) against <span class="html-italic">Escherichia coli</span> and <span class="html-italic">Staphylococcus aureus</span> after 24 h of incubation at 37 °C [(<b>b</b>,<b>f</b>): reproduced from reference [<a href="#B17-polymers-16-03211" class="html-bibr">17</a>] with permission from Elsevier].</p>
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<p>Viability of <span class="html-italic">Escherichia coli</span> (<b>a1</b>–<b>a3</b>) and <span class="html-italic">Staphylococcus aureus</span> (<b>b1</b>–<b>b3</b>) in the presence of P(NiPAAm/IA) hydrogels (green) and Ag-P(NiPAAm/IA) hydrogel nanocomposites (orange) after 24 h of incubation at 37 °C. Control samples are untreated bacterial cultures (blue).</p>
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<p>Viability of human keratinocytes HaCaT cell line exposed to P(NiPAAm/IA) hydrogels (green) and Ag-P(NiPAAm/IA) hydrogel nanocomposites (orange) after 24 h of treatment. The control sample is an untreated HaCaT cell line (blue).</p>
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16 pages, 5151 KiB  
Article
Multi-Stimuli Responsive Viologen-Imprinted Polyvinyl Alcohol and Tricarboxy Cellulose Nanocomposite Hydrogels
by Salhah D. Al-Qahtani, Ghadah M. Al-Senani, Muneera Alrasheedi and Ard elshifa M. E. Mohammed
Sensors 2024, 24(21), 6860; https://doi.org/10.3390/s24216860 - 25 Oct 2024
Viewed by 757
Abstract
Photochromic inks have shown disadvantages, such as poor durability and high cost. Self-healable hydrogels have shown photostability and durability. Herein, a viologen-based covalent polymer was printed onto a paper surface toward the development of a multi-stimuli responsive chromogenic sheet with thermochromic, photochromic, and [...] Read more.
Photochromic inks have shown disadvantages, such as poor durability and high cost. Self-healable hydrogels have shown photostability and durability. Herein, a viologen-based covalent polymer was printed onto a paper surface toward the development of a multi-stimuli responsive chromogenic sheet with thermochromic, photochromic, and vapochromic properties. Viologen polymer was created by polymerizing a dialdehyde-based viologen with a hydroxyl-bearing dihydrazide in an acidic aqueous medium. The viologen polymer was well immobilized as a colorimetric agent into a polyvinyl alcohol (PVA)/tricarboxy cellulose (TCC)-based self-healable hydrogel. The viologen/hydrogel nanocomposite films were applied onto a paper surface. The coloration measurements showed that when exposed to ultraviolet light, the orange layer printed on the paper surface switched to green. The photochromic film was used to develop anti-counterfeiting prints using the organic hydrogel composed of a PVA/TCC composite and a viologen polymer. Reversible photochromism with strong photostability was observed when the printed papers were exposed to UV irradiation. A detection limit was monitored in the range of 0.5–300 ppm for NH3(aq). The exposure to heat (70 °C) was found to reversibly initiate a colorimetric change. Full article
(This article belongs to the Section Nanosensors)
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<p>Preparation of tricarboxy cellulose.</p>
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<p>TEM analysis of viologen polymer particles at different magnifications and different positions in the tested sample (<b>a</b>–<b>f</b>).</p>
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<p>XRD spectrum of polymer nanoparticles.</p>
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<p>SEM analysis of cast hydrogel film; VP<sub>6</sub> (<b>a</b>–<b>c</b>).</p>
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<p>SEM images of printed paper (VP<sub>6</sub>) at different positions on the sample surface (<b>a</b>–<b>c</b>).</p>
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<p>Absorption spectra of VP<sub>6</sub> below visible (Vis) and ultraviolet (UV) irradiation.</p>
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<p>Reversibility of absorbance of VP<sub>6</sub> over numerous cycles of ultraviolet (598 nm) and visible (430 nm) illumination.</p>
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<p>Effect of viologen content on mechanical performance of stamped samples, including tensile strength, strain, and Young’s modulus.</p>
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<p>Effect of shearing rate on the viscosity of VP<sub>6</sub>.</p>
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<p>Absorption spectra of VP<sub>6</sub> at different temperatures.</p>
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<p>Thermochromism of VP<sub>6</sub> showing a change in color from orange (<b>a</b>) to greenish (<b>b</b>) with heating from 25 °C to 70 °C, respectively.</p>
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<p>Absorbance spectra of paper (VP<sub>6</sub>) under air and different concentrations of NH<sub>3(g)</sub>.</p>
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<p>Absorption intensity of VP<sub>6</sub> versus various concentrations of NH<sub>3(aq)</sub>.</p>
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<p>Synthesis process of viologen polymer.</p>
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18 pages, 12959 KiB  
Article
Multifunctional Nanocomposite Hydrogel with Enhanced Chemodynamic Therapy and Starvation Therapy for Inhibiting Postoperative Tumor Recurrence
by Zeliang Li and Xiaoxuan Ma
Int. J. Mol. Sci. 2024, 25(21), 11465; https://doi.org/10.3390/ijms252111465 - 25 Oct 2024
Viewed by 741
Abstract
Surgical resection is the primary treatment for melanoma; however, preventing tumor recurrence after resection remains a significant clinical challenge. To address this, we developed a multifunctional nanocomposite hydrogel (H-CPG) composed of glucose oxidase (GOx)-coated CuS@PDA@GOx (CPG) nanoparticles, aminated hyaluronic acid (HA-ADH), and oxidized [...] Read more.
Surgical resection is the primary treatment for melanoma; however, preventing tumor recurrence after resection remains a significant clinical challenge. To address this, we developed a multifunctional nanocomposite hydrogel (H-CPG) composed of glucose oxidase (GOx)-coated CuS@PDA@GOx (CPG) nanoparticles, aminated hyaluronic acid (HA-ADH), and oxidized rhizomatous polysaccharides (OBSP), which are interconnected through hydrogen bonds and dynamic Schiff base linkages. In the acidic tumor micro-environment, the hydrogel releases GOx, catalyzing the production of hydrogen peroxide (H2O2), which enhances chemokinetic activity through a Cu2+-mediated Fenton-like reaction. This process generates hydroxyl radicals that intensify oxidative stress and promote macrophage polarization from the M2 to M1 phenotype. This polarization triggers the release of pro-inflammatory cytokines, thereby inhibiting tumor recurrence. Additionally, the hydrogel induces photothermal effects that help eradicate residual bacteria at the wound site. Overall, the H-CPG hydrogel offers a dual mechanism to prevent melanoma recurrence and reduce resistance to monotherapy, presenting a promising strategy for postoperative tumor management. Full article
(This article belongs to the Section Molecular Nanoscience)
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<p>Mechanism diagram of the synthesis of CuS@PDA@GOx nanoparticles and H-CPG hydrogel. Mechanism diagram of recurrence inhibition in postoperative melanoma application of H-CPG hydrogel.</p>
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<p>Preparation and characterization of CPG: (<b>A</b>) EDS image of CPG. (<b>B</b>) Size distribution and TEM image of CPG. (<b>C</b>) XRD image of CPG. (<b>D</b>) zeta potential maps of CuS, CP, CPG. (<b>E</b>) CAS-H<sub>2</sub>O<sub>2</sub>, CuS-H<sub>2</sub>O<sub>2</sub>, CP-H<sub>2</sub>O<sub>2</sub>, CPG-H<sub>2</sub>O<sub>2</sub>, CPG-Glucose (Glu) for the determination of -OH generation. (<b>F</b>) Photothermal heating curves for 10 min at different concentrations of CPG. (<b>G</b>) Photothermal stability of CPG with 3 on/off cycles. (Mean ± SD (<span class="html-italic">n</span> = 3)). *** <span class="html-italic">p</span> &lt; 0.001.</p>
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<p>Morphology, degradation properties, mechanical properties, and photothermal properties of H-CPG hydrogels: (<b>A</b>) Optical images of hydrogels. The two solutions of HA-ADH and OBSP were mixed in the same volume. (<b>B</b>) SEM plots of the hydrogels of H-CPG. (<b>C</b>) FTIR plots of H-CPG, HA-ADH, OBSP. (<b>D</b>) Tensile stress–strain curves of the hydrogels of H, H-C, H-CP, H-CPG. (<b>E</b>) H, H-C, H-CP, H-CPG hydrogels of maximum withstand pressure plots. (<b>F</b>) H-CPG strain scans showing gel–sol transition points. (<b>G</b>) G′ and G″ change curves of H-CPG hydrogel at alternating high strain (400%) and low strain (1%). (<b>H</b>) Oscillation frequencies (1–100 rad/s) of scanned H-CPG hydrogels at 37 °C and 1 Hz. (<b>I</b>) H, H-C, H-CP, H-CPG hydrogels swelling properties in PBS at 37 °C. (<b>J</b>) Photothermal images of PBS, H, and H-CPG at 10 min. (<b>K</b>) Standard curve of CuS@PDA@GOx. (<b>L</b>) CPG release profiles of H-CPG at (pH = 7.4) and (pH = 6.5). (<b>M</b>) Degradation of glucose by H-CPG hydrogels. (Mean ± SD (<span class="html-italic">n</span> = 3) ). ** <span class="html-italic">p</span> &lt; 0.01, and *** <span class="html-italic">p</span> &lt; 0.001.</p>
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<p>In vitro antitumor activity of hydrogels: (<b>A</b>) Live/dead staining images of B16F10 cells after various treatments. Scale bar: 100 µm. (<b>B</b>) Cell viability of B16F10 cells after different materials treatments. (<b>C</b>) Migration images of B16F10 cells after different materials treatments. Scale bar: 100 µm. (<b>D</b>) Visualized mobility of B16F10 cells after different materials treatments. (<b>E</b>) Flow-through apoptosis images of B16F10 cells after different materials treatments. (Mean ± SD (<span class="html-italic">n</span> = 3)). ns indicates no significant difference. ** <span class="html-italic">p</span> &lt; 0.01, and *** <span class="html-italic">p</span> &lt; 0.001.</p>
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<p>(<b>A</b>) Intracellular H<sub>2</sub>S levels after different treatments using WSP-5 as a probe. Scale bar: 200 µm. (<b>B</b>) Mean fluorescence intensity of H<sub>2</sub>S corresponding to A. (<b>C</b>) Microscopic measurements of intracellular mitochondrial damage by JC-1 probe. Scale bar: 100 µm. (<b>D</b>) Mean fluorescence intensity of JC-monomers corresponding to Figure B. (<b>E</b>) Mean fluorescence intensity of JC-aggregates corresponding to Figure B. (<b>F</b>) By staining with Dichloride hydro fluorescein diacetate (DCFH-DA) probe to assess the ROS levels of B16F10 cells after different materials treatments. Scale bar: 200 µm. (<b>G</b>) Fluorescence intensity of the DCFH-DA probe corresponding to Figure E. (<b>H</b>) ROS levels of B16F10 cells were analyzed by flow cytometry. (Mean ± SD (<span class="html-italic">n</span> = 3)), ns indicates no significant difference. ** <span class="html-italic">p</span> &lt; 0.01, and *** <span class="html-italic">p</span> &lt; 0.001.</p>
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<p>H-CPG-induced immunotherapy: (<b>a</b>) Immunofluorescence of TAM cells after different materials treatments. Scale bar: 100 µm. (<b>b</b>) Percentage of CD206 positive cells corresponding to Figure A. (<b>c</b>) Percentage of CD86 positive cells corresponding to Figure A. (<b>d</b>) Percentage of CD86/CD206 cells corresponding to Figure A. (<b>e</b>) Flow chart of TAMs cells after different materials treatments. (Mean ± SD (<span class="html-italic">n</span> = 3)). *** <span class="html-italic">p</span> &lt; 0.001).</p>
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<p>Evaluation of the antimicrobial effect: (<b>a</b>) Antimicrobial effect of different materials against <span class="html-italic">E. Coil</span>. The arrow points to the damaged bacterial structure. Scale bar: 2 µm. (<b>b</b>) Relative survival of <span class="html-italic">E. coli</span> corresponding to Figure a. (<b>c</b>) Antimicrobial effect of different materials against <span class="html-italic">S. aureus</span>. Scale bar: 2 µm. (<b>d</b>) Relative survival of <span class="html-italic">S. aureus</span> corresponding to Figure d. (Mean ± SD (n = 3). *** <span class="html-italic">p</span> &lt; 0.001).</p>
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<p>(<b>A</b>) Postoperative treatment protocols for tumors in mice in vivo. (<b>B</b>) Postoperative tumor resection model. (<b>C</b>) Thermograms of Control, H, and H-CPG group mice after 10 min of irradiation with 808 nm near-infrared radiation (1.0 W/cm<sup>2</sup>). (<b>D</b>) Tumor and wound repair in mice after 18 days of treatment, The red circle part represents the tumor size and wound distribution after 18 days of treatment. (<b>E</b>) Temperature distribution range corresponding to Figure C. (<b>F</b>) Tumor size in mice after 18 days of treatment. (<b>G</b>) Corresponds to (<b>F</b>) the size of the tumor volume. (Mean ± SD (<span class="html-italic">n</span> = 5)). *** <span class="html-italic">p</span> &lt; 0.001.</p>
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<p>(<b>A</b>) Photographs associated with histological analysis of tumor cells after 18 days of treatment. The red arrow represents the tumor vascular marker. Scale bar: 200 µm. (<b>B</b>) Percentage of CD206 immune cells after treatment with different drugs.(<b>C</b>) Percentage of IL-6 immune cells after treatment with different drugs. (<b>D</b>) Percentage of TNF-α immune cells after treatment with different drugs. (Mean ± SD (<span class="html-italic">n</span> = 5)), ns indicates no significant difference. * <span class="html-italic">p</span> &lt; 0.05, and *** <span class="html-italic">p</span> &lt; 0.001.</p>
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25 pages, 3181 KiB  
Review
Smart Nanocomposite Hydrogels as Next-Generation Therapeutic and Diagnostic Solutions
by Anna Valentino, Sorur Yazdanpanah, Raffaele Conte, Anna Calarco and Gianfranco Peluso
Gels 2024, 10(11), 689; https://doi.org/10.3390/gels10110689 - 24 Oct 2024
Viewed by 856
Abstract
Stimuli-responsive nanocomposite gels combine the unique properties of hydrogels with those of nanoparticles, thus avoiding the suboptimal results of single components and creating versatile, multi-functional platforms for therapeutic and diagnostic applications. These hybrid materials are engineered to respond to various internal and external [...] Read more.
Stimuli-responsive nanocomposite gels combine the unique properties of hydrogels with those of nanoparticles, thus avoiding the suboptimal results of single components and creating versatile, multi-functional platforms for therapeutic and diagnostic applications. These hybrid materials are engineered to respond to various internal and external stimuli, such as temperature, pH, light, magnetic fields, and enzymatic activity, allowing precise control over drug release, tissue regeneration, and biosensing. Their responsiveness to environmental cues permits personalized medicine approaches, providing dynamic control over therapeutic interventions and real-time diagnostic capabilities. This review explores recent advances in stimuli-responsive hybrid gels’ synthesis and application, including drug delivery, tissue engineering, and diagnostics. Overall, these platforms have significant clinical potential, and future research is expected to lead to unique solutions to address unmet medical needs. Full article
(This article belongs to the Special Issue Designing Hydrogels for Sustained Delivery of Therapeutic Agents)
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<p>Releasing mechanism for stimuli-responsive hydrogels.</p>
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<p>Schematic illustration of the biomedical applications of internal stimuli-responsive hydrogels.</p>
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<p>Schematic illustration of the biomedical applications of external stimuli-responsive hydrogels.</p>
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<p>Example of hydrogel modified with light-activatable cell adhesive motifs. (<b>a</b>,<b>b</b>) Fluorescence images of live-dead staining of L929 fibroblasts encapsulated in PEG hydrogels modified with cyclo[RGDfC] modified with (<b>a</b>) and without (<b>b</b>) UCNP-PMAOs (5 mg/mL). Cells were labelled 24 h after irradiation with a 974 nm laser (10 W/cm<sup>2</sup>) for 12 min. Green color indicates living cells and red color dead cells. Scale bar: 50 μm. (<b>c</b>) Quantification of viability of L929 cells in (<b>a</b>,<b>b</b>). (<b>d</b>,<b>e</b>) Z-stack fluorescence images showing the morphology of L929 cultured in cyclo[RGD(PMNB)fC] modified PEG hydrogel containing UCNP-PMAOs (5 mg/mL). with (<b>d</b>) or without (<b>e</b>) NIR laser exposure. Green color indicates living cells. (<b>f</b>) Quantification of the aspect ratio (the ratio of the longest to shortest dimension) of L929 fibroblasts from (<b>d</b>,<b>e</b>). mean± s.d., n = 10 cells, * <span class="html-italic">p</span> &lt; 0.05. (<b>g</b>,<b>h</b>) Z-stack fluorescence images of Human Umbilical Vein Endothelial Cells (HUVECs) within cyclo[RGD(DMNPB)fC] modified PEG hydrogels containing UCNP-PMAOs (5 mg/mL) with (<b>g</b>) and without (<b>h</b>) NIR exposure. Nucleus was stained by DAPI (blue), actin fibers with Phalloidin (green), and cell body with PECAM-1 (red). (<b>i</b>) Quantification of vascular area coverage percentage for (<b>g</b>,<b>h</b>). mean ± s.d., n ≥ 9 ROI with totals of 200–500 cells analyzed, * <span class="html-italic">p</span> &lt; 0.05. Reproduced from Ref. [<a href="#B82-gels-10-00689" class="html-bibr">82</a>] with permission from The Royal Society of Chemistry.</p>
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<p>Example of magnetic to heath stimulus. (<b>a</b>) Snapshots and IR thermal images of light-response shape recovery processes; (<b>b</b>) snapshots of magnetic-and light-responsive controlled reconfiguration; (<b>c</b>) the evolution of bending behavior induced by magnetic response; (<b>d</b>) the evolution of bending behavior induced by light response. Reproduced from Ref. [<a href="#B112-gels-10-00689" class="html-bibr">112</a>] with permission from The Royal Society of Chemistry.</p>
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15 pages, 1890 KiB  
Article
Studies of the Sorption-Desorption of Pesticides from Cellulose-Based Derivative Nanocomposite Hydrogels
by Fabrício C. Tanaka, Uilian G. Yonezawa, Marcia R. de Moura and Fauze A. Aouada
Molecules 2024, 29(20), 4932; https://doi.org/10.3390/molecules29204932 - 18 Oct 2024
Viewed by 629
Abstract
This study analyzed the effect of cellulose derivatives, namely methylcellulose (MC) and carboxymethylcellulose (CMC), on the stability of zeolite in a polymeric solution that would synthesize a three-dimensional network of poly(methacrylic acid)-co-polyacrylamide (PMAA-co-PAAm). Additionally, it investigated the effect of pH on the release [...] Read more.
This study analyzed the effect of cellulose derivatives, namely methylcellulose (MC) and carboxymethylcellulose (CMC), on the stability of zeolite in a polymeric solution that would synthesize a three-dimensional network of poly(methacrylic acid)-co-polyacrylamide (PMAA-co-PAAm). Additionally, it investigated the effect of pH on the release of paraquat (PQ) and difenzoquat (DFZ) herbicides. Similar to previous studies with hydrogels containing CMC, the presence of bi and trivalent salts, such as Ca+2 and Al+3, also drastically reduced their swelling degree from 6.7 g/g in NaCl (0.15 mol·L−1) to 2.1 g/g in an AlCl3 solution (0.15 mol·L−1) for the MC nanocomposite. The viscosity results may suggest that the formation of a polysaccharide-zeolite complex contributed to the zeolite stabilization. As for the adsorption results, all samples adsorbed practically the entire concentration of both herbicides in an aqueous solution. Finally, it was also observed that the valence of the salts and molecular weight of the herbicide affect the release process, where DFZ was the herbicide with the highest concentration released. Both nanostructured hydrogels with CMC and MC exhibited lower release at pH = 7.0. These results demonstrated that a more in-depth evaluation of the phenomena involved in the application of these materials in controlled-release systems could help mitigate the impact caused by pesticides. Full article
(This article belongs to the Special Issue Hydrogels: Preparation, Characterization, and Applications)
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<p>(<b>a</b>) TG curves of zeolite (in black), matrix hydrogel (in red), and hydrogel with MC (in blue). (<b>b</b>) TG curves of hydrogel with MC (in black) and its nanocomposites with 0.5%, 1.0%, and 1.5% <span class="html-italic">w</span>/<span class="html-italic">v</span> of zeolite (in red, blue, and green, respectively). (<b>c</b>,<b>d</b>) DTG curves obtained from (<b>a</b>,<b>b</b>), respectively.</p>
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<p>Bar graph of <span class="html-italic">SD<sub>eq</sub></span> as a function of NaCl (<b>a</b>) and NaCl, CaCl<sub>2</sub>, or AlCl<sub>3</sub> at 0.15 mol·L<sup>−1</sup> (<b>b</b>) solution concentrations for the matrix hydrogels, MC-containing hydrogels, and their nanocomposites with 1.5% <span class="html-italic">w</span>/<span class="html-italic">v</span> of zeolite.</p>
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<p>Kinetic curves of the matrix hydrogel, hydrogel with polysaccharide, and hydrogel nanocomposite with CMC concerning the concentration of adsorbed paraquat over time (<b>a</b>), adsorptive capacity (<span class="html-italic">q<sub>eq</sub></span>) over time (<b>b</b>), and percentage adsorbed over time (<b>c</b>). Kinetic curves of the matrix hydrogel, hydrogel with polysaccharide, and hydrogel nanocomposite with CMC regarding the concentration of adsorbed difenzoquat over time (<b>d</b>), adsorptive capacity (<span class="html-italic">q<sub>eq</sub></span>) over time (<b>e</b>), and percentage adsorbed over time (<b>f</b>). Kinetic curves of the matrix hydrogel, hydrogel with polysaccharide, and hydrogel nanocomposite with MC in relation to the concentration of adsorbed paraquat over time (<b>g</b>), adsorptive capacity (<span class="html-italic">q<sub>eq</sub></span>) over time (<b>h</b>), and percentage adsorbed over time (<b>i</b>). Lastly, kinetic curves of the matrix hydrogel, hydrogel with polysaccharide, and hydrogel nanocomposite with MC concerning the concentration of adsorbed difenzoquat over time (<b>j</b>), adsorptive capacity (<span class="html-italic">q<sub>eq</sub></span>) over time (<b>k</b>), and percentage adsorbed over time (<b>l</b>).</p>
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<p>Kinetic release curves of the matrix hydrogel, hydrogel, and hydrogel nanocomposite with CMC, regarding the concentration of paraquat (pH 4 (<b>a</b>), 7 (<b>b</b>), and 10 (<b>c</b>)), and difenzoquat (pH 4 (<b>d</b>), 7 (<b>e</b>), and 10 (<b>f</b>)) desorbed over time. Kinetic release curves of the matrix hydrogel, hydrogel, and hydrogel nanocomposite with MC, regarding the concentration of paraquat (pH 4 (<b>g</b>), 7 (<b>h</b>), and 10 (<b>i</b>)) and difenzoquat (pH 4 (<b>j</b>), 7 (<b>k</b>), and 10 (<b>l</b>)) desorbed over time.</p>
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<p>PMAA-co-PAAm hydrogel nanocomposites with cellulose derivatives (CMC or MC) and zeolite synthesis process illustration.</p>
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