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16 pages, 3276 KiB

Open AccessArticle

Tough Bioplastics from Babassu Oil-Based Acrylic Monomer, Hemicellulose Xylan, and Carnauba Wax

by Yehor Polunin, Vasylyna Kirianchuk, Najah Mhesn, Liying Wei, Sergiy Minko, Igor Luzinov and Andriy Voronov

Int. J. Mol. Sci. 2023, 24(7), 6103; https://doi.org/10.3390/ijms24076103 - 23 Mar 2023

Cited by 3 | Viewed by 1474

Abstract

We describe here the fabrication, characterization, and properties of tough bioplastics made of a babassu oil-based acrylic polymer (PBBM), hemicellulose xylan grafted with PBBM chains, and carnauba wax (CW). The plastic was primarily designed to obtain bioderived materials that can replace low-density polyethylene [...] Read more.

We describe here the fabrication, characterization, and properties of tough bioplastics made of a babassu oil-based acrylic polymer (PBBM), hemicellulose xylan grafted with PBBM chains, and carnauba wax (CW). The plastic was primarily designed to obtain bioderived materials that can replace low-density polyethylene (LDPE) in certain food packaging applications. To obtain plastic, the radical polymerization of an original babassu oil-based acrylic monomer (BBM) in the presence of xylan macromolecules modified with maleic anhydride (X-MA) was conducted. The polymerization resulted in a material (PBBM-X) mostly consisting of highly branched PBBM/X-MA macromolecules. PBBM-X has a glass transition of 42 °C, a storage modulus of 130 MPa (at 25 °C, RT), and a Young’s modulus of 30 MPa at RT. To increase the moduli, we blended PBBM-X with carnauba wax, a natural material with a high modulus and a melting temperature of ~80 °C. It was found that PBBM-X is compatible with the wax, as evidenced by the alternation of the material’s thermal transitions and the co-crystallization of BBM side alkyl fragments with CW. As a result, the PBBM-X/CW blend containing 40% of the wax had a storage modulus of 475 MPa (RT) and a Young’s modulus of 248 MPa (RT), which is close to that of LDPE. As polyethylene, the PBBM-X and PBBM-X/CW bioplastics have the typical stress-strain behavior demonstrated by ductile (tough) plastics. However, the bioplastic’s yield strength and elongation-at-yield are considerably lower than those of LDPE. We evaluated the moisture barrier properties of the PBBM-X/(40%)CW material and found that the bioplastic’s water vapor permeability (WVP) is quite close to that of LDPE. Our bioderived material demonstrates a WVP that is comparable to polyethylene terephthalate and lower than the WVP of nylon and polystyrene. Taking into account the obtained results, the fabricated materials can be considered as polyethylene alternatives to provide sustainability in plastics production in the packaging areas where LDPE currently dominates. Full article

(This article belongs to the Special Issue Synthesis of Advanced Polymer Materials)

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12 pages, 10535 KiB

Open AccessArticle

Amphiphilic Polyethylene-b-poly(L-lysine) Block Copolymer: Synthesis, Self-Assembly, and Responsivity

by Lixia Pei, Hongyu Ma, Yan Jiang, Handou Zheng and Haiyang Gao

Int. J. Mol. Sci. 2023, 24(6), 5495; https://doi.org/10.3390/ijms24065495 - 13 Mar 2023

Cited by 3 | Viewed by 1437

Abstract

Polyethylene-b-polypeptide copolymers are biologically interesting, but studies of their synthesis and properties are very few. This paper reports synthesis and characterization of well-defined amphiphilic polyethylene-block-poly(L-lysine) (PE-b-PLL) block copolymers by combining nickel-catalyzed living ethylene polymerization with controlled ring-opening [...] Read more.

Polyethylene-b-polypeptide copolymers are biologically interesting, but studies of their synthesis and properties are very few. This paper reports synthesis and characterization of well-defined amphiphilic polyethylene-block-poly(L-lysine) (PE-b-PLL) block copolymers by combining nickel-catalyzed living ethylene polymerization with controlled ring-opening polymerization (ROP) of ε-benzyloxycarbonyl-L-lysine-N-carboxyanhydride (Z-Lys-NCA) and sequential post-functionalization. Amphiphilic PE-b-PLL block copolymers self-assembled into spherical micelles with a hydrophobic PE core in aqueous solution. The pH and ionic responsivities of PE-b-PLL polymeric micelles were investigated by means of fluorescence spectroscopy, dynamic light scattering, UV-circular dichroism, and transmission electron microscopy. The variation of pH values led to the conformational alteration of PLL from α-helix to coil, thereby changing the micelle dimensions. Full article

(This article belongs to the Special Issue Synthesis of Advanced Polymer Materials)

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13 pages, 3336 KiB

Open AccessArticle

Fabrication of Polyurethane Elastomer/Hindered Phenol Composites with Tunable Damping Property

by Xiuying Zhao, Ruiheng Jin, Zhihao Niu, Yangyang Gao and Shikai Hu

Int. J. Mol. Sci. 2023, 24(5), 4662; https://doi.org/10.3390/ijms24054662 - 28 Feb 2023

Cited by 2 | Viewed by 1563

Abstract

Vibration and noise-reduction materials are indispensable in various fields. Polyurethane (PU)-based damping materials can dissipate the external mechanical and acoustic energy through molecular chain movements to mitigate the adverse effects of vibrations and noise. In this study, PU-based damping composites were obtained by [...] Read more.

Vibration and noise-reduction materials are indispensable in various fields. Polyurethane (PU)-based damping materials can dissipate the external mechanical and acoustic energy through molecular chain movements to mitigate the adverse effects of vibrations and noise. In this study, PU-based damping composites were obtained by compositing PU rubber prepared using 3-methyltetrahydrofuran/tetrahydrofuran copolyether glycol, 4,4′-diphenylmethane diisocyanate, and trimethylolpropane monoallyl ether as raw materials with hindered phenol, viz., and 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)proponyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane (AO-80). Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, and tensile tests were conducted to evaluate the properties of the resulting composites. The glass transition temperature of the composite increased from −40 to −23 °C, and the tan δ_Max of the PU rubber increased by 81%, from 0.86 to 1.56 when 30 phr of AO-80 was added. This study provides a new platform for the design and preparation of damping materials for industrial applications and daily life. Full article

(This article belongs to the Special Issue Synthesis of Advanced Polymer Materials)

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15 pages, 4309 KiB

Open AccessArticle

Biodegradable Scaffolds for Vascular Regeneration Based on Electrospun Poly(L-Lactide-co-Glycolide)/Poly(Isosorbide Sebacate) Fibers

by Monika Śmiga-Matuszowicz, Jakub Włodarczyk, Małgorzata Skorupa, Dominika Czerwińska-Główka, Kaja Fołta, Małgorzata Pastusiak, Małgorzata Adamiec-Organiściok, Magdalena Skonieczna, Roman Turczyn, Michał Sobota and Katarzyna Krukiewicz

Int. J. Mol. Sci. 2023, 24(2), 1190; https://doi.org/10.3390/ijms24021190 - 07 Jan 2023

Cited by 3 | Viewed by 1489

Abstract

Vascular regeneration is a complex process, additionally limited by the low regeneration potential of blood vessels. Hence, current research is focused on the design of artificial materials that combine biocompatibility with a certain rate of biodegradability and mechanical robustness. In this paper, we [...] Read more.

Vascular regeneration is a complex process, additionally limited by the low regeneration potential of blood vessels. Hence, current research is focused on the design of artificial materials that combine biocompatibility with a certain rate of biodegradability and mechanical robustness. In this paper, we have introduced a scaffold material made of poly(L-lactide-co-glycolide)/poly(isosorbide sebacate) (PLGA/PISEB) fibers fabricated in the course of an electrospinning process, and confirmed its biocompatibility towards human umbilical vein endothelial cells (HUVEC). The resulting material was characterized by a bimodal distribution of fiber diameters, with the median of 1.25 µm and 4.75 µm. Genotyping of HUVEC cells collected after 48 h of incubations on the surface of PLGA/PISEB scaffolds showed a potentially pro-angiogenic expression profile, as well as anti-inflammatory effects of this material. Over the course of a 12-week-long hydrolytic degradation process, PLGA/PISEB fibers were found to swell and disintegrate, resulting in the formation of highly developed structures resembling seaweeds. It is expected that the change in the scaffold structure should have a positive effect on blood vessel regeneration, by allowing cells to penetrate the scaffold and grow within a 3D structure of PLGA/PISEB, as well as stabilizing newly-formed endothelium during hydrolytic expansion. Full article

(This article belongs to the Special Issue Synthesis of Advanced Polymer Materials)

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18 pages, 4175 KiB

Open AccessArticle

Double Stimuli-Responsive di- and Triblock Copolymers of Poly(N-isopropylacrylamide) and Poly(1-vinylimidazole): Synthesis and Self-Assembly

by Elena Yu. Kozhunova, Anna V. Plutalova, Andrey V. Sybachin, Alexander V. Chertovich and Elena V. Chernikova

Int. J. Mol. Sci. 2023, 24(1), 879; https://doi.org/10.3390/ijms24010879 - 03 Jan 2023

Viewed by 1907

Abstract

For the first time, double stimuli-responsive properties of poly(N-isopropylacrylamide) (PNIPA) and poly(1-vinylimidazole) (PVIM) block copolymers in aqueous solutions were studied. The synthesis of PNIPA₆₀-b-PVIM₉₀ and PNIPA₂₈-b-PVIM₆₂-b-PNIPA₂₉ was performed using [...] Read more.

For the first time, double stimuli-responsive properties of poly(N-isopropylacrylamide) (PNIPA) and poly(1-vinylimidazole) (PVIM) block copolymers in aqueous solutions were studied. The synthesis of PNIPA₆₀-b-PVIM₉₀ and PNIPA₂₈-b-PVIM₆₂-b-PNIPA₂₉ was performed using reversible addition–fragmentation chain transfer (RAFT) polymerization. The polymers were characterized by size exclusion chromatography and ¹H NMR spectroscopy. The conformational behavior of the polymers was studied using dynamic light scattering (DLS) and fluorescence spectroscopy (FS). It was found that PNIPA and block copolymers conformation and ability for self-assembly in aqueous medium below and above cloud point temperature depend on the locus of hydrophobic groups derived from the RAFT agent within the chain. Additionally, the length of PVIM block, its locus in the chain and charge perform an important role in the stabilization of macromolecular micelles and aggregates below and above cloud point temperature. At 25 °C the average hydrodynamic radius (R_h) of the block copolymer particles at pH 3 is lower than at pH 9 implying the self-assembling of macromolecules in the latter case. Cloud points of PNIPA₆₀-b-PVIM₉₀ are ~43 °C and ~37 °C at a pH of 3 and 9 and of PNIPA₂₈-b-PVIM₆₂-b-PNIPA₂₉ they are ~35 °C and 31 °C at a pH of 3 and 9. Around cloud point independently of pH, the R_h value for triblock copolymer rises sharply, achieves the maximum value, then falls and reaches the constant value, while for diblock copolymer, it steadily grows after reaching cloud point. The information about polarity of microenvironment around polymer obtained by FS accords with DLS data. Full article

(This article belongs to the Special Issue Synthesis of Advanced Polymer Materials)

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10 pages, 2316 KiB

Open AccessArticle

Photoluminescent Polymer Aerogels with R, G and B Emission

by Loredana Stan, Teodor Malutan, Irina Volf, Marcel Popa, Camelia E. Tincu and Corneliu S. Stan

Int. J. Mol. Sci. 2022, 23(24), 16004; https://doi.org/10.3390/ijms232416004 - 15 Dec 2022

Cited by 2 | Viewed by 1437

Abstract

In this work, three new polymer aerogels based on 2-hydroxy ethyl methacrylate (HEMA) complexes with Eu(III), Tb(III) and La(III) are prepared and investigated. The polymer aerogels present strong photoluminescence with emissions located in the red, green and blue regions of the visible spectrum. [...] Read more.

In this work, three new polymer aerogels based on 2-hydroxy ethyl methacrylate (HEMA) complexes with Eu(III), Tb(III) and La(III) are prepared and investigated. The polymer aerogels present strong photoluminescence with emissions located in the red, green and blue regions of the visible spectrum. Depending on the water content used during the preparation path, the consistency of the photoluminescent aerogels varies from rigid, regularly shaped monoliths to a flexible, fibrous material with very low density. The morpho-structural investigation was performed by FT-IR, XPS and SEM. Thermal behavior was also evaluated, while steady-state fluorescence spectroscopy, absolute PLQY and lifetime were used for the investigation of their luminescent properties. The impressive photoluminescent emission located in the red, green and blue areas of the visible spectrum is preserved irrespective of the selected porosity. Their photo-emissive properties, tunable porosity and the convenience of the preparation path could be some arguments for applications as photonic conversion mediums in special-purpose optoelectronic devices or sensors. Full article

(This article belongs to the Special Issue Synthesis of Advanced Polymer Materials)

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13 pages, 3872 KiB

Open AccessArticle

Optical and Flame-Retardant Properties of a Series of Polyimides Containing Side Chained Bulky Phosphaphenanthrene Units

by Mihaela Homocianu, Diana Serbezeanu, Gabriela Lisa, Mihai Brebu and Tăchiță Vlad-Bubulac

Int. J. Mol. Sci. 2022, 23(21), 13174; https://doi.org/10.3390/ijms232113174 - 29 Oct 2022

Cited by 5 | Viewed by 1434

Abstract

Among the multitude of polymers with carbon-based macromolecular architectures that easily ignite in certain applications where short circuits may occur, polyimide has evolved as a class of polymers with high thermal stability while exhibiting intrinsic flame retardancy at elevated temperatures via a char-forming [...] Read more.

Among the multitude of polymers with carbon-based macromolecular architectures that easily ignite in certain applications where short circuits may occur, polyimide has evolved as a class of polymers with high thermal stability while exhibiting intrinsic flame retardancy at elevated temperatures via a char-forming mechanism. However, high amounts of aromatic rings in the macromolecular backbone are required for these results, which may affect other properties such as film-forming capacity or mechanical properties; thus, much work has been done to structurally derivatize or make hybrid polyimide systems. In this respect, flexible polyimide films (PI(1–4)) containing bulky 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) units have been developed starting from commercial dianhydrides and an aromatic diamine containing two side chain bulky DOPO groups. The chemical structure of PI(1–4)) was characterized by ¹H NMR, ¹³C NMR and ³¹P NMR spectroscopy. The optical properties, including absorption and luminescence spectra of these polymers, were analyzed. All polyimides containing DOPO derivatives emitted blue light with an emission maxima in the range of 340–445 nm, in solvents such as N,N-dimethylformamide, N-methyl-2-pyrrolidone, chloroform, and N,N-dimethylacetamide, while green light emission (λ_em = 487 nm for PI-4) was evidenced in a thin-film state. The thermal decomposition mechanism and flame-retardant behavior of the resulting materials were investigated by pyrolysis-gas-chromatography spectrometry (Py-GC), scanning electron microscopy (SEM), EDX maps and FTIR spectroscopy. The residues resulting from the TGA experiments were examined by SEM microscopy images and FTIR spectra to understand the pyrolysis mechanism. Full article

(This article belongs to the Special Issue Synthesis of Advanced Polymer Materials)

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Review

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15 pages, 1924 KiB

Open AccessReview

Microbial Synthesis of High-Molecular-Weight, Highly Repetitive Protein Polymers

by Juya Jeon, Shri Venkatesh Subramani, Kok Zhi Lee, Bojing Jiang and Fuzhong Zhang

Int. J. Mol. Sci. 2023, 24(7), 6416; https://doi.org/10.3390/ijms24076416 - 29 Mar 2023

Cited by 6 | Viewed by 2690

Abstract

High molecular weight (MW), highly repetitive protein polymers are attractive candidates to replace petroleum-derived materials as these protein-based materials (PBMs) are renewable, biodegradable, and have outstanding mechanical properties. However, their high MW and highly repetitive sequence features make them difficult to synthesize in [...] Read more.

High molecular weight (MW), highly repetitive protein polymers are attractive candidates to replace petroleum-derived materials as these protein-based materials (PBMs) are renewable, biodegradable, and have outstanding mechanical properties. However, their high MW and highly repetitive sequence features make them difficult to synthesize in fast-growing microbial cells in sufficient amounts for real applications. To overcome this challenge, various methods were developed to synthesize repetitive PBMs. Here, we review recent strategies in the construction of repetitive genes, expression of repetitive proteins from circular mRNAs, and synthesis of repetitive proteins by ligation and protein polymerization. We discuss the advantages and limitations of each method and highlight future directions that will lead to scalable production of highly repetitive PBMs for a wide range of applications. Full article

(This article belongs to the Special Issue Synthesis of Advanced Polymer Materials)

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24 pages, 2620 KiB

Open AccessReview

Polyphosphazene-Based Biomaterials for Biomedical Applications

by Geun-Woo Jin, N. Sanoj Rejinold and Jin-Ho Choy

Int. J. Mol. Sci. 2022, 23(24), 15993; https://doi.org/10.3390/ijms232415993 - 15 Dec 2022

Cited by 4 | Viewed by 2179

Abstract

Recently, synthetic polymers have attracted great interest in the field of biomedical science. Among these, polyphosphazenes (PPZs) are regarded as one of the most promising materials, due to their structural flexibility and biodegradability compared to other materials. PPZs have been developed through numerous [...] Read more.

Recently, synthetic polymers have attracted great interest in the field of biomedical science. Among these, polyphosphazenes (PPZs) are regarded as one of the most promising materials, due to their structural flexibility and biodegradability compared to other materials. PPZs have been developed through numerous studies. In particular, multi-functionalized PPZs have been proven to be potential biomaterials in various forms, such as nanoparticles (NPs) and hydrogels, through the introduction of various functional groups. Thus, PPZs have been applied for the delivery of therapeutic molecules (low molecular weight drugs, genes and proteins), bioimaging, phototherapy, bone regeneration, dental liners, modifiers and medical devices. The main goal of the present review is to highlight the recent and the most notable existing PPZ-based biomaterials for aforementioned applications, with future perspectives in mind. Full article

(This article belongs to the Special Issue Synthesis of Advanced Polymer Materials)

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