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14 pages, 4049 KiB

Open AccessArticle

Morphology and Selected Properties of Modified Potato Thermoplastic Starch

by Regina Jeziorska, Agnieszka Szadkowska, Maciej Studzinski, Michal Chmielarek and Ewa Spasowka

Polymers 2023, 15(7), 1762; https://doi.org/10.3390/polym15071762 - 01 Apr 2023

Cited by 3 | Viewed by 1451

Abstract

Potato thermoplastic starch (TPS) containing 1 wt.% of pure halloysite (HNT), glycerol-modified halloysite (G-HNT) or polyester plasticizer-modified halloysite (PP-HNT) was prepared by melt-extrusion. Halloysites were characterized by FTIR, SEM, TGA, and DSC. Interactions between TPS and halloysites were studied by FTIR, SEM, and [...] Read more.

Potato thermoplastic starch (TPS) containing 1 wt.% of pure halloysite (HNT), glycerol-modified halloysite (G-HNT) or polyester plasticizer-modified halloysite (PP-HNT) was prepared by melt-extrusion. Halloysites were characterized by FTIR, SEM, TGA, and DSC. Interactions between TPS and halloysites were studied by FTIR, SEM, and DMTA. The Vicat softening temperature, tensile, and flexural properties were also determined. FTIR proved the interactions between halloysite and the organic compound as well as between starch, plasticizers and halloysites. Pure HNT had the best thermal stability, but PP-HNT showed better thermal stability than G-HNT. The addition of HNT and G-HNT improved the TPS’s thermal stability, as evidenced by significantly higher T_5%. Modified TPS showed higher a Vicat softening point, suggesting better hot water resistance. Halloysite improved TPS stiffness due to higher storage modulus. However, TPS/PP-HNT had the lowest stiffness, and TPS/HNT the highest. Halloysite increased T_α and lowered T_β due to its simultaneous reinforcing and plasticizing effect. TPS/HNT showed an additional β-relaxation peak, suggesting the formation of a new crystalline phase. The mechanical properties of TPS were also improved in the presence of both pure and modified halloysites. Full article

(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers II)

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18 pages, 3822 KiB

Open AccessArticle

Starch-Derived Superabsorbent Polymer in Remediation of Solid Waste Sludge Based on Water–Polymer Interaction

by Juan Matmin, Salizatul Ilyana Ibrahim, Mohd Hayrie Mohd Hatta, Raidah Ricky Marzuki, Khairulazhar Jumbri and Nik Ahmad Nizam Nik Malek

Polymers 2023, 15(6), 1471; https://doi.org/10.3390/polym15061471 - 16 Mar 2023

Cited by 2 | Viewed by 2018

Abstract

The purpose of this study is to assess water–polymer interaction in synthesized starch-derived superabsorbent polymer (S-SAP) for the treatment of solid waste sludge. While S-SAP for solid waste sludge treatment is still rare, it offers a lower cost for the safe disposal of [...] Read more.

The purpose of this study is to assess water–polymer interaction in synthesized starch-derived superabsorbent polymer (S-SAP) for the treatment of solid waste sludge. While S-SAP for solid waste sludge treatment is still rare, it offers a lower cost for the safe disposal of sludge into the environment and recycling of treated solid as crop fertilizer. For that to be possible, the water–polymer interaction on S-SAP must first be fully comprehended. In this study, the S-SAP was prepared through graft polymerization of poly (methacrylic acid-co-sodium methacrylate) on the starch backbone. By analyzing the amylose unit, it was possible to avoid the complexity of polymer networks when considering S-SAP using molecular dynamics (MD) simulations and density functional theory (DFT). Through the simulations, formation of hydrogen bonding between starch and water on the H06 of amylose was assessed for its flexibility and less steric hindrance. Meanwhile, water penetration into S-SAP was recorded by the specific radial distribution function (RDF) of atom–molecule interaction in the amylose. The experimental evaluation of S-SAP correlated with high water capacity by measuring up to 500% of distilled water within 80 min and more than 195% of the water from solid waste sludge for 7 days. In addition, the S-SAP swelling showed a notable performance of a 77 g/g swelling ratio within 160 min, while a water retention test showed that S-SAP was capable of retaining more than 50% of the absorbed water within 5 h of heating at 60 °C. The water retention of S-SAP adheres to pseudo-second-order kinetics for chemisorption reactions. Therefore, the prepared S-SAP might have potential applications as a natural superabsorbent, especially for the development of sludge water removal technology. Full article

(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers II)

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13 pages, 2683 KiB

Open AccessArticle

Hyaluronic Acid-Coated Chitosan Nanoparticles as an Active Targeted Carrier of Alpha Mangostin for Breast Cancer Cells

by Lisna Meylina, Muchtaridi Muchtaridi, I Made Joni, Khaled M. Elamin and Nasrul Wathoni

Polymers 2023, 15(4), 1025; https://doi.org/10.3390/polym15041025 - 18 Feb 2023

Cited by 7 | Viewed by 2489

Abstract

Alpha mangostin (AM) has potential anticancer properties for breast cancer. This study aims to assess the potential of chitosan nanoparticles coated with hyaluronic acid for the targeted delivery of AM (AM-CS/HA) against MCF-7 breast cancer cells. AM-CS/HA showed a spherical shape with an [...] Read more.

Alpha mangostin (AM) has potential anticancer properties for breast cancer. This study aims to assess the potential of chitosan nanoparticles coated with hyaluronic acid for the targeted delivery of AM (AM-CS/HA) against MCF-7 breast cancer cells. AM-CS/HA showed a spherical shape with an average diameter of 304 nm, a polydispersity index of 0.3, and a negative charge of 24.43 mV. High encapsulation efficiency (90%) and drug loading (8.5%) were achieved. AM released from AM-CS/HA at an acidic pH of 5.5 was higher than the physiological pH of 7.4 and showed sustained release. The cytotoxic effect of AM-CS/HA (IC₅₀ 4.37 µg/mL) on MCF-7 was significantly higher than AM nanoparticles without HA coating (AM-CS) (IC₅₀ 4.48 µg/mL) and AM (IC₅₀ 5.27 µg/mL). These findings suggest that AM-CS/HA enhances AM cytotoxicity and has potential applications for breast cancer therapy. Full article

(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers II)

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12 pages, 35786 KiB

Open AccessArticle

Strengthening Polylactic Acid by Salification: Surface Characterization Study

by Jessica Schlosser, Michael Keller, Kamran Fouladi and Babak Eslami

Polymers 2023, 15(3), 492; https://doi.org/10.3390/polym15030492 - 17 Jan 2023

Cited by 1 | Viewed by 1514

Abstract

Polylactic acid (PLA) is one of the market’s most commonly used biodegradable polymers, with diverse applications in additive manufacturing, specifically fused deposition modeling (FDM) 3D printing. The use of PLA in complex and sophisticated FDM applications is continually growing. However, the increased range [...] Read more.

Polylactic acid (PLA) is one of the market’s most commonly used biodegradable polymers, with diverse applications in additive manufacturing, specifically fused deposition modeling (FDM) 3D printing. The use of PLA in complex and sophisticated FDM applications is continually growing. However, the increased range of applications requires a better understanding of the material properties of this polymer. For example, recent studies have shown that PLA has the potential to be used in artificial heart valves. Still, the durability and longevity of this material in such a harsh environment are unknown, as heart valve failures have been attributed to salification. Additionally, there is a gap in the field for in situ material characterization of PLA surfaces during stiffening. The present study aims to benchmark different dynamic atomic force microscopy (AFM) techniques available to study the salification phenomenon of PLA at micro-scales using different PLA thin films with various salt concentrations (i.e., 10%, 15%, and 20% of sodium chloride (NaCl)). The measurements are conducted by tapping mode AFM, bimodal AFM, the force spectroscopy technique, and energy quantity analysis. These measurements showed a stiffening phenomenon occurring as the salt solution is increased, but the change was not equally sensitive to material property differences. Tapping mode AFM provided accurate topographical information, while the associated phase images were not considered reliable. On the other hand, bimodal AFM was shown to be capable of providing the topographical information and material compositional mapping through the higher eigenmode’s phase channel. The dissipated power energy quantities indicated that how the polymers become less dissipative as salt concentration increases can be measured. Lastly, it was shown that force spectroscopy is the most sensitive technique in detecting the differences in properties. The comparison of these techniques can provide a helpful guideline for studying the material properties of PLA polymers at micro- and nano-scales that can prove beneficial in various fields. Full article

(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers II)

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14 pages, 8649 KiB

Open AccessArticle

Green Composites Based on Mater-Bi^® and Solanum lycopersicum Plant Waste for 3D Printing Applications

by Roberto Scaffaro, Maria Clara Citarrella and Marco Morreale

Polymers 2023, 15(2), 325; https://doi.org/10.3390/polym15020325 - 08 Jan 2023

Cited by 16 | Viewed by 1575

Abstract

3D printability of green composites is currently experiencing a boost in importance and interest, envisaging a way to valorise agricultural waste, in order to obtain affordable fillers for the preparation of biodegradable polymer-based composites with reduced cost and environmental impact, without undermining processability [...] Read more.

3D printability of green composites is currently experiencing a boost in importance and interest, envisaging a way to valorise agricultural waste, in order to obtain affordable fillers for the preparation of biodegradable polymer-based composites with reduced cost and environmental impact, without undermining processability and mechanical performance. In this work, an innovative green composite was prepared by combining a starch-based biodegradable polymer (Mater-Bi^®, MB) and a filler obtained from the lignocellulosic waste coming from Solanum lycopersicum (i.e., tomato plant) harvesting. Different processing parameters and different filler amounts were investigated, and the obtained samples were subjected to rheological, morphological, and mechanical characterizations. Regarding the adopted filler amounts, processability was found to be good, with adequate dispersion of the filler in the matrix. Mechanical performance was satisfactory, and it was found that this is significantly affected by specific process parameters such as the raster angle. The mechanical properties were compared to those predictable from the Halpin–Tsai model, finding that the prepared systems exceed the expected values. Full article

(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers II)

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13 pages, 3512 KiB

Open AccessArticle

Enhanced Synaptic Properties in Biocompatible Casein Electrolyte via Microwave-Assisted Efficient Solution Synthesis

by Hwi-Su Kim, Hamin Park and Won-Ju Cho

Polymers 2023, 15(2), 293; https://doi.org/10.3390/polym15020293 - 06 Jan 2023

Cited by 4 | Viewed by 1415

Abstract

In this study, we fabricated an electric double-layer transistor (EDLT), a synaptic device, by preparing a casein biopolymer electrolyte solution using an efficient microwave-assisted synthesis to replace the conventional heating (heat stirrer) synthesis. Microwave irradiation (MWI) is more efficient in transferring energy to [...] Read more.

In this study, we fabricated an electric double-layer transistor (EDLT), a synaptic device, by preparing a casein biopolymer electrolyte solution using an efficient microwave-assisted synthesis to replace the conventional heating (heat stirrer) synthesis. Microwave irradiation (MWI) is more efficient in transferring energy to materials than heat stirrer, which significantly reduces the preparation time for casein electrolytes. The capacitance–frequency characteristics of metal–insulator–metal configurations applying the casein electrolyte prepared through MWI or a heat stirrer were measured. The capacitance of the MWI synthetic casein was 3.58 μF/cm² at 1 Hz, which was higher than that of the heat stirrer (1.78 μF/cm²), confirming a stronger EDL gating effect. Electrolyte-gated EDLTs using two different casein electrolytes as gate-insulating films were fabricated. The MWI synthetic casein exhibited superior EDLT electrical characteristics compared to the heat stirrer. Meanwhile, essential synaptic functions, including excitatory post-synaptic current, paired-pulse facilitation, signal filtering, and potentiation/depression, were successfully demonstrated in both EDLTs. However, MWI synthetic casein electrolyte-gated EDLT showed higher synaptic facilitation than the heat stirrer. Furthermore, we performed an MNIST handwritten-digit-recognition task using a multilayer artificial neural network and MWI synthetic casein EDLT achieved a higher recognition rate of 91.24%. The results suggest that microwave-assisted casein solution synthesis is an effective method for realizing biocompatible neuromorphic systems. Full article

(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers II)

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12 pages, 3007 KiB

Open AccessArticle

Composite Cement Materials Based on β-Tricalcium Phosphate, Calcium Sulfate, and a Mixture of Polyvinyl Alcohol and Polyvinylpyrrolidone Intended for Osteanagenesis

by Kseniya Stepanova, Daria Lytkina, Rustam Sadykov, Kseniya Shalygina, Toir Khojazoda, Rashidjon Mahmadbegov and Irina Kurzina

Polymers 2023, 15(1), 210; https://doi.org/10.3390/polym15010210 - 31 Dec 2022

Cited by 1 | Viewed by 1467

Abstract

The primary purpose of the study, presented in this article, was to obtain a composite cement material intended for osteanagenesis. The β-tricalcium phosphate powder (β-TCP, β-Ca₃(PO₄)₂) was obtained by the liquid-phase method. Setting and hardening of the [...] Read more.

The primary purpose of the study, presented in this article, was to obtain a composite cement material intended for osteanagenesis. The β-tricalcium phosphate powder (β-TCP, β-Ca₃(PO₄)₂) was obtained by the liquid-phase method. Setting and hardening of the cement system were achieved by adding calcium sulfate hemihydrate (CSH, CaSO₄·1/2H₂O). An aqueous solution of polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), and a PVA/PVP mixture were used as a polymer component. The methods of capillary viscometry and Fourier-transform infrared spectroscopy (FTIR) revealed the formation of intermolecular hydrogen bonds between polymer components, which determines the good miscibility of polymers. The physicochemical properties of the synthesized materials were characterized by X-ray diffraction (XRD) and FTIR methods, and the added amount of polymers does not significantly influence the processes of phase formation and crystallization of the system. The size of crystallites CSD remained in the range of 32–36 nm, regardless of the ratio of polymer components. The influence of the composition of composites on their solubility was investigated. In view of the lower solubility of pure β-TCP, as compared to calcium sulfate dihydrate (CSD, CaSO₄·2H₂O), the solubility of composite materials is determined to a greater degree by the CSD solubility. Complexometric titration showed that the interaction between PVA and PVP impeded the diffusion of calcium ions, and at a ratio of PVA to PVP of 1/1, the smallest exit of calcium ions from the system is observed. The cytotoxicity analysis results allowed us to establish the fact that the viability of human macrophages in the presence of the samples varied from 80% to 125% as compared to the control. Full article

(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers II)

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11 pages, 3398 KiB

Open AccessArticle

Crystallinity Dependence of PLLA Hydrophilic Modification during Alkali Hydrolysis

by Jiahui Shi, Jiachen Zhang, Yan Zhang, Liang Zhang, Yong-Biao Yang, Ofer Manor and Jichun You

Polymers 2023, 15(1), 75; https://doi.org/10.3390/polym15010075 - 25 Dec 2022

Cited by 7 | Viewed by 1692

Abstract

Poly(L-lactic acid) (PLLA) has been extensively used in tissue engineering, in which its surface hydrophilicity plays an important role. In this work, an efficient and green strategy has been developed to tailor surface hydrophilicity via alkali hydrolysis. On one hand, the ester bond [...] Read more.

Poly(L-lactic acid) (PLLA) has been extensively used in tissue engineering, in which its surface hydrophilicity plays an important role. In this work, an efficient and green strategy has been developed to tailor surface hydrophilicity via alkali hydrolysis. On one hand, the ester bond in PLLA has been cleaved and generates carboxyl and hydroxyl groups, both of which are beneficial to the improvement of hydrophilicity. On the other hand, the degradation of PLLA increases the roughness on the film surface. The resultant surface wettability of PLLA exhibits crucial dependence on its crystallinity. In the specimen with high crystallinity, the local enrichment of terminal carboxyl and hydroxyl groups in amorphous regions accelerates the degradation of ester group, producing more hydrophilic groups and slit valleys on film surface. The enhanced contact between PLLA and water in aqueous solution (i.e., the Wenzel state) contributes to the synergistic effect between generated hydrophilic groups and surface roughness, facilitating further degradation. Consequently, the hydrophilicity has been improved significantly in the high crystalline case. On the contrary, the competition effect between them leads to the failure of this strategy in the case of low crystallinity. Full article

(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers II)

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18 pages, 3948 KiB

Open AccessArticle

Effects of Accelerating the Ageing of 1D PLA Filaments after Fused Filament Fabrication

by Jaime Orellana-Barrasa, Sandra Tarancón and José Ygnacio Pastor

Polymers 2023, 15(1), 69; https://doi.org/10.3390/polym15010069 - 24 Dec 2022

Viewed by 1670

Abstract

The effects of post-treatment temperature-based methods for accelerating the ageing of PLA were studied on 1D single-PLA filaments after fused filament fabrication (FFF). The goal was to answer the questions whether the PLA can be safely aged—i.e., without degrading—at higher temperatures; at which [...] Read more.

The effects of post-treatment temperature-based methods for accelerating the ageing of PLA were studied on 1D single-PLA filaments after fused filament fabrication (FFF). The goal was to answer the questions whether the PLA can be safely aged—i.e., without degrading—at higher temperatures; at which temperatures, if any; how long it takes for the PLA to fully age at the chosen temperature; and which are the main differences between the material aged at room temperature and the material aged at higher temperatures. We also share other helpful information found. The use of 1D filaments allows for decoupling the variables related to the 3D structure (layer height, raster angle, infill density, and layers adhesion) from the variables solely related to the material (here, we analysed the molecular weight, the molecular orientation, and the crystallinity). 1D PLA filaments were aged at 20, 39, 42, 51, 65, 75, and 80 °C in a water-bath-inspired process in which the hydrolytic degradation of the PLA was minimised for the ageing temperatures of interest. Those temperatures were selected based on a differential scanning calorimetry (DSC) scan of the PLA right after it was printed in order to study the most effective ageing temperature, 39 °C, and highlight possible degradation mechanisms during ageing. The evolution of the thermal and mechanical properties of the PLA filaments at different temperatures was recorded and compared with those of the material aged at room temperature. A DSC scan was used to evaluate the thermal and physical properties, in which the glass transition, enthalpic relaxation, crystallisation, and melting reactions were analysed. A double glass transition was found, and its potential implications for the scientific community are discussed. Tensile tests were performed to evaluate the tensile strength and elastic modulus. The flow-induced molecular orientation, the degradation, the logistic fitting, and the so-called summer effect—the stabilisation of properties at higher values when aged at higher temperatures—are discussed to assess the safety of accelerating the ageing rate and the differences between the materials aged at different temperatures. It was found that the PLA aged at 39 °C (1) reached almost stable properties with just one day of ageing, i.e., the ageing rate accelerated by 875% for the elastic modulus and by 1635% for the yield strength; (2) the stable properties were higher than those from the PLA aged at room temperature; and (3) no signs of degradation were identified for the ageing temperature of interest. Full article

(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers II)

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11 pages, 382 KiB

Open AccessArticle

Thermo-Mechanical and Creep Behaviour of Polylactic Acid/Thermoplastic Polyurethane Blends

by Yi-Sheng Jhao, Hao Ouyang, Fuqian Yang and Sanboh Lee

Polymers 2022, 14(23), 5276; https://doi.org/10.3390/polym14235276 - 02 Dec 2022

Cited by 4 | Viewed by 1547

Abstract

There is a great need to develop biodegradable thermoplastics for a variety of applications in a wide range of temperatures. In this work, we prepare polymer blends from polylactic acid (PLA) and thermoplastic polyurethane (TPU) via a melting blend method at 200 °C [...] Read more.

There is a great need to develop biodegradable thermoplastics for a variety of applications in a wide range of temperatures. In this work, we prepare polymer blends from polylactic acid (PLA) and thermoplastic polyurethane (TPU) via a melting blend method at 200 °C and study the creep deformation of the PLA/TPU blends in a temperature range of 10 to 40 °C with the focus on transient and steady-state creep. The stress exponent for the power law description of the steady state creep of PLA/TPU blends decreases linearly with the increase of the mass fraction of TPU from 1.73 for the PLA to 1.17 for the TPU. The activation energies of the rate processes for the steady-state creep and transient creep decrease linearly with the increase of the mass fraction of TPU from 97.7 ± 3.9 kJ/mol and 59.4 ± 2.9 kJ/mol for the PLA to 26.3 ± 1.3 kJ/mol and 25.4 ± 1.7 kJ/mol for the TPU, respectively. These linearly decreasing trends can be attributed to the weak interaction between the PLA and the TPU. The creep deformation of the PLA/TPU blends consists of the contributions of individual PLA and TPU. Full article

(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers II)

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23 pages, 6350 KiB

Open AccessArticle

Blending PLA with Polyesters Based on 2,5-Furan Dicarboxylic Acid: Evaluation of Physicochemical and Nanomechanical Properties

by Zoi Terzopoulou, Alexandra Zamboulis, Lazaros Papadopoulos, Maria-Eirini Grigora, Konstantinos Tsongas, Dimitrios Tzetzis, Dimitrios N. Bikiaris and George Z. Papageorgiou

Polymers 2022, 14(21), 4725; https://doi.org/10.3390/polym14214725 - 04 Nov 2022

Cited by 4 | Viewed by 1614

Abstract

Poly(lactic acid) (PLA) is a readily available, compostable biobased polyester with high strength and toughness, and it is excellent for 3D printing applications. Polymer blending is an economic and easy way to improve its properties, such as its slow degradation and crystallization rates [...] Read more.

Poly(lactic acid) (PLA) is a readily available, compostable biobased polyester with high strength and toughness, and it is excellent for 3D printing applications. Polymer blending is an economic and easy way to improve its properties, such as its slow degradation and crystallization rates and its small elongation, and thus, make it more versatile. In this work, the effects of different 2,5-furan dicarboxylic acid (FDCA)-based polyesters on the physicochemical and mechanical properties of PLA were studied. Poly(butylene furan 2,5-dicarboxylate) (PBF) and its copolymers with poly(butylene adipate) (PBAd) were synthesized in various comonomer ratios and were blended with 70 wt% PLA using melt compounding. The thermal, morphological and mechanical properties of the blends are investigated. All blends were immiscible, and the presence of the dispersed phases improved the crystallization ability of PLA. Mechanical testing revealed the plasticization of PLA after blending, and a small but measurable mass loss after burying in soil for 7 months. Reactive blending was evaluated as a compatibilizer-free method to improve miscibility, and it was found that when the thermal stability of the blend components allowed it, some transesterification reactions occurred between the PLA matrix and the FDCA-based dispersed phase after 20 min at 250 °C. Full article

(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers II)

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16 pages, 4034 KiB

Open AccessArticle

Nano-Hydroxyapatite from White Seabass Scales as a Bio-Filler in Polylactic Acid Biocomposite: Preparation and Characterization

by Preeyaporn Injorhor, Tatiya Trongsatitkul, Jatuporn Wittayakun, Chaiwat Ruksakulpiwat and Yupaporn Ruksakulpiwat

Polymers 2022, 14(19), 4158; https://doi.org/10.3390/polym14194158 - 04 Oct 2022

Cited by 8 | Viewed by 1780

Abstract

Nano-hydroxyapatite (nHAp) as a bio-filler used in PLA composites was prepared from fish by acid deproteinization (1DP) and a combination of acid-alkali deproteinization (2DP) followed by alkali heat treatment. Moreover, the PLA/nHAp composite films were developed using solution casting method. The mechanical and [...] Read more.

Nano-hydroxyapatite (nHAp) as a bio-filler used in PLA composites was prepared from fish by acid deproteinization (1DP) and a combination of acid-alkali deproteinization (2DP) followed by alkali heat treatment. Moreover, the PLA/nHAp composite films were developed using solution casting method. The mechanical and thermal properties of the PLA composite films with nHAp from different steps deproteinization and contents were compared. The physical properties analysis confirmed that the nHAp can be prepared from fish scales using both steps deproteinization. 1DP-nHAp showed higher surface area and lower crystallinity than 2DP-nHAp. This gave advantage of 1DP-nHAp for use as filler. PLA composite with 1DP-nHAp gave tensile strength of 66.41 ± 3.63 MPa and Young’s modulus of 2.65 ± 0.05 GPa which were higher than 2DP-nHAp at the same content. The addition of 5 phr 1DP-nHAp into PLA significantly improved the tensile strength and Young’s modulus. PLA composite solution with 1DP-nHAp at 5 phr showed electrospinnability by giving continuous fibers without beads. Full article

(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers II)

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18 pages, 3451 KiB

Open AccessArticle

A Feature of the Crystalline and Amorphous Structure of Ultra Thin Fibers Based on Poly(3-hydroxybutyrate) (PHB) Containing Minor Concentrations of Hemin and a Complex of Tetraphenylporphyrin with Iron

by Svetlana G. Karpova, Ivetta A. Varyan, Anatoly A. Olkhov, Polina M. Tyubaeva and Anatoly A. Popov

Polymers 2022, 14(19), 4055; https://doi.org/10.3390/polym14194055 - 27 Sep 2022

Cited by 3 | Viewed by 1466 | Correction

Abstract

Comprehensive studies combining X-ray diffraction analysis, thermophysical, dynamic measurements by probe method and scanning electron microscopy have been carried out. The peculiarity of the crystalline and amorphous structure of ultra-thin fibers based on poly(3-hydroxybutyrate) (PHB) containing minor concentrations (0–5%) of a gene and [...] Read more.

Comprehensive studies combining X-ray diffraction analysis, thermophysical, dynamic measurements by probe method and scanning electron microscopy have been carried out. The peculiarity of the crystalline and amorphous structure of ultra-thin fibers based on poly(3-hydroxybutyrate) (PHB) containing minor concentrations (0–5%) of a gene and a tetraphenylporphyrin (TFP) complex with iron (in the form of FeCl) are considered. When these complexes are added to the PHB fibers, the morphology of the fibers change: a sharp change in the crystallinity and molecular mobility in the amorphous regions of PHB is observed. When adding a gel to the fibers of PHB, a significant decrease in the degree of crystallinity, melting enthalpy, and correlation time can be observed. The reverse pattern is observed in a system with the addition of FeCl-TFP—there is a significant increase in the degree of crystallinity, melting enthalpy and correlation time. Exposure of PHB fibers with gemin in an aqueous medium at 70 °C leads to a decrease in the enthalpy of melting in modified fibers—to an increase in this parameter. The molecular mobility of chains in amorphous regions of PHB/gemin fibers increases at the same time, a nonlinear dependence of changes in molecular dynamics is observed in PHB/FeCl-TFP fibers. Ozonolysis has a complex effect on the amorphous structure of the studied systems. The obtained fibrous materials have bactericidal properties and should be used in the creation of new therapeutic systems of antibacterial and antitumor action. Full article

(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers II)

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19 pages, 10900 KiB

Open AccessArticle

Bio-Based Poly(lactic acid)/Poly(butylene sebacate) Blends with Improved Toughness

by Adriana Nicoleta Frone, Marius Stelian Popa, Cătălina Diana Uşurelu, Denis Mihaela Panaitescu, Augusta Raluca Gabor, Cristian Andi Nicolae, Monica Florentina Raduly, Anamaria Zaharia and Elvira Alexandrescu

Polymers 2022, 14(19), 3998; https://doi.org/10.3390/polym14193998 - 24 Sep 2022

Cited by 6 | Viewed by 2080

Abstract

A series of poly(butylene sebacate) (PBSe) aliphatic polyesters were successfully synthesized by the melt polycondensation of sebacic acid (Se) and 1,4-butanediol (BDO), two monomers manufactured on an industrial scale from biomass. The number average molecular weight (M_n) in the range from [...] Read more.

A series of poly(butylene sebacate) (PBSe) aliphatic polyesters were successfully synthesized by the melt polycondensation of sebacic acid (Se) and 1,4-butanediol (BDO), two monomers manufactured on an industrial scale from biomass. The number average molecular weight (M_n) in the range from 6116 to 10,779 g/mol and the glass transition temperature (T_g) of the PBSe polyesters were tuned by adjusting the feed ratio between the two monomers. Polylactic acid (PLA)/PBSe blends with PBSe concentrations between 2.5 to 20 wt% were obtained by melt compounding. For the first time, PBSe’s effect on the flexibility and toughness of PLA was studied. As shown by the torque and melt flow index (MFI) values, the addition of PBSe endowed PLA with both enhanced melt processability and flexibility. The tensile tests and thermogravimetric analysis showed that PLA/PBSe blends containing 20 wt% PBSe obtained using a BDO molar excess of 50% reached an increase in elongation at break from 2.9 to 108%, with a negligible decrease in Young’s modulus from 2186 MPa to 1843 MPa, and a slight decrease in thermal performances. These results demonstrated the plasticizing efficiency of the synthesized bio-derived polyesters in overcoming PLA’s brittleness. Moreover, the tunable properties of the resulting PBSe can be of great industrial interest in the context of circular bioeconomy. Full article

(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers II)

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28 pages, 7623 KiB

Open AccessArticle

Development of a New Eco-Friendly Copolymer Based on Chitosan for Enhanced Removal of Pb and Cd from Water

by Iolanda-Veronica Ganea, Alexandrina Nan, Carmen Roba, Iulia Neamțiu, Eugen Gurzău, Rodica Turcu, Xenia Filip and Călin Baciu

Polymers 2022, 14(18), 3735; https://doi.org/10.3390/polym14183735 - 07 Sep 2022

Cited by 1 | Viewed by 2056

Abstract

Worldwide, concerns about heavy metal contamination from manmade and natural sources have increased in recent decades. Metals released into the environment threaten human health, mostly due to their integration into the food chain and persistence. Nature offers a large range of materials with [...] Read more.

Worldwide, concerns about heavy metal contamination from manmade and natural sources have increased in recent decades. Metals released into the environment threaten human health, mostly due to their integration into the food chain and persistence. Nature offers a large range of materials with different functionalities, providing also a source of inspiration for scientists working in the field of material synthesis. In the current study, a new type of copolymer is introduced, which was synthesized for the first time by combining chitosan and poly(benzofurane-co-arylacetic acid), for use in the adsorption of toxic heavy metals. Such naturally derived materials can be easily and inexpensively synthesized and separated by simple filtration, thus becoming an attractive alternative solution for wastewater treatment. The new copolymer was investigated by solid-state nuclear magnetic resonance, thermogravimetric analysis, scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray photon electron microscopy. Flame atomic absorption spectrometry was utilized to measure heavy metal concentrations in the investigated samples. Equilibrium isotherms, kinetic 3D models, and artificial neural networks were applied to the experimental data to characterize the adsorption process. Additional adsorption experiments were performed using metal-contaminated water samples collected in two seasons (summer and winter) from two former mining areas in Romania (Roșia Montană and Novăț-Borșa). The results demonstrated high (51–97%) adsorption efficiency for Pb and excellent (95–100%) for Cd, after testing on stock solutions and contaminated water samples. The recyclability study of the copolymer indicated that the removal efficiency decreased to 89% for Pb and 58% for Cd after seven adsorption–desorption cycles. Full article

(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers II)

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14 pages, 1598 KiB

Open AccessArticle

Chitin Nanocrystals Provide Antioxidant Activity to Polylactic Acid Films

by Murat Yanat, Ivanna Colijn and Karin Schroën

Polymers 2022, 14(14), 2965; https://doi.org/10.3390/polym14142965 - 21 Jul 2022

Cited by 4 | Viewed by 1793

Abstract

About 1/3rd of produced food goes to waste, and amongst others, advanced packaging concepts need to be developed to prevent this from happening. Here, we target the antioxidative functionality of food packaging to thus address food oxidation without the need for the addition [...] Read more.

About 1/3rd of produced food goes to waste, and amongst others, advanced packaging concepts need to be developed to prevent this from happening. Here, we target the antioxidative functionality of food packaging to thus address food oxidation without the need for the addition of antioxidants to the food product, which is not desirable from a consumer point of view. Chitin nanocrystals (ChNC) have been shown to be promising bio-fillers for improving the mechanical strength of biodegradable plastics, but their potential as active components in plastic films is rather unexplored. In the current study, we investigate the antioxidant activity of chitin nanocrystals as such and as part of polylactic acid (PLA) films. This investigation was conducted using DPPH (1,1-diphenyl-2-picrylhydrazyl) radical scavenging activity. Chitin nanocrystals produced via acid hydrolysis showed five times higher activity compared to crude chitin powder. When using these crystals as part of a polylactic acid film (either inside or on top), in both scenarios, antioxidant activity was found, but the effect was considerably greater when the particles were at the surface of the film. This is an important proof of the principle that it is possible to create biodegradable plastics with additional functionality through the addition of ChNC. Full article

(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers II)

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Review

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25 pages, 4960 KiB

Open AccessReview

Therapeutic Efficacy of Polymeric Biomaterials in Treating Diabetic Wounds—An Upcoming Wound Healing Technology

by Weslen Vedakumari Sathyaraj, Lokesh Prabakaran, Jayavardhini Bhoopathy, Sankari Dharmalingam, Ramadoss Karthikeyan and Raji Atchudan

Polymers 2023, 15(5), 1205; https://doi.org/10.3390/polym15051205 - 27 Feb 2023

Cited by 6 | Viewed by 2411

Abstract

Diabetic wounds are one of the serious, non-healing, chronic health issues faced by individuals suffering from diabetic mellitus. The distinct phases of wound healing are either prolonged or obstructed, resulting in the improper healing of diabetic wounds. These injuries require persistent wound care [...] Read more.

Diabetic wounds are one of the serious, non-healing, chronic health issues faced by individuals suffering from diabetic mellitus. The distinct phases of wound healing are either prolonged or obstructed, resulting in the improper healing of diabetic wounds. These injuries require persistent wound care and appropriate treatment to prevent deleterious effects such as lower limb amputation. Although there are several treatment strategies, diabetic wounds continue to be a major threat for healthcare professionals and patients. The different types of diabetic wound dressings that are currently used differ in their properties of absorbing wound exudates and may also cause maceration to surrounding tissues. Current research is focused on developing novel wound dressings incorporated with biological agents that aid in a faster rate of wound closure. An ideal wound dressing material must absorb wound exudates, aid in the appropriate exchange of gas, and protect from microbial infections. It must support the synthesis of biochemical mediators such as cytokines, and growth factors that are crucial for faster healing of wounds. This review highlights the recent advances in polymeric biomaterial-based wound dressings, novel therapeutic regimes, and their efficacy in treating diabetic wounds. The role of polymeric wound dressings loaded with bioactive compounds, and their in vitro and in vivo performance in diabetic wound treatment are also reviewed. Full article

(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers II)

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63 pages, 11683 KiB

Open AccessReview

Recent Advances in the Investigation of Poly(lactic acid) (PLA) Nanocomposites: Incorporation of Various Nanofillers and their Properties and Applications

by Nikolaos D. Bikiaris, Ioanna Koumentakou, Christina Samiotaki, Despoina Meimaroglou, Despoina Varytimidou, Anastasia Karatza, Zisimos Kalantzis, Magdalini Roussou, Rizos D. Bikiaris and George Z. Papageorgiou

Polymers 2023, 15(5), 1196; https://doi.org/10.3390/polym15051196 - 27 Feb 2023

Cited by 35 | Viewed by 7743

Abstract

Poly(lactic acid) (PLA) is considered the most promising biobased substitute for fossil-derived polymers due to its compostability, biocompatibility, renewability, and good thermomechanical properties. However, PLA suffers from several shortcomings, such as low heat distortion temperature, thermal resistance, and rate of crystallization, whereas some [...] Read more.

Poly(lactic acid) (PLA) is considered the most promising biobased substitute for fossil-derived polymers due to its compostability, biocompatibility, renewability, and good thermomechanical properties. However, PLA suffers from several shortcomings, such as low heat distortion temperature, thermal resistance, and rate of crystallization, whereas some other specific properties, i.e., flame retardancy, anti-UV, antibacterial or barrier properties, antistatic to conductive electrical characteristics, etc., are required by different end-use sectors. The addition of different nanofillers represents an attractive way to develop and enhance the properties of neat PLA. Numerous nanofillers with different architectures and properties have been investigated, with satisfactory achievements, in the design of PLA nanocomposites. This review paper overviews the current advances in the synthetic routes of PLA nanocomposites, the imparted properties of each nano-additive, as well as the numerous applications of PLA nanocomposites in various industrial fields. Full article

(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers II)

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21 pages, 9852 KiB

Open AccessReview

Fabrication of Biodegradable and Biocompatible Functional Polymers for Anti-Infection and Augmenting Wound Repair

by Shuhua Deng, Anfu Chen, Weijia Chen, Jindi Lai, Yameng Pei, Jiahua Wen, Can Yang, Jiajun Luo, Jingjing Zhang, Caihong Lei, Swastina Nath Varma and Chaozong Liu

Polymers 2023, 15(1), 120; https://doi.org/10.3390/polym15010120 - 28 Dec 2022

Cited by 6 | Viewed by 2751

Abstract

The problem of bacteria-induced infections threatens the lives of many patients. Meanwhile, the misuse of antibiotics has led to a significant increase in bacterial resistance. There are two main ways to alleviate the issue: one is to introduce antimicrobial agents to medical devices [...] Read more.

The problem of bacteria-induced infections threatens the lives of many patients. Meanwhile, the misuse of antibiotics has led to a significant increase in bacterial resistance. There are two main ways to alleviate the issue: one is to introduce antimicrobial agents to medical devices to get local drug releasing and alleviating systemic toxicity and resistance, and the other is to develop new antimicrobial methods to kill bacteria. New antimicrobial methods include cationic polymers, metal ions, hydrophobic structures to prevent bacterial adhesion, photothermal sterilization, new biocides, etc. Biodegradable biocompatible synthetic polymers have been widely used in the medical field. They are often used in tissue engineering scaffolds as well as wound dressings, where bacterial infections in these medical devices can be serious or even fatal. However, such materials usually do not have inherent antimicrobial properties. They can be used as carriers for drug delivery or compounded with other antimicrobial materials to achieve antimicrobial effects. This review focuses on the antimicrobial behavior, preparation methods, and biocompatibility testing of biodegradable biocompatible synthetic polymers. Degradable biocompatible natural polymers with antimicrobial properties are also briefly described. Finally, the medical applications of these polymeric materials are presented. Full article

(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers II)

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19 pages, 3407 KiB

Open AccessReview

A Review on Fully Bio-Based Materials Development from Polylactide and Cellulose Nanowhiskers

by Purba Purnama, Muhammad Samsuri and Ihsan Iswaldi

Polymers 2022, 14(19), 4009; https://doi.org/10.3390/polym14194009 - 25 Sep 2022

Cited by 7 | Viewed by 1713

Abstract

This review covers the development of eco-friendly, bio-based materials based on polylactide (PLA) and cellulose nanowhiskers (CNWs). As a biodegradable polymer, PLA is one of the promising materials to replace petroleum-based polymers. In the field of nanocomposites, CNWs offer many advantages; they are [...] Read more.

This review covers the development of eco-friendly, bio-based materials based on polylactide (PLA) and cellulose nanowhiskers (CNWs). As a biodegradable polymer, PLA is one of the promising materials to replace petroleum-based polymers. In the field of nanocomposites, CNWs offer many advantages; they are made from renewable resources and exhibit beneficial mechanical and thermal properties in combination with polymer matrix. A wide range of surface modifications has been done to improve the miscibility of CNW with the PLA homopolymer, which generally gives rise to hydrophobic properties. PLA–CNW nanocomposite materials are fully degradable and sustainable and also offer improved mechanical and thermal properties. Limitations pertaining to the miscibility of CNWs with PLA were solved through surface modification and chemical grafting on the CNW surfaces. Further development has been done by combining PLA-based material via stereocomplexation approaches in the presence of CNW particles, known as bio-stereo-nanocomposite PLA–CNW. The combination of stereocomplex crystalline structures in the presence of well-distributed CNW particles produces synergetic effects that enhance the mechanical and thermal properties, including stereocomplex memory (melt stability). The bio-based materials from PLA and CNWs may serve as eco-friendly materials owing to their sustainability (obtained from renewable resources), biodegradability, and tunability properties. Full article

(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers II)

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