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Macromol, Volume 5, Issue 2 (June 2025) – 10 articles

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24 pages, 7153 KiB  
Article
A Comparative Study on the Compatibilization of Thermoplastic Starch/Polybutylene Succinate Blends by Chain Extender and Epoxidized Linseed Oil
by Ke Gong, Yinshi Lu, Alexandre Portela, Soheil Farshbaf Taghinezhad, David Lawlor, Shane Connolly, Mengli Hu, Yuanyuan Chen and Maurice N. Collins
Macromol 2025, 5(2), 24; https://doi.org/10.3390/macromol5020024 - 12 May 2025
Viewed by 171
Abstract
The immiscibility of thermoplastic starch (TPS) and polybutylene succinate (PBS) complicates the thermal processing of these materials. This study provides the first comparative assessment of two compatibilizers with differing reaction mechanisms, Joncryl® ADR 4468 and epoxidized linseed oil (ELO), for the optimization [...] Read more.
The immiscibility of thermoplastic starch (TPS) and polybutylene succinate (PBS) complicates the thermal processing of these materials. This study provides the first comparative assessment of two compatibilizers with differing reaction mechanisms, Joncryl® ADR 4468 and epoxidized linseed oil (ELO), for the optimization of biobased TPS/PBS blends. A total of 13 batches, varying in compatibilizer and blend composition, were processed via hot melt extrusion and injection molding to produce pellets. Blends were analyzed using tensile and impact testing, differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), rheology, and scanning electron microscopy (SEM). The findings suggest that both compatibilizers can improve the compatibility of these blends, as evidenced by higher glass transition temperatures (Tg) compared to the reference batch (100-0-N/A). Joncryl® ADR 4468 batches exhibit superior tensile strength and Young’s moduli, while ELO batches demonstrate greater elongation at break. The enhanced processability observed in Joncryl® ADR 4468 is attributed to the increased polymer chain entanglement and molecular weight, whereas ELO facilitates greater chain mobility due to its plasticizing effect. These differences arise from the distinct mechanisms of action: Joncryl® ADR 4468 promotes chain extension and crosslinking, whereas ELO mainly enhances flexibility through plasticization. Overall, this study provides a comparative assessment of these compatibilizers in TPS/PBS blends, laying the groundwork for future investigations into optimizing compatibilizer concentration and blend composition. Full article
(This article belongs to the Collection Advances in Biodegradable Polymers)
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18 pages, 5182 KiB  
Review
Evolutionary Routes to Modern Metabolic Pathways
by Alberto Vázquez-Salazar and Israel Muñoz-Velasco
Macromol 2025, 5(2), 23; https://doi.org/10.3390/macromol5020023 - 8 May 2025
Viewed by 411
Abstract
Metabolism, the network of biochemical reactions that powers life, arose under conditions radically different from those on Earth today. Investigating its origins reveals how initially simple chemical processes gradually integrated nucleic acid and then protein catalysts, becoming progressively more complex and regulated until [...] Read more.
Metabolism, the network of biochemical reactions that powers life, arose under conditions radically different from those on Earth today. Investigating its origins reveals how initially simple chemical processes gradually integrated nucleic acid and then protein catalysts, becoming progressively more complex and regulated until they evolved into the enzyme-rich systems observed in modern organisms. Here, we integrate multiple perspectives on the origin of metabolism, focusing primarily on an evolutionary trajectory from an RNA-based world, where ribozymes, metal ions, coenzymes, small peptides, and other small organic molecules worked in concert, to enzyme-driven metabolic networks. We also address the longstanding debates on whether these early metabolic pathways were largely autotrophic or heterotrophic, and consider so-called “pre-metabolisms” (non-enzymatic networks) as an alternative conceptual framework. We discuss key examples such as the Wood–Ljungdahl (W–L) pathway and the reverse tricarboxylic acid (TCA) cycle, both posited to function under early Earth conditions. Finally, we examine how the environment (e.g., minerals, clays, hydrothermal vents) shaped early metabolism, describe unresolved questions about the Last Common Ancestor’s catalytic repertoire and propose future directions that link geochemical insights with molecular biology and synthetic approaches. Full article
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12 pages, 13721 KiB  
Article
Description of Paper–UV-Curable Thermochromic Ink Interactions with Surface-Free Energy Measurements
by Marina Vukoje, Rahela Kulčar and Tomislav Cigula
Macromol 2025, 5(2), 22; https://doi.org/10.3390/macromol5020022 - 6 May 2025
Viewed by 137
Abstract
The adhesion of printing inks to printing substrates is a complex process influenced by both the physical and chemical properties of the printing substrate and of the printing ink. Synthetic paper, being a polymer with no absorption capability, limits the interaction between the [...] Read more.
The adhesion of printing inks to printing substrates is a complex process influenced by both the physical and chemical properties of the printing substrate and of the printing ink. Synthetic paper, being a polymer with no absorption capability, limits the interaction between the ink and substrate, leading to lower adhesion values. On synthetic paper, the thicker polymer resin layer covering the microcapsules results in a more stable ink film and lighter print coloration. In contrast, UV-curable ink applied to bulky and recycled papers, which have porous structures, exhibits more dynamic interactions. The polymer resin in the ink penetrates the paper’s pores, forming a stronger bond with the paper fibers and improving adhesion quality. Surface roughness also plays a significant role in ink adhesion. Rough surfaces increase contact between ink and paper, enhancing mechanical adhesion by allowing the ink to “lock” into the surface’s irregularities. The surface energy (SFE) at the interphase between paper and ink is also a key factor. Low SFE promotes better wetting and ink absorption, improving adhesion. Ink penetration into the printing substrate is crucial for achieving high-quality adhesion. Full article
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34 pages, 2173 KiB  
Review
Advances in Microbial and Plant-Based Biopolymers: Synthesis and Applications in Next-Generation Materials
by Poova Kattil Drishya, M. Venkateswar Reddy, Gunda Mohanakrishna, Omprakash Sarkar, Isha, M. V. Rohit, Aesha Patel and Young-Cheol Chang
Macromol 2025, 5(2), 21; https://doi.org/10.3390/macromol5020021 - 6 May 2025
Viewed by 296
Abstract
Biopolymers are revolutionizing the materials landscape, driven by a growing demand for sustainable alternatives to traditional petroleum-based materials. Sourced from biological origins, these polymers are not only environment friendly but also present exciting solutions in healthcare, packaging, biosensors, high performance, and durable materials [...] Read more.
Biopolymers are revolutionizing the materials landscape, driven by a growing demand for sustainable alternatives to traditional petroleum-based materials. Sourced from biological origins, these polymers are not only environment friendly but also present exciting solutions in healthcare, packaging, biosensors, high performance, and durable materials as alternatives to crude oil-based products. Recently, biopolymers derived from plants, such as lignin and cellulose, alongside those produced by bacteria, like polyhydroxyalkanoates (PHAs), have captured the spotlight, drawing significant interest for their industrial and eco-friendly applications. The growing interest in biopolymers stems from their potential as sustainable, renewable materials across diverse applications. This review provides an in-depth analysis of the current advancements in plant-based and bacterial biopolymers, covering aspects of bioproduction, downstream processing, and their integration into high-performance next-generation materials. Additionally, we delve into the technical challenges of cost-effectiveness, processing, and scalability, which are critical barriers to widespread adoption. By highlighting these issues, this review aims to equip researchers in the bio-based domain with a comprehensive understanding of how plant-based and bacterial biopolymers can serve as viable alternatives to petroleum-derived materials. Ultimately, we envision a transformative shift from a linear, fossil fuel-based economy to a circular, bio-based economy, fostering more sustainable and environmentally conscious material solutions using novel biopolymers aligning with the framework of the United Nations Sustainable Development Goals (SDGs), including clean water and sanitation (SDG 6), industry, innovation, and infrastructure (SDG 9), affordable and clean energy (SDG 7), sustainable cities and communities (SDG 11), responsible production and consumption (SDG 12), and climate action (SDG 13). Full article
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37 pages, 2896 KiB  
Review
Degradation Mechanisms of Cellulose-Based Transformer Insulation: The Role of Dissolved Gases and Macromolecular Characterisation
by Andrew Adewunmi Adekunle, Samson Okikiola Oparanti, Issouf Fofana, Patrick Picher, Esperanza Mariela Rodriguez-Celis, Oscar Henry Arroyo-Fernandez and Fethi Meghnefi
Macromol 2025, 5(2), 20; https://doi.org/10.3390/macromol5020020 - 1 May 2025
Viewed by 249
Abstract
The ageing of cellulose paper-based transformer insulation is a critical factor influencing the reliability and lifespan of power transformers, as insulating paper is not easily replaced or repaired. Therefore, this review explores the degradation mechanisms of insulating paper, emphasising the roles of dissolved [...] Read more.
The ageing of cellulose paper-based transformer insulation is a critical factor influencing the reliability and lifespan of power transformers, as insulating paper is not easily replaced or repaired. Therefore, this review explores the degradation mechanisms of insulating paper, emphasising the roles of dissolved gases, chemical markers, and macromolecular characterisation in assessing paper deterioration. Likewise, the impact of moisture and thermal stress on the breakdown of cellulose fibres are discussed, especially acid hydrolysis, which serves as the main degradation mechanism in cellulose insulating paper. Advanced diagnostic techniques for insulation condition monitoring, such as molecular simulations, glass transition temperature analysis, and DP estimation models, are highlighted. Furthermore, special attention is given to natural esters as alternative insulating liquids, demonstrating their ability to slow cellulose ageing through moisture absorption, hydrogen bonding stabilisation, and transesterification reactions. This paper also evaluates key chemical markers, including 2FAL and methanol, for estimating paper degradation. A comprehensive understanding of these mechanisms and diagnostic approaches can enhance predictive maintenance strategies and improve transformer longevity. Full article
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34 pages, 1224 KiB  
Review
An Overview of Starch-Based Materials for Sustainable Food Packaging: Recent Advances, Limitations, and Perspectives
by Tarsila Rodrigues Arruda, Gabriela de Oliveira Machado, Clara Suprani Marques, Amanda Lelis de Souza, Franciele Maria Pelissari, Taíla Veloso de Oliveira and Rafael Resende Assis Silva
Macromol 2025, 5(2), 19; https://doi.org/10.3390/macromol5020019 - 15 Apr 2025
Viewed by 710
Abstract
As the global plastic pollution crisis intensifies, the development of sustainable food packaging materials has become a priority. Starch-based films present a viable, biodegradable alternative to petroleum-derived plastics but face challenges such as poor moisture resistance and mechanical fragility. This review comprehensively examines [...] Read more.
As the global plastic pollution crisis intensifies, the development of sustainable food packaging materials has become a priority. Starch-based films present a viable, biodegradable alternative to petroleum-derived plastics but face challenges such as poor moisture resistance and mechanical fragility. This review comprehensively examines state-of-the-art advancements in starch-based packaging, including polymer modifications, bio-nanocomposite incorporation, and innovative processing techniques that enhance functionality. Furthermore, the role of advanced analytical tools in elucidating the structure–performance relationships of starch films is highlighted. In particular, we provide an in-depth exploration of advanced characterization techniques, not only to assess starch-based food packaging but also to monitor starch retrogradation, including Fourier-transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), nuclear magnetic resonance (NMR), and iodine binding (Blue Value). We also explore cutting-edge developments in active and intelligent packaging, where starch films are functionalized with bioactive compounds for antimicrobial protection and freshness monitoring. While substantial progress has been made, critical challenges remain in upscaling these technologies for industrial production. This review provides a roadmap for future research and the industrial adoption of starch-derived packaging solutions. Full article
(This article belongs to the Collection Advances in Biodegradable Polymers)
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17 pages, 2194 KiB  
Article
Polysaccharides from Brown Seaweeds (Padina boergesenii and Sargassum euryphyllum) as Promising Inhibitors of SARS-CoV-2: Characterization, Mechanisms, and Therapeutic Potential
by Saly Gheda, Ali M. Karkour, Shimaa El Shafay, Mohamed GabAllah, João Cotas and Leonel Pereira
Macromol 2025, 5(2), 18; https://doi.org/10.3390/macromol5020018 - 10 Apr 2025
Viewed by 1346
Abstract
Unexpected mutations in SARS-CoV-2 produce unique variations. While numerous vaccines and antiviral medications are available for SARS-CoV-2, their use in controlling and preventing COVID-19 is restricted in some areas and countries due to accessibility and cost issues. This study investigated polysaccharides produced from [...] Read more.
Unexpected mutations in SARS-CoV-2 produce unique variations. While numerous vaccines and antiviral medications are available for SARS-CoV-2, their use in controlling and preventing COVID-19 is restricted in some areas and countries due to accessibility and cost issues. This study investigated polysaccharides produced from two brown seaweed (Padina boergesenii and Sargassum euryphyllum) for their capacity to inhibit SARS-CoV-2. The seaweed polysaccharides were characterized and identified using ultraviolet and visible (UV/VIS) and Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectra. The polysaccharides inhibited SARS-CoV-2 propagation with inhibitory concentration 50% (IC50) values ranging from 24.2 to 29.3 µg/mL and cytotoxicity concentration 50% (CC50) values for Vero-E6 cells ranging from 587.7 to 396.4 µg/mL for P. boergesenii and S. euryphyllum, respectively. P. boergesenii polysaccharide had a more substantial antiviral potential than S. euryphyllum against SARS-CoV-2 and appeared more promising. At a concentration of 575 µL/mL of P. boergesenii polysaccharide, the virucidal mechanism was found to be the most effective, followed by viral adsorption and replication, with viral inhibition percentages of 68.6% ± 0.8, 57.1% ± 1.4, and 37.2 ± 3, respectively, compared to remdesivir as an antiviral drug. Thus, we concluded that brown seaweed alginate polysaccharides efficiently inhibit SARS-CoV-2 from spreading by preventing viral entry. Finally, P. boergesenii polysaccharide looked promising as a potential therapeutic candidate for the treatment of COVID-19. Full article
(This article belongs to the Special Issue Recent Trends in Carbohydrate-Based Therapeutics)
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14 pages, 6307 KiB  
Article
The Clear Choice: Developing Transparent Cork for Next-Generation Sustainable Materials
by Pedro Gil, Pedro L. Almeida, Maria H. Godinho and Ana P. C. Almeida
Macromol 2025, 5(2), 17; https://doi.org/10.3390/macromol5020017 - 8 Apr 2025
Viewed by 320
Abstract
Many modern technologies rely on materials that harm the environment. Glass manufacturing, for instance, is both expensive and environmentally damaging. In response, scientists have developed a technique to replace glass with transparent wood, an innovative, versatile, and sustainable alternative. Wood naturally retains heat, [...] Read more.
Many modern technologies rely on materials that harm the environment. Glass manufacturing, for instance, is both expensive and environmentally damaging. In response, scientists have developed a technique to replace glass with transparent wood, an innovative, versatile, and sustainable alternative. Wood naturally retains heat, is durable, and remains cost-effective, making it promising substitute for glass and plastic in window production. This innovation highlights the urgent need for eco-friendly technologies to replace or improve existing materials. This work explores cork as a sustainable alternative for producing transparent materials, potentially replacing transparent wood. Unlike wood, cork can be harvested from the same tree for up to 300 years. The process followed a method like transparent wood production, involving delignification, bleaching, and forced polymer impregnation. The choice of bleaching agent significantly impacted results—samples treated with sodium hypochlorite solution appeared whiter but became extremely fragile, whereas hydrogen peroxide preserved mechanical properties better. The resin-to-hardener ratio was crucial, with higher resin content improving polymer infiltration and transparency. While fully transparent cork was not achieved, the resulting translucent material lays the groundwork for future research in this field. Full article
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17 pages, 3883 KiB  
Article
Thermal Evaluation of Biocomposites Made from Poly(Lactic Acid) and Cottonseed Byproducts
by Zhongqi He, Sunghyun Nam, Sourabh Kulkarni, Mohammad Bagheri Kashani and Ramaswamy Nagarajan
Macromol 2025, 5(2), 16; https://doi.org/10.3390/macromol5020016 - 8 Apr 2025
Viewed by 294
Abstract
Poly(lactic acid) (PLA) is derived from sugar-based materials. While it is a leading sustainable biopolymer, PLA has been integrated with other agricultural coproducts (e.g., lignin, protein, and starch) to reduce its cost and enhance its modulus and biodegradability. Cottonseed oil and meal are [...] Read more.
Poly(lactic acid) (PLA) is derived from sugar-based materials. While it is a leading sustainable biopolymer, PLA has been integrated with other agricultural coproducts (e.g., lignin, protein, and starch) to reduce its cost and enhance its modulus and biodegradability. Cottonseed oil and meal are the byproducts of the cotton fiber industry. In this work, four biocomposites were formulated with PLA, cottonseed oil, washed cottonseed meal, and plasticizing reagent glycerol with different formulation ratios. The thermal degradation behaviors were examined via thermogravimetric (TG) analysis under air and nitrogen conditions with the neat PLA sample as a control. The thermal decomposition characteristic values were impacted by both the biocomposite formulation and the heating rates of 1, 2, 5, and 10 °C min−1. Results from two kinetic modeling methods that were examined indicated that the activation energy was relatively steady for the neat PLA in the whole degradation process. Generally, the low activation energy values of biocomposites other than PLA under nitrogen conditions implied that these cottonseed byproduct constituents promote the thermal decomposition of these biocomposites. However, the presence of oxygen would confound the thermal decomposition of the biocomposites, as shown by variable activation energy curves with higher values under air conditions. TG-FTIR analysis revealed that the major gaseous compounds were carbonyl, carbon dioxide, carbon monoxide, methane, and water, which were derived from the thermal decomposition of the biocomposites. Full article
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19 pages, 2035 KiB  
Review
Chitin, Chitosan and Its Derivatives: Antimicrobials and/or Mitigators of Water
by Eva Scarcelli, Alessia Catalano, Domenico Iacopetta, Jessica Ceramella, Maria Stefania Sinicropi and Francesca Aiello
Macromol 2025, 5(2), 15; https://doi.org/10.3390/macromol5020015 - 8 Apr 2025
Viewed by 512
Abstract
Antimicrobial resistance (AMR) is a major global health problem, exacerbated by the excessive and inappropriate use of antibiotics in human medicine, animal care and agriculture. Therefore, new strategies and compounds are needed to overcome this issue. In this view, it may be appropriate [...] Read more.
Antimicrobial resistance (AMR) is a major global health problem, exacerbated by the excessive and inappropriate use of antibiotics in human medicine, animal care and agriculture. Therefore, new strategies and compounds are needed to overcome this issue. In this view, it may be appropriate to reconsider existing biomaterials to alleviate antibiotic overuse. Chitin, a naturally abundant amino mucopolysaccharide, is a poly-β-1, 4-N-acetylglucosamine (GlcNAc). It is a white, hard, inelastic, nitrogenous polysaccharide and the major source of surface pollution in coastal areas. Chitosan derives from the partial N-deacetylation of chitin and originates from the shells of crustaceans and the fungi cell walls. It is a nontoxic natural antimicrobial polymer approved by GRAS (Generally Recognized as Safe by the United States Food and Drug Administration). Chitin and chitosan, as non-toxic biopolymers, are useful compounds for wastewater treatment to remove pollutants, such as pharmaceuticals, heavy metals and dyes. The described features make these biopolymers intriguing compounds to be investigated for their application as antibacterials. Full article
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