Materials Science â€ș Biomaterials

biodegradable polymer synthesis and properties

Description

This cluster of papers focuses on the development, synthesis, properties, and applications of biodegradable polymers such as polylactic acid (PLA) and polyhydroxyalkanoates. It covers topics including sustainable polymers, tissue engineering materials, ring-opening polymerization, biomedical applications, nanocomposites, and the production of green plastics.

Keywords

Biodegradable Polymers; Polylactic Acid; Polyhydroxyalkanoates; Sustainable Polymers; Tissue Engineering Materials; Ring-Opening Polymerization; Biomedical Applications; Nanocomposites; Green Plastics; Polyester Synthases

Introduction to Biotechnical and Biomedical Applications of Poly(Ethylene Glycol) J.M. Harris. Water Structure and PEG Solutions by DSC Measurement K.P. Antonsen, A.S. Hoffman. Molecular Simulation of Protein-PEG Interaction K. Lim, 
 Introduction to Biotechnical and Biomedical Applications of Poly(Ethylene Glycol) J.M. Harris. Water Structure and PEG Solutions by DSC Measurement K.P. Antonsen, A.S. Hoffman. Molecular Simulation of Protein-PEG Interaction K. Lim, J.N. Herron. PEG Derivatized Ligands with Hydrophobic and Immunological Specificity D.E. Brooks, et al. Affinity Partitioning in PEG Containing TwoPhase Systems G. Johansson. Aqueous Two-Phase Partitioning on Industrial Scale F. Tjerneld. PEGModified Protein Hybrid Catalyst K. Yoshinaga, et al. PEGCouple Semisynthetic Oxidases T. Yomao, et al. Preparation and Properties of Monomethoxypoly(Ethylene Glycol)Modified Enzymes for Therapeutic Applications F.M. Veronese, et al. Suppression of Antibody Responses by Conjugates of Antigens and Monomethoxypoly(Ethylene Glycol) A. Sehon. 12 additional articles. Index.
Polyhydroxyalkanoates (PHAs), of which polyhydroxybutyrate (PHB) is the most abundant, are bacterial carbon and energy reserve materials of widespread occurrence. They are composed of 3-hydroxyacid monomer units and exist as 
 Polyhydroxyalkanoates (PHAs), of which polyhydroxybutyrate (PHB) is the most abundant, are bacterial carbon and energy reserve materials of widespread occurrence. They are composed of 3-hydroxyacid monomer units and exist as a small number of cytoplasmic granules per cell. The properties of the C4 homopolymer PHB as a biodegradable thermoplastic first attracted industrial attention more than 20 years ago. Copolymers of C4 (3-hydroxybutyrate [3HB]) and C5 (3-hydroxyvalerate [3HV]) monomer units have modified physical properties; e.g., the plastic is less brittle than PHB, whereas PHAs containing C8 to C12 monomers behave as elastomers. This family of materials is the centre of considerable commercial interest, and 3HB-co-3HV copolymers have been marketed by ICI plc as Biopol. The known polymers exist as 2(1) helices with the fiber repeat decreasing from 0.596 nm for PHB to about 0.45 nm for C8 to C10 polymers. Novel copolymers with a backbone of 3HB and 4HB have been obtained. The native granules contain noncrystalline polymer, and water may possibly act as a plasticizer. Although the biosynthesis and regulation of PHB are generally well understood, the corresponding information for the synthesis of long-side-chain PHAs from alkanes, alcohols, and organic acids is still incomplete. The precise mechanisms of action of the polymerizing and depolymerizing enzymes also remain to be established. The structural genes for the three key enzymes of PHB synthesis from acetyl coenzyme A in Alcaligenes eutrophus have been cloned, sequenced, and expressed in Escherichia coli. Polymer molecular weights appear to be species specific. The factors influencing the commercial choice of organism, substrate, and isolation process are discussed. The physiological functions of PHB as a reserve material and in symbiotic nitrogen fixation and its presence in bacterial plasma membranes and putative role in transformability and calcium signaling are also considered.
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTControlled Ring-Opening Polymerization of Lactide and GlycolideOdile Dechy-Cabaret, Blanca Martin-Vaca, and Didier BourissouView Author Information Laboratoire HĂ©tĂ©rochimie Fondamentale et AppliquĂ©e du CNRS (UMR 5069), UniversitĂ© Paul Sabatier, 
 ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTControlled Ring-Opening Polymerization of Lactide and GlycolideOdile Dechy-Cabaret, Blanca Martin-Vaca, and Didier BourissouView Author Information Laboratoire HĂ©tĂ©rochimie Fondamentale et AppliquĂ©e du CNRS (UMR 5069), UniversitĂ© Paul Sabatier, 118, route de Narbonne, 31062 Toulouse Cedex 04, France Cite this: Chem. Rev. 2004, 104, 12, 6147–6176Publication Date (Web):October 5, 2004Publication History Received26 April 2004Published online5 October 2004Published inissue 1 December 2004https://pubs.acs.org/doi/10.1021/cr040002shttps://doi.org/10.1021/cr040002sresearch-articleACS PublicationsCopyright © 2004 American Chemical SocietyRequest reuse permissionsArticle Views34594Altmetric-Citations2015LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Ligands,Monomers,Organic polymers,Plastics,Ring-opening polymerization Get e-Alerts
In recent years, much attention has been focused on research to replace petroleum-based commodity plastics, in a cost-effective manner, with biodegradable materials offering competitive mechanical properties. Biopolymers have been considered 
 In recent years, much attention has been focused on research to replace petroleum-based commodity plastics, in a cost-effective manner, with biodegradable materials offering competitive mechanical properties. Biopolymers have been considered as the most promising materials for this purpose. However, they generally present poor mechanical properties regarding processability and end-use application, since the fragility and brittleness exhibited during thermoformation can limit their potential for application. In order to overcome this problem, plasticizers are added to provide the necessary workability to biopolymers. This class of products became more visible when biodegradable additives and plasticizers also became the focus of material scientists. The use of natural and/or biodegradable plasticizers, with low toxicity and good compatibility with several plastics, resins, rubber and elastomers in substitution of conventional plasticizers, such as phthalates and other synthetic conventional plasticizers attracted the market along with the increasing worldwide trend towards use of biopolymers. Here we discuss the main results and developments in natural plasticizer/synthetic and biopolymer-based films during the last decades.
Biodegradable polymers are designed to degrade upon disposal by the action of living organisms. Extraordinary progress has been made in the development of practical processes and products from polymers such 
 Biodegradable polymers are designed to degrade upon disposal by the action of living organisms. Extraordinary progress has been made in the development of practical processes and products from polymers such as starch, cellulose, and lactic acid. The need to create alternative biodegradable water-soluble polymers for down-the-drain products such as detergents and cosmetics has taken on increasing importance. Consumers have, however, thus far attached little or no added value to the property of biodegradability, forcing industry to compete head-to-head on a cost-performance basis with existing familiar products. In addition, no suitable infrastructure for the disposal of biodegradable materials exists as yet.
Poly(lactic-co-glycolic) acid (PLGA) has attracted considerable interest as a base material for biomedical applications due to its: (i) biocompatibility; (ii) tailored biodegradation rate (depending on the molecular weight and copolymer 
 Poly(lactic-co-glycolic) acid (PLGA) has attracted considerable interest as a base material for biomedical applications due to its: (i) biocompatibility; (ii) tailored biodegradation rate (depending on the molecular weight and copolymer ratio); (iii) approval for clinical use in humans by the U.S. Food and Drug Administration (FDA); (iv) potential to modify surface properties to provide better interaction with biological materials; and (v) suitability for export to countries and cultures where implantation of animal-derived products is unpopular. This paper critically reviews the scientific challenge of manufacturing PLGA-based materials with suitable properties and shapes for specific biomedical applications, with special emphasis on bone tissue engineering. The analysis of the state of the art in the field reveals the presence of current innovative techniques for scaffolds and material manufacturing that are currently opening the way to prepare biomimetic PLGA substrates able to modulate cell interaction for improved substitution, restoration, or enhancement of bone tissue function.
Aliphatic polyesters prepared by ring-opening polymerization of lactones are now used worldwide as bioresorbabale devices in surgery (orthopaedic devices, sutures, stents, tissue engineering, and adhesion barriers) and in pharmacology (control 
 Aliphatic polyesters prepared by ring-opening polymerization of lactones are now used worldwide as bioresorbabale devices in surgery (orthopaedic devices, sutures, stents, tissue engineering, and adhesion barriers) and in pharmacology (control drug delivery). This review presents the various methods of the synthesis of polyesters and tailoring the properties by proper control of molecular weight, composition, and architecture so as to meet the stringent requirements of devices in the medical field. The effect of structure on properties and degradation has been discussed. The applications of these polymers in the biomedical field are described in detail.
Polylactic acid is proving to be a viable alternative to petrochemical-based plastics for many applications. It is produced from renewable resources and is biodegradable, decomposing to give H2O, CO2, and 
 Polylactic acid is proving to be a viable alternative to petrochemical-based plastics for many applications. It is produced from renewable resources and is biodegradable, decomposing to give H2O, CO2, and humus, the black material in soil. In addition, it has unique physical properties that make it useful in diverse applications including paper coating, fibers, films, and packaging (see Figure).
Abstract Summary: Polylactide polymers have gained enormous attention as a replacement for conventional synthetic packaging materials in the last decade. By being truly biodegradable, derived from renewable resources and by 
 Abstract Summary: Polylactide polymers have gained enormous attention as a replacement for conventional synthetic packaging materials in the last decade. By being truly biodegradable, derived from renewable resources and by providing consumers with extra end‐use benefits such as avoiding paying the “green tax” in Germany or meeting environmental regulations in Japan, polylactides (PLAs) are a growing alternative as a packaging material for demanding markets. The aim of this paper is to review the production techniques for PLAs, summarize the main properties of PLA and to delineate the main advantages and disadvantages of PLA as a polymeric packaging material. PLA films have better ultraviolet light barrier properties than low density polyethylene (LDPE), but they are slightly worse than those of cellophane, polystyrene (PS) and poly(ethylene terephthalate) (PET). PLA films have mechanical properties comparable to those of PET and better than those of PS. PLA also has lower melting and glass transition temperatures than PET and PS. The glass transition temperature of PLA changes with time. Humidity between 10 and 95% and storage temperatures of 5 to 40 °C do not have an effect on the transition temperature of PLA, which can be explained by its low water sorption values (i.e. <100 ppm at A w = 1). PLA seals well at temperatures below the melting temperature but an appreciable shrinking of the films has been noted when the material is sealed near its melting temperature. Solubility parameter predictions indicate that PLA will interact with nitrogen compounds, anhydrides and some alcohols and that it will not interact with aromatic hydrocarbons, ketones, esters, sulfur compounds or water. The CO 2 , O 2 and water permeability coefficients of PLA are lower than those of PS and higher than those of PET. Its barrier to ethyl acetate and D ‐limonene is comparable to PET. The amount of lactic acid and its derivatives that migrate to food simulant solutions from PLA is much lower than any of the current average dietary lactic acid intake values allowed by several governmental agencies. Thus, PLA is safe for use in fabricating articles for contact with food. Percent transmission versus wavelength for PLA(98% L ‐lactide), PS, LDPE, PET and cellophane films. image Percent transmission versus wavelength for PLA(98% L ‐lactide), PS, LDPE, PET and cellophane films.
Abstract: Environmental, economic, and safety challenges have provoked packaging scientists and producers to partially substitute petrochemical‐based polymers with biodegradable ones. The general purpose of this review is to introduce poly‐lactic 
 Abstract: Environmental, economic, and safety challenges have provoked packaging scientists and producers to partially substitute petrochemical‐based polymers with biodegradable ones. The general purpose of this review is to introduce poly‐lactic acid (PLA), a compostable, biodegradable thermoplastic made from renewable sources. PLA properties and modifications via different methods, like using modifiers, blending, copolymerizing, and physical treatments, are mentioned; these are rarely discussed together in other reviews. Industrial processing methods for producing different PLA films, wrappings, laminates, containers (bottles and cups), are presented. The capabilities of PLA for being a strong active packaging material in different areas requiring antimicrobial and antioxidant characteristics are discussed. Consequently, applications of nanomaterials in combination with PLA structures for creating new PLA nanocomposites with greater abilities are also covered. These approaches may modify PLA weaknesses for some food packaging applications. Nanotechnology approaches are being broadened in food science, especially in packaging material science with high performances and low concentrations and prices, so this category of nano‐research is estimated to be revolutionary in food packaging science in the near future. The linkage of a 100% bio‐originated material and nanomaterials opens new windows for becoming independent, primarily, of petrochemical‐based polymers and, secondarily, for answering environmental and health concerns will undoubtedly be growing with time.
In past two decades poly lactic-co-glycolic acid (PLGA) has been among the most attractive polymeric candidates used to fabricate devices for drug delivery and tissue engineering applications. PLGA is biocompatible 
 In past two decades poly lactic-co-glycolic acid (PLGA) has been among the most attractive polymeric candidates used to fabricate devices for drug delivery and tissue engineering applications. PLGA is biocompatible and biodegradable, exhibits a wide range of erosion times, has tunable mechanical properties and most importantly, is a FDA approved polymer. In particular, PLGA has been extensively studied for the development of devices for controlled delivery of small molecule drugs, proteins and other macromolecules in commercial use and in research. This manuscript describes the various fabrication techniques for these devices and the factors affecting their degradation and drug release.
This paper reviews biodegradable synthetic polymers focusing on their potential in tissue engineering applications.The major classes of polymers are briefly discussed with regard to synthesis, properties and biodegradability, and known 
 This paper reviews biodegradable synthetic polymers focusing on their potential in tissue engineering applications.The major classes of polymers are briefly discussed with regard to synthesis, properties and biodegradability, and known degradation modes and products are indicated based on studies reported in the literature.A vast majority of biodegradable polymers studied belongs to the polyester family, which includes polyglycolides and polylactides.Some disadvantages of these polymers in tissue engineering applications are their poor biocompatibility, release of acidic degradation products, poor processability and loss of mechanical properties very early during degradation.Other degradable polymers such as polyorthoesters, polyanhydrides, polyphosphazenes, and polyurethanes are also discussed and their advantages and disadvantages summarised.With advancements in tissue engineering it has become necessary to develop polymers that meet more demanding requirements.Recent work has focused on developing injectable polymer compositions based on poly (propylene fumarate) and poly (anhydrides) to meet these requirements in orthopaedic tissue engineering.Polyurethanes have received recent attention for development of degradable polymers because of their great potential in tailoring polymer structure to achieve mechanical properties and biodegradability to suit a variety of applications.
Numerous biodegradable polymers have been developed in the last two decades. In terms of application, biodegradable polymers are classified into three groups: medical, ecological, and dual application, while in terms 
 Numerous biodegradable polymers have been developed in the last two decades. In terms of application, biodegradable polymers are classified into three groups: medical, ecological, and dual application, while in terms of origin they are divided into two groups: natural and synthetic. This review article will outline classification, requirements, applications, physical properties, biodegradability, and degradation mechanisms of representative biodegradable polymers that have already been commercialized or are under investigation. Among the biodegradable polymers, recent developments of aliphatic polyesters, especially polylactides and poly(lactic acid)s, will be mainly described in the last part.
The Institute of Food Technologists has issued this Scientific Status Summary to update readers on food packaging and its impact on the environment. The Institute of Food Technologists has issued this Scientific Status Summary to update readers on food packaging and its impact on the environment.
Polycaprolactone (PCL) is an important polymer due to its mechanical properties, miscibility with a large range of other polymers and biodegradability. Two main pathways to produce polycaprolactone have been described 
 Polycaprolactone (PCL) is an important polymer due to its mechanical properties, miscibility with a large range of other polymers and biodegradability. Two main pathways to produce polycaprolactone have been described in the literature: the polycondensation of a hydroxycarboxylic acid: 6-hydroxyhexanoic acid, and the ring-opening polymerisation (ROP) of a lactone: Δ-caprolactone (Δ-CL). This critical review summarises the different conditions which have been described to synthesise PCL, and gives a broad overview of the different catalytic systems that were used (enzymatic, organic and metal catalyst systems). A surprising variety of catalytic systems have been studied, touching on virtually every section of the periodic table. A detailed list of reaction conditions and catalysts/initiators is given and reaction mechanisms are presented where known. Emphasis is put on the ROP pathway due to its prevalence in the literature and the superior polymer that is obtained. In addition, ineffective systems that have been tried to catalyse the production of PCL are included in the electronic supplementary information for completeness (141 references).
Biopolyesters polyhydroxyalkanoates (PHA) produced by many bacteria have been investigated by microbiologists, molecular biologists, biochemists, chemical engineers, chemists, polymer experts and medical researchers. PHA applications as bioplastics, fine chemicals, implant 
 Biopolyesters polyhydroxyalkanoates (PHA) produced by many bacteria have been investigated by microbiologists, molecular biologists, biochemists, chemical engineers, chemists, polymer experts and medical researchers. PHA applications as bioplastics, fine chemicals, implant biomaterials, medicines and biofuels have been developed and are covered in this critical review. Companies have been established or involved in PHA related R&D as well as large scale production. Recently, bacterial PHA synthesis has been found to be useful for improving robustness of industrial microorganisms and regulating bacterial metabolism, leading to yield improvement on some fermentation products. In addition, amphiphilic proteins related to PHA synthesis including PhaP, PhaZ or PhaC have been found to be useful for achieving protein purification and even specific drug targeting. It has become clear that PHA and its related technologies are forming an industrial value chain ranging from fermentation, materials, energy to medical fields (142 references).
Poly(3-hydroxyalkanoates) (PHAs) are a class of microbially produced polyesters that have potential applications as conventional plastics, specifically thermoplastic elastomers. A wealth of biological diversity in PHA formation exists, with at 
 Poly(3-hydroxyalkanoates) (PHAs) are a class of microbially produced polyesters that have potential applications as conventional plastics, specifically thermoplastic elastomers. A wealth of biological diversity in PHA formation exists, with at least 100 different PHA constituents and at least five different dedicated PHA biosynthetic pathways. This diversity, in combination with classical microbial physiology and modern molecular biology, has now opened up this area for genetic and metabolic engineering to develop optimal PHA-producing organisms. Commercial processes for PHA production were initially developed by W. R. Grace in the 1960s and later developed by Imperial Chemical Industries, Ltd., in the United Kingdom in the 1970s and 1980s. Since the early 1990s, Metabolix Inc. and Monsanto have been the driving forces behind the commercial exploitation of PHA polymers in the United States. The gram-negative bacterium Ralstonia eutropha, formerly known as Alcaligenes eutrophus, has generally been used as the production organism of choice, and intracellular accumulation of PHA of over 90% of the cell dry weight have been reported. The advent of molecular biological techniques and a developing environmental awareness initiated a renewed scientific interest in PHAs, and the biosynthetic machinery for PHA metabolism has been studied in great detail over the last two decades. Because the structure and monomeric composition of PHAs determine the applications for each type of polymer, a variety of polymers have been synthesized by cofeeding of various substrates or by metabolic engineering of the production organism. Classical microbiology and modern molecular bacterial physiology have been brought together to decipher the intricacies of PHA metabolism both for production purposes and for the unraveling of the natural role of PHAs. This review provides an overview of the different PHA biosynthetic systems and their genetic background, followed by a detailed summation of how this natural diversity is being used to develop commercially attractive, recombinant processes for the large-scale production of PHAs.
Abstract Galactomannan oligosaccharides (GMOS), composed of 2–10 mannose units linked with ÎČ-1, 4 glycosidic bond as the main chain and galactose linked with α-1, 6 glycosidic bond as the side 
 Abstract Galactomannan oligosaccharides (GMOS), composed of 2–10 mannose units linked with ÎČ-1, 4 glycosidic bond as the main chain and galactose linked with α-1, 6 glycosidic bond as the side chain, are crucial for probiotic food synthesis due to their ability to promote the growth and activity of beneficial intestinal microbiota, enhance the host immune system, and improve nutrient digestion. GMOS is usually obtained by hydrolyzing plants such as locust bean gum and guar gum with mannanase. ÎČ-mannanase ManA from Alkaliphilic Bacillus sp. N16-5 can hydrolyze ÎČ-1, 4 glycosidic bond of galactomannan. In this study, an immobilization system was employed utilizing polyhydroxyalkanoate (PHA) biopolymers, which naturally have an affinity mainly mediated by hydrophobic interaction for PhaP protein. Fusion protein combining ManA with PhaP from Aeromonas hydrophila , was subsequently immobilized on PHA support to form a multi-enzyme complex, facilitating the hydrolysis of locust bean gum to generate GMOS. This immobilized enzyme enhances enzyme stability and reusability, can be reused up to 32 times while maintaining ~ 80% of its activity, offering substantial cost savings through in-situ enzyme and product separation. Additionally, the different PHA forms were developed to hydrolyze locust bean gum to produce GMOS, such as nano PHA particles, PHA electrospun materials, while these preliminary investigations show promise, further research is needed to optimize their performance and practical application. Graphical Abstract
This work showcases the synthesis of unprecedented thermosensitive biohybrid carboxymethyl cellulose (CMC)-based comb copolymers by a Passerini three-component reaction (P-3CR) in aqueous conditions. CMC was concomitantly functionalized by various hydrophobic 
 This work showcases the synthesis of unprecedented thermosensitive biohybrid carboxymethyl cellulose (CMC)-based comb copolymers by a Passerini three-component reaction (P-3CR) in aqueous conditions. CMC was concomitantly functionalized by various hydrophobic aldehydes and a set of isocyanide-terminated poly(ethylene oxide-co-propylene oxide) (P(EO-co-PO)) segments, exhibiting a lower critical solution temperature (LCST) in water. The P-3CR allowed us to design a library of copolymers differing in their structural compositions (degrees of substitution up to 0.35). The graft copolymers exhibit a thermoinduced sol-gel transition in water due to the reversible formation of hydrophobic domains between dehydrated polyether segments that behave as stickers. From the structure-function relationship, the pivotal result lies in the possibility to tune the thermal response of the biohybrids by the structure of the grafted aldehyde, whose hydrophobicity strongly promotes the thermoassociation process. Thus, the P-3CR paves the way for targeting thermoresponsiveness that can be cleverly adjusted to specific end-uses, which is highly desired for biological applications.
Abstract The last three decades have witnessed a paradigm shift in the polymer industry, driven by the urgent need for sustainable materials. Growing awareness of environmental sustainability, coupled with increasingly 
 Abstract The last three decades have witnessed a paradigm shift in the polymer industry, driven by the urgent need for sustainable materials. Growing awareness of environmental sustainability, coupled with increasingly stringent chemical regulations, has catalyzed significant investments in sustainable polymer materials. While much of the focus has been on plastics, rubbery materials have received comparatively less attention. With mechanical and chemical recycling as the current primary mode for disposing rubber waste, prospects for a suitable pathway to minimize hazardous microplastics derived from these highly crosslinked polymers sources seem bleak. This article aims to envision a future where the pathway toward biodegradable rubber materials becomes a more realistic possibility. We delve into the challenges, advancements, and future perspectives of biodegradable rubbery materials, with a particular emphasis on exploring the potential of utilizing polysaccharides derived from biomass combined with synthetic elastomers – including the utilization of dynamic covalent bonding and supramolecular chemistry approaches. In addition to the discussion on scientific questions, we address complementary issues on STEM education to put forth a more comprehensive vision for sustainability relating to broader society.
Rice starch, as one of the most abundant and renewable polysaccharide resources in nature, holds great potential for applications in the food, pharmaceutical, and industrial fields due to its wide 
 Rice starch, as one of the most abundant and renewable polysaccharide resources in nature, holds great potential for applications in the food, pharmaceutical, and industrial fields due to its wide availability, low cost, and biodegradability. However, its inherent limitations—such as susceptibility to retrogradation and poor emulsifying capacity—have hindered its development into high-value-added products. Emulsion technology presents a promising strategy to overcome these challenges by constructing stable oil–water interfacial systems using various stabilizers. This review highlights recent advances in the functional modification of rice starch through emulsion-based techniques, with a particular focus on four key approaches: polysaccharide–protein complexation, chemical and physical modifications, Pickering emulsions, and microcapsule formation. These strategies significantly improve the emulsifying ability of rice starch, inhibit retrogradation, and expand its potential applications in sustained drug delivery, functional foods, and intelligent packaging. Overall, interfacial engineering of rice starch offers an innovative and effective pathway for its high-value utilization, demonstrating substantial promise for future industrial applications.
ABSTRACT Poly(lactic acid) (PLA) is a widely used biodegradable polymer, especially in food packaging, due to its environmentally friendly properties. In order to enhance its antimicrobial activity, this study investigates 
 ABSTRACT Poly(lactic acid) (PLA) is a widely used biodegradable polymer, especially in food packaging, due to its environmentally friendly properties. In order to enhance its antimicrobial activity, this study investigates the incorporation of pomegranate peel (PP) powder into PLA. PLA composites filled with varying percentages of PP powder (10, 15, and 20 wt%) were produced using a twin‐screw extruder at different screw speeds (400, 500, and 600 rpm). The effects of PP content and screw speed of extrusion on the antimicrobial properties, mechanical performance, thermal stability, and morphological characteristics were evaluated. Antimicrobial tests revealed that PLA/PP composites exhibited significant inhibition against Staphylococcus aureus and Escherichia coli . The antimicrobial activity of PP‐filled PLA composites was slightly affected by the screw speed during extrusion. The mechanical properties, thermal behavior, and crystallinity were adversely affected by the increasing PP content, particularly at higher screw speeds. The study concludes that PP powder significantly enhances the antimicrobial activity of PLA, but the mechanical and thermal properties require optimization, especially at higher filler content and screw speeds.
This study aimed to develop polylactic acid (PLA)-based membranes incorporating tramadol (TMD) using air jet spinning (AJS), ensuring stable physicochemical properties and biocompatibility. Two groups were fabricated: 10% PLA membranes 
 This study aimed to develop polylactic acid (PLA)-based membranes incorporating tramadol (TMD) using air jet spinning (AJS), ensuring stable physicochemical properties and biocompatibility. Two groups were fabricated: 10% PLA membranes (control) and 10% PLA membranes loaded with TMD in an 80:1 ratio (experimental). Characterization included scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FT-IR), ultraviolet-visible spectroscopy (UV-VIS), and biocompatibility assays with human osteoblasts using resazurin, crystal violet staining, and 5-chloromethylfluorescein diacetate for fluorescence microscopy. SEM revealed a homogeneous, randomly distributed fiber pattern, with diameters under 5 ”m and no structural voids. DSC and TGA indicated that TMD was uniformly incorporated, increased the thermal capacity, and slightly lowered the onset and inflection degradation temperatures. FT-IR confirmed the chemical compatibility of TMD with PLA, showing no structural alterations. UV-VIS detected sustained TMD release over 72 h. Biocompatibility tests showed no cytotoxic effects; cell viability and proliferation in TMD-loaded membranes were comparable to controls. Statistical analysis used ANOVA and Wilcoxon tests. 10% PLA membranes loaded with TMD at an 80:1 ratio exhibited stable physicochemical characteristics and favorable biocompatibility, supporting their potential use in drug delivery systems.
Abstract With 300 billion tons available in the biosphere, lignin is the second most abundant biopolymer on Earth. However, less than two percent is used for value‐added applications. One potential 
 Abstract With 300 billion tons available in the biosphere, lignin is the second most abundant biopolymer on Earth. However, less than two percent is used for value‐added applications. One potential application is the use of lignin as a building block for thermoplastics. The majority of plastics today are made from fossil‐based feedstocks. Therefore, the use of lignin can counteract the increasingly scarce petroleum resources. A highly useful approach is the copolymerization with cyclic lactones such as caprolactone (CL) via ring‐opening polymerization (ROP). The synthesis of lignin‐polycaprolactone (PCL) copolymers can help to combine the beneficial properties of PCL and lignin to create potential new applications. In this work, lignin‐PCL copolymers are synthesized in a sustainable approach using the nontoxic, highly active, and robust zinc‐based guanidine catalyst [Zn{( R,R )‐DMEG 2 (1,2)ch} 2 ]OTf 2 · THF. Analyzing the reaction kinetics, it was found that the pseudo‐first order reaction kinetics do not proceed with a uniform rate constant over the entire reaction. An acceleration occurs after the initial formation of PCL chains at the lignin core, with reaction rates depending on both the catalyst and lignin content. These new findings contribute to the mechanistic understanding behind lignin functionalization, highlighting the potential of such bio‐based copolymers for a sustainable plastic use.
Biobased polymers are gaining traction towards more sustainable flexible‐film packaging, yet overcoming trade‐offs between their performance properties and end‐of‐life (EoL) options still remains a challenge. Here, we show that biobased 
 Biobased polymers are gaining traction towards more sustainable flexible‐film packaging, yet overcoming trade‐offs between their performance properties and end‐of‐life (EoL) options still remains a challenge. Here, we show that biobased poly(dodecylene 2,5‐furanoate) (PDDF), synthesized via both step‐growth polycondensation and chain‐growth ring‐opening polymerization methods, exhibits advantages not only in gas barrier properties but also in EoL options due to its biodegradability and closed‐loop chemical circularity. Specifically, PDDF displays significantly lower oxygen and carbon dioxide permeability than commercial poly(butylene adipate‐co‐terephthalate) (PBAT) and linear low‐density polyethylene (LLDPE), alongside a markedly higher modulus (by ~3®) and reduced water vapor transmission rate compared to PBAT. This superior performance is attributed to the inherently rigid, polar, H‐bonding furan rings that enhance chain interaction, packing and crystallinity and thus reduce free volume impeding gas diffusion, while the long hydrophobic dodecylene segments inhibit water permeation. Furthermore, PDDF can be recycled back to its cyclic monomer by base‐catalyzed depolymerization or diester and diol monomers by simple methanolysis. These superior barrier properties, coupled with biodegradation and closed‐loop circularity, highlight the potential of the biobased PDDF as a more sustainable alternative for packaging.
ABSTRACT Studies that focus on turning biodiesel byproducts into valuable products have recently garnered increasing attention. This investigation highlights the utilization of waste substrates for a circular economy approach using 
 ABSTRACT Studies that focus on turning biodiesel byproducts into valuable products have recently garnered increasing attention. This investigation highlights the utilization of waste substrates for a circular economy approach using glycerine pitch as the main carbon source to produce biodegradable poly(3‐hydroxybutyrate‐ co ‐3‐hydroxyvalerate) [(P(3HB‐ co ‐3HV)] by Cupriavidus malaysiensis USMAA1020. The primary use of glycerine pitch, along with several parameters that may affect the growth and biosynthesis of copolymers, are investigated. The utilization of glycerine pitch along with 1‐pentanol and oleic acid has the most effective effect on bacterial growth and copolymer accumulation. Response surface methodology (RSM) was used to optimize these variables. The polyhydroxyalkanoate (PHA) content increased up to 77.7 wt% from 68.9 wt%, with residual dry cell weight (RDCW) of 6.5 g/L from 4.5 g/L. The optimal conditions for producing various compositions of the 3HVs were also determined. The three selected copolymer compositions were P(3HB‐ co ‐4%3HV), P(3HB‐ co ‐11%3HV), and P(3HB‐ co ‐18%3HV). Moreover, varying the copolymer compositions produced distinct polymer characteristics. According to this study, P(3HB‐ co ‐3HV) with variable properties can be produced for a range of applications using glycerine pitch as a potential primary carbon source. In addition to reducing the cost of production, this would enhance efficient waste management.
Developing sustainable packaging materials has become a global priority in response to environmental concerns associated with conventional plastics. This study used a wheat flour byproduct (glue flour, GF) and poly(butylene 
 Developing sustainable packaging materials has become a global priority in response to environmental concerns associated with conventional plastics. This study used a wheat flour byproduct (glue flour, GF) and poly(butylene adipate-co-terephthalate) (PBAT) to produce films via blown extrusion, incorporating rosemary extract (RE) at 2% (FRE2) and 4% (FRE4) (w/w). A control film (FCO) was formulated without RE. The physicochemical, thermal, mechanical, and biodegradation properties of the films were evaluated. FCO, FRE2, and FRE4 exhibited tensile strength (TS) values between 8.16 and 9.29 MPa and elongation at break (ELO) above 889%. Incorporating 4% RE decreased luminosity (91.38 to 80.89) and increased opacity (41.14 to 50.95%). A thermogravimetric analysis revealed a main degradation stage between 200 °C and 450 °C, with FRE2 showing the highest residual mass (~15% at 600 °C). Sorption isotherms indicated enhanced hydrophobicity with RE, thereby reducing the monolayer moisture content from 5.23% to 3.03%. Biodegradation tests revealed mass losses of 64%, 58%, and 66% for FCO, FRE2, and FRE4, respectively, after 180 days. These findings demonstrate that incorporating RE into GF/PBAT blends via blown extrusion is a promising strategy for developing biodegradable films with enhanced thermal behavior, mechanical integrity, and water resistance, contributing to the advancement of sustainable packaging materials.
In this work, we present an innovative, crosslinker-free method for preparing chitosan-based hydrogel precursors, fully aligned with green chemistry principles and composed of only five non-toxic, readily available reagents. The 
 In this work, we present an innovative, crosslinker-free method for preparing chitosan-based hydrogel precursors, fully aligned with green chemistry principles and composed of only five non-toxic, readily available reagents. The key novelty lies in the use of glycerin, which, during thermal annealing, evaporates and triggers a surface or bulk chemical transformation of chitosan, depending on its concentration. This process significantly enhances the material’s mechanical properties after swelling—with up to a 35% increase in tensile strength and a notable reduction in water uptake compared to systems containing AMPS-based crosslinkers. FTIR analysis indicates a partial re-acetylation of chitosan, shifting its structure toward that of chitin, which correlates with improved hydrophobicity (as shown by increased contact angles up to 92°) and greater structural integrity. These improvements are particularly pronounced at glycerin concentrations of 10–20%, whereas higher concentrations (50%) result in brittle, non-moldable films. Importantly, preliminary biological tests confirm that the resulting hydrogels are effectively colonized by mammalian cells, making them promising candidates for bioimplant or tissue engineering applications. Surface morphology and compatibility were further assessed via SEM, AFM, and contact angle measurements.
The linear polymer polyphosphate (polyP) is found across all three domains of life and fulfills diverse physiological functions, including phosphorus storage, chaperone activity, and stress tolerance. In bacteria, polyP synthesis 
 The linear polymer polyphosphate (polyP) is found across all three domains of life and fulfills diverse physiological functions, including phosphorus storage, chaperone activity, and stress tolerance. In bacteria, polyP synthesis is catalyzed by polyphosphate kinase (Ppk), whereas its degradation is carried out by exopolyphosphatases (Ppx). Intracellular polyP levels are determined by the balance between these opposing enzymatic activities, although the regulatory mechanisms governing this balance remain incompletely understood. In higher eukaryotes, polyP participates in diverse physiological processes from cell signaling to blood clotting. In relation to this, polyP from Levilactobacillus brevis has been identified as a protective factor against intestinal damage in a mouse model of acute colitis. Subsequent evidence has confirmed that polyP can confer beneficial effects on human intestinal health, prompting an increased interest in the production of polyP by probiotic lactic acid bacteria. Furthermore, polyP is extensively used in the food industry to enhance food quality, preservation, and nutritional value. This review summarizes the current knowledge on polyP metabolism in these bacteria and explores its functional properties and potential applications.
ABSTRACT Renewable feedstocks pave the way to reduce the demand for petroleum‐derived chemicals. Castor oil is one such plant‐based raw material that can be used to synthesize chemicals and materials 
 ABSTRACT Renewable feedstocks pave the way to reduce the demand for petroleum‐derived chemicals. Castor oil is one such plant‐based raw material that can be used to synthesize chemicals and materials with diverse applications. Herein, we report the synthesis of a novel monomer, 18‐methoxy‐18‐oxooctadec‐9‐en‐7‐yl methyl oxalate ( 3 ), from castor oil‐derived ricinoleic acid. The identity of the monomer 3 has been unambiguously ascertained using 1‐2D NMR spectroscopic analysis. Monomer 3 was then subjected to condensation polymerization with potentially bio‐renewable long‐chain aliphatic diols to yield degradable linear polyoxalates having molecular weights in the range of 8000–22,000 g/mol. The polymerization reactions were performed using pTSA and [Sn(Oct) 2 ] as catalysts, and the polymerization conditions were optimized. The structure of the polymer was confirmed by 1‐2D NMR spectroscopy, IR spectroscopy, and GPC analysis. The thermal characterizations of the polyoxalates were carried out by DSC and TGA analysis. The polyoxalates were found to degrade in acidic media. These renewable polyoxalates were further reacted with thiols by “thiol‐ene” click reaction to produce a cross‐linked rubbery polymer, which retained degradability.
In this work, biocomposites of polylactic acid (PLA) and polypropylene (PP) with micronized cellulose (MC) were produced by mold injection and subjected to accelerated aging with ultraviolet (UV) radiation. The 
 In this work, biocomposites of polylactic acid (PLA) and polypropylene (PP) with micronized cellulose (MC) were produced by mold injection and subjected to accelerated aging with ultraviolet (UV) radiation. The tests took place over 10 weeks, during which the produced specimens were exposed to a total of 1050 h of ultraviolet light. During the UV aging test, images were captured, and spectral reflectance and colorimetric measurements were carried out on the specimens exposed to UV and on specimens of the same materials kept in the dark (originals). As expected, only residual color differences were observed in the original specimens with values of ΔE*ab always below 0.5. On the other hand, spectral reflectance and colorimetric changes were noticed over time in the specimens subjected to UV radiation. In particular, the values of ΔE*ab increased over time and were found to be higher for PLA with MC compared to PP with MC. Values of ΔE*ab = 4.7, 9.0, and 10.4 were obtained for weeks 1, 5, and 10, respectively, for the specimens of PLA with MC, whereas ΔE*ab = 4.5, 6.8, and 7.3 were obtained for weeks 1, 5, and 10, respectively, for the specimens of PP with MC. Therefore, it was found that the specimens of PLA with MC showed greater color fading compared to the specimens of PP with MC when subjected to UV exposure. In addition, it was also found in this work that besides the color differences noted in the tested specimens, those made of PP with MC also showed signs of surface damage.
Objective: The main aim of this project is to formulate and in vitro evaluation of effervescent drug delivery using Propanolol HCl as a model drug. Methodology: The effervescent floating drug 
 Objective: The main aim of this project is to formulate and in vitro evaluation of effervescent drug delivery using Propanolol HCl as a model drug. Methodology: The effervescent floating drug delivery was prepared using hydrophilic polymer in two different grades, HPMC K4M and HPMC K200M. Sodium carbonate is used as a gas-generating agent in floating tablets. The tablets were prepared by the wet granulation method. The ratio of HPMC to ethyl cellulose was kept constant at 2:1. The formulated tablets were evaluated for physicochemical properties, in vitro buoyancy, floating properties, swelling studies, in vitro dissolution studies, and drug release kinetics. Results: The result of in vitro dissolution showed that the sustained release can be achieved using HPMC and increasing the concentration of hydrophilic polymers like HPMC K4M and HPMC K200M increases the capacity of holding the drug within the polymer for a longer time. However, changing the viscosity of the HPMC had no significant difference in the drug release profile. The floating lag time for all the formulations was found to be less than 2 minutes with a floating time of more than 24 hours which showed the adequate buoyancy of the tablets. Conclusion: The present studies showed that using hydrophilic polymers like HPMC K4M and HPMC K200M along with ethyl cellulose and sodium carbonate as gas generating agents can be used for developing sustained released effervescent floating tablets.
This research investigates the biochemical and microbiological characteristics of a composite comprising poly(lactide) (PLA) combined with polyethersulfone (PESf) and copper-complexed cellulose phosphate (CelP-Cu). The material was produced using the pneumothermic 
 This research investigates the biochemical and microbiological characteristics of a composite comprising poly(lactide) (PLA) combined with polyethersulfone (PESf) and copper-complexed cellulose phosphate (CelP-Cu). The material was produced using the pneumothermic melt-blown method and then modified with polyethersulfone and cellulose phosphate, followed by complexation with copper ions using the dip-coating technique. Comprehensive physicochemical and biological evaluations were conducted to characterize the composite. The physicochemical assessments involved elemental analysis (C, O, Cu) and morphology examination. The biological evaluations encompassed microbiological testing and biochemical–hematological analysis, including activated partial thromboplastin time (aPTT) and prothrombin time (PT). Antimicrobial activity was assessed according to the EN ISO 20645:2006 and EN 14119:2005 standards, by placing material specimens on agar plates inoculated with representative microorganisms. The results revealed that the composites exhibited significant antimicrobial effects against model microorganisms: Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, Bacillus atrophaeus, Candida albicans, Saccharomyces cerevisiae, Aspergillus niger, Chaetomium globosum. This study highlights the potential of PLA/PESf/CelP-Cu composites for novel biomedical applications, demonstrating their biocompatibility and their influence on hemostatic processes and antimicrobial properties.
In the face of accelerating urbanization and the growing demand for environmentally responsible materials and designs, this study presents the development and implementation of a modular parklet demonstrator fabricated using 
 In the face of accelerating urbanization and the growing demand for environmentally responsible materials and designs, this study presents the development and implementation of a modular parklet demonstrator fabricated using dual-material 3D printing. The structure integrates polylactic acid (PLA) and wood-filled PLA (wood/PLA), combining the mechanical robustness of pure PLA in the core with the tactile and aesthetic appeal of wood-based biocomposite on the surface. The newly developed dual-nozzle 3D printing approach enabled precise spatial control over material distribution, optimizing both structural integrity and sustainability. A comprehensive evaluation was conducted for developed filaments and printed materials, including optical microscopy, coupled thermogravimetry analysis and Fourier Transform Infrared Spectroscopy (TG/FTIR), differential scanning calorimetry (DSC), and chemical and mechanical resistance testing. Results revealed distinct thermal behaviors and degradation pathways between filaments and printed parts composed of PLA and PLA/wood. The biocomposite exhibited slightly increased sensitivity to aggressive chemical environments and mechanical wear, dual-material prints maintained high thermal stability and interlayer adhesion. The 3D-printed demonstrator bench and stools were successfully deployed in public spaces as a functional urban intervention. This work demonstrates the feasibility and advantages of using biocomposite materials and dual-head 3D printing for the rapid, local, and sustainable fabrication of small-scale urban infrastructure.
The development of innovative poly(ether‐ester)s with perfectly alternating ether and ester functionalities to overcome the trade‐offs between the polymer's depolymerizability and performance properties is in high demand for advanced material 
 The development of innovative poly(ether‐ester)s with perfectly alternating ether and ester functionalities to overcome the trade‐offs between the polymer's depolymerizability and performance properties is in high demand for advanced material applications and sustainable development. Herein, we prepared a series of enantiopure cyclic thioether‐ester monomers bearing various pendant substituents by a facile “polycondensation‐depolymerization” strategy. The controlled ring‐opening polymerizations of these enantiopure monomers will afford stereoregular poly(thioether‐alt‐ester)s with structural diversity. The varieties of substituent size, position and stereo‐configuration provide the opportunity to systematically investigate polymerization kinetics and thermodynamics as well as structure‐properties relationship for the resulting poly(thiother‐alt‐ester)s. The strategic positioning of α‐, γ‐, and ή‐substituents coupled with stereoregular chain architectures and stereocomplex formation enables wide‐range modulation of the polymer's thermal and mechanical properties. A(hard)‐B(soft)‐A(hard) triblock thermoplastic elastomers with good mechanical performance and elastic recovery were also created by sequential polymerization. Of note, these polymers can be chemically recycled by either ring‐closing depolymerization or anchylosis, with high monomer regeneration efficiency. The systematic investigation of substitution effects and structure‐property relationships in this work provides a molecular blueprint for designing novel chemically recyclable polymers with high performance.
The development of effective drug delivery systems, in terms of their application route and release profile, is crucial for improving the therapeutic outcomes of all bioactive compounds. In this study, 
 The development of effective drug delivery systems, in terms of their application route and release profile, is crucial for improving the therapeutic outcomes of all bioactive compounds. In this study, we explored the encapsulation of 5-fluorouracil, a commonly used chemotherapeutic agent, in poly(lactic acid) films for the first time and the role of chitosan particles in the structure, as no previous studies have examined their potential for this purpose. The objective is to enhance the sustained release of 5-FU and minimise the burst release step while leveraging the biocompatibility and biodegradability of these polymers. PLA films were fabricated using a solvent casting method, and 5-FU was encapsulated either directly within the PLA matrix or loaded into chitosan particles, which were then incorporated into the film. The physicochemical properties of the films, including morphology, wettability, phase state of the drug, thermal stability, drug loading efficiency, and release kinetics, were evaluated along with their barrier and mechanical properties. The results indicate a change in morphology after the addition of the drug and/or particles compared to the empty film. Additionally, the strain value at break decreased from nearly 400% to below 15%. Young’s modulus also changes from 292 MPa to above 500 MPa. The addition of chitosan particles lowered the permeability and vapour transmission rate slightly, while dissolving 5-FU increased them to 241 g/m2·24 h and 1.56 × 10−13 g·mm/m2·24 h·kPa, respectively. Contact angle and surface energy values went from 71° and 34 mJ/m2 for pure PLA to below 53° and around 58 mJ/m2 for the composite structures, respectively. Drug release tests, conducted for 8 h, indicated a nearly 2-fold decrease in the amount of drug released from the film with particles within this period, from around 45% for bare particles and PLA film to 25% for the combined structure, indicating the potential of this system for sustained release of 5-FU.
Brewery’s spent grain (BSG) consists of the largest by-product by volume in the beer production sector and offers potential for both bio-composite material production, high-added-value molecular extraction and bioenergy recovery. 
 Brewery’s spent grain (BSG) consists of the largest by-product by volume in the beer production sector and offers potential for both bio-composite material production, high-added-value molecular extraction and bioenergy recovery. Aiming at exploring the ideal biorefinery approach for this agro-industrial residual, the present study experimentally investigated several methodologies to enhance the reuse of BSG and proposed a scheme of biorefinery focused on it. According to it, BSGs were firstly tested to produce high-added-value byproducts, such as protein hydrolysates and for the extraction of lignin via ionic liquids-based methods. The residuals were then used for biogas/biomethane production via anaerobic codigestion. The different matrices were rearranged in varying mixtures, aiming at ensuring high availability of nutrients for methanogens, thus achieving higher energy production than what achievable with untreated BSG. For the scope, further agro-industrial wastes were considered. The resulted digestate was finally composted. Untreated BSGs were also directly tested as fillers for bio-composite material production (in a mixture with PHB). Different concentrations were tested and the mechanical properties of each sample were compared with those of pure PHB. Disintegration tests were finally carried out to measure the improved biodegradability of the produced bio-composite material.
The development of innovative poly(ether‐ester)s with perfectly alternating ether and ester functionalities to overcome the trade‐offs between the polymer's depolymerizability and performance properties is in high demand for advanced material 
 The development of innovative poly(ether‐ester)s with perfectly alternating ether and ester functionalities to overcome the trade‐offs between the polymer's depolymerizability and performance properties is in high demand for advanced material applications and sustainable development. Herein, we prepared a series of enantiopure cyclic thioether‐ester monomers bearing various pendant substituents by a facile “polycondensation‐depolymerization” strategy. The controlled ring‐opening polymerizations of these enantiopure monomers will afford stereoregular poly(thioether‐alt‐ester)s with structural diversity. The varieties of substituent size, position and stereo‐configuration provide the opportunity to systematically investigate polymerization kinetics and thermodynamics as well as structure‐properties relationship for the resulting poly(thiother‐alt‐ester)s. The strategic positioning of α‐, γ‐, and ή‐substituents coupled with stereoregular chain architectures and stereocomplex formation enables wide‐range modulation of the polymer's thermal and mechanical properties. A(hard)‐B(soft)‐A(hard) triblock thermoplastic elastomers with good mechanical performance and elastic recovery were also created by sequential polymerization. Of note, these polymers can be chemically recycled by either ring‐closing depolymerization or anchylosis, with high monomer regeneration efficiency. The systematic investigation of substitution effects and structure‐property relationships in this work provides a molecular blueprint for designing novel chemically recyclable polymers with high performance.
ABSTRACT Poly(lactic acid) (PLA) is a promising biopolymer for packaging applications. However, efforts have been focused on improving its processability. Metal stearates are applied in the thermoplastic polymer industry as 
 ABSTRACT Poly(lactic acid) (PLA) is a promising biopolymer for packaging applications. However, efforts have been focused on improving its processability. Metal stearates are applied in the thermoplastic polymer industry as lubricating agents to enhance the processability of these polymers, although the comprehension regarding their thermostability is still unclear. Herein, a melt‐mixing technique was employed to produce PLA composites modified with calcium stearate. The effects of the additive were evaluated from 0.1 to 0.7 wt.% of calcium stearate, all incorporated into the PLA matrix at 200°C. Melt flow index (MFI) indicated a reduction in the viscosity of the modified materials. However, the significant decrease observed at concentrations above 0.3 wt.% suggested a potential polymer degradation due to the addition of calcium stearate. This phenomenon was related to the scission of the PLA chains in the presence of metal stearates during processing, which was supported by results from gel permeation chromatography (GPC) and thermal analyses. As the calcium stearate content increased, the materials exhibited a decrease in molecular weight, degradation temperature, and degree of crystallinity. In addition, calcium stearate could be incorporated into PLA at 180°C and low frequencies, conditions that avoided polymer degradation, as shown by parallel plate rheometry.
ABSTRACT The impact of high‐dose e‐beam and γ‐irradiation, followed by long‐term aging, on the structural properties of poly(L‐lactide) (PLA) was investigated. Due to prolonged exposure, γ‐irradiation caused more extensive oxidative 
 ABSTRACT The impact of high‐dose e‐beam and γ‐irradiation, followed by long‐term aging, on the structural properties of poly(L‐lactide) (PLA) was investigated. Due to prolonged exposure, γ‐irradiation caused more extensive oxidative degradation, accelerating the aging process compared to e‐beam irradiation. Aging effects were most pronounced in samples irradiated at doses exceeding 600 kGy. Structural analysis using 1 H NMR revealed distinct mechanisms of chain scission during irradiation and aging, resulting in the formation of different end groups. Irradiation‐induced deterioration of PLA's phase structure occurred during irradiation was observed, including the formation of conformationally disordered αâ€Č crystalline form. Aging at doses exceeding 1000 kGy led to amorphization. The degradation behavior of aged PLA in water and its recycling potential were also evaluated. While partial dissolution of aged samples occurred in a short‐term, further degradation was hindered by water‐induced crystallization. Unirradiated and low‐dose irradiated PLA demonstrated promising recyclability to lactide, highlighting its potential for industrial‐scale chemical recycling as a sustainable alternative to landfilling or composting.
Abstract A series of well‐defined homoleptic magnesium complexes 1 – 9 bearing [NNN]‐tridentate pyrrolylaldiminate ligands were prepared and fully characterized by NMR spectroscopic techniques. Their application to the ring‐opening polymerization 
 Abstract A series of well‐defined homoleptic magnesium complexes 1 – 9 bearing [NNN]‐tridentate pyrrolylaldiminate ligands were prepared and fully characterized by NMR spectroscopic techniques. Their application to the ring‐opening polymerization (ROP) of rac ‐lactide ( rac ‐LA) to produce polylactide was investigated under solution and bulk conditions. The polymerizations initiated by all complexes in the presence of benzyl alcohol proceeded to completion within 5 min at 70 °C. The polymerizations were controlled and living, as evidenced by the obtained predetermined molar mass PLAs with narrow dispersities. Kinetic investigations revealed an unexpected zero‐order rate dependence on monomer concentration. The NMR reaction studies revealed that the polymerizations proceeded via an insertion‐coordination mechanism in the presence or absence of benzyl alcohol. All complexes demonstrated the ability to facilitate PLA methanolysis into methyl lactate (Me‐La) under mild conditions at 50 °C, achieving complete PLA consumption ( X int = 100%) within 24 h and affording Me‐La in excellent yield and selectivity ( Y Me‐La = 83–99%, S Me‐La = 83–99%). The depolymerization of poly(L‐lactide) (PLLA) and commercial PLLAs to L‐LA monomer was demonstrated utilizing the complex 1 /glycerol ethoxylate (GEO) catalyst system at 160 °C under reduced pressure, resulting in high‐purity L‐LA.
As the global plastic pollution problem intensifies and the environmental hazards of traditional petroleum-based plastics become increasingly significant, the development of sustainable alternative materials has become an urgent need. This 
 As the global plastic pollution problem intensifies and the environmental hazards of traditional petroleum-based plastics become increasingly significant, the development of sustainable alternative materials has become an urgent need. This paper systematically reviews the research progress, application status and future trends of new generation bioplastics in the field of food packaging. Bioplastics are categorized into three main groups according to their sources and degradability: biobased biodegradable materials (e.g., polylactic acid PLA, polyhydroxy fatty acid ester PHA, chitosan, and cellulose-based materials); biobased non-biodegradable materials (e.g., Bio-PE, Bio-PET); and non-biobased biodegradable materials (e.g., PBAT, PCL, PBS). Different processing technologies, such as thermoforming, injection molding, extrusion molding and coating technologies, can optimize the mechanical properties, barrier properties and freshness retention of bioplastics and promote their application in scenarios such as food containers, films and smart packaging. Although bioplastics still face challenges in terms of cost, degradation conditions and industrial support, promising future directions are found in the development of the large-scale utilization of non-food raw materials (e.g., agricultural waste, algae), nano-composite technology to enhance the performance, and the development of intelligent packaging functions. Through technological innovation and industry chain integration, bioplastics are expected to transform from an environmentally friendly alternative to a mainstream packaging material, helping to realize the goal of global carbon neutrality.
Soy molasses, a byproduct of soy protein concentrate production, offers potential as a substrate for biotechnological applications due to its rich composition of carbohydrates, proteins, lipids, and bioactive compounds. Despite 
 Soy molasses, a byproduct of soy protein concentrate production, offers potential as a substrate for biotechnological applications due to its rich composition of carbohydrates, proteins, lipids, and bioactive compounds. Despite this, it remains underutilized, often relegated to low-value applications such as animal feed or waste, largely due to variability in its composition, the presence of microbial inhibitors, and limited industrial awareness of its potential. This review explores the biotechnological strategies for valorizing soy molasses, focusing on its chemical and physical properties, potential applications, and the challenges associated with its use. Its high carbohydrate content supports its utilization in producing biofuels, organic acids, and polyhydroxyalkanoates (PHA), addressing the global demand for sustainable energy and materials while costing approximately 20% of the value of conventional carbohydrate sources. Additionally, bioactive compounds have extended applications to nutraceuticals and cosmetics, while proteins and lipids enable enzyme and biosurfactant production. However, challenges such as variability in composition, the presence of inhibitory compounds, and scalability issues require innovative approaches, including pre-treatment methods and strain engineering. By integrating soy molasses into a circular bioeconomy framework, industries can reduce waste, lower their carbon footprint, valorize agro-industrial residues, and generate economic value. This review underscores the untapped potential of soy molasses as a versatile, sustainable resource, while highlighting the need for continued advancements to transform it into a key player in industrial biotechnology.
Plastic disposal has become a serious environmental and social problem. Mechanical recycling of waste plastics is the most widely adopted strategy to address this issue, but if used to recycle 
 Plastic disposal has become a serious environmental and social problem. Mechanical recycling of waste plastics is the most widely adopted strategy to address this issue, but if used to recycle mixed plastics, it usually requires the addition of amphiphilic block copolymers. Polyolefins account for almost half of all synthetic plastics, making them ubiquitous in the plastic waste stream. Within this perspective, polyolefin‐based multiblock copolymers are highly desirable, but they are difficult to access using traditional strategies. In this contribution, a cascade ring‐opening metathesis polymerization (ROMP) and reversible addition‐fragmentation chain transfer (RAFT) polymerization strategy was developed to prepare various polyolefin‐based multiblock copolymers with tunable polar segments and microstructures. Using this strategy, tunable amounts of the trithiocarbonate RAFT agents were installed in the polyolefin main chain via ROMP. Subsequent chain extension of various polar vinyl monomers via controlled RAFT polymerization formed various polyolefin‐based multiblock copolymers with high molecular weight and good physical properties. These multiblock copolymers were used to compatibilize and upcycle mixtures of high‐density polyethylene/polymethyl methacrylate (HDPE/PMMA) and high‐density polyethylene/polyethylene terephthalate (HDPE/PET).
Plastic disposal has become a serious environmental and social problem. Mechanical recycling of waste plastics is the most widely adopted strategy to address this issue, but if used to recycle 
 Plastic disposal has become a serious environmental and social problem. Mechanical recycling of waste plastics is the most widely adopted strategy to address this issue, but if used to recycle mixed plastics, it usually requires the addition of amphiphilic block copolymers. Polyolefins account for almost half of all synthetic plastics, making them ubiquitous in the plastic waste stream. Within this perspective, polyolefin‐based multiblock copolymers are highly desirable, but they are difficult to access using traditional strategies. In this contribution, a cascade ring‐opening metathesis polymerization (ROMP) and reversible addition‐fragmentation chain transfer (RAFT) polymerization strategy was developed to prepare various polyolefin‐based multiblock copolymers with tunable polar segments and microstructures. Using this strategy, tunable amounts of the trithiocarbonate RAFT agents were installed in the polyolefin main chain via ROMP. Subsequent chain extension of various polar vinyl monomers via controlled RAFT polymerization formed various polyolefin‐based multiblock copolymers with high molecular weight and good physical properties. These multiblock copolymers were used to compatibilize and upcycle mixtures of high‐density polyethylene/polymethyl methacrylate (HDPE/PMMA) and high‐density polyethylene/polyethylene terephthalate (HDPE/PET).
ABSTRACT Processing biodegradable polymer films implies challenges, including thermal sensitivity, complex flow behavior, and the need to add plasticizers to confer properties similar to conventional plastics. Two extrusion processes were 
 ABSTRACT Processing biodegradable polymer films implies challenges, including thermal sensitivity, complex flow behavior, and the need to add plasticizers to confer properties similar to conventional plastics. Two extrusion processes were compared and studied to evaluate the processability of polyvinyl alcohol (PVA) and corn starch (CS) blends. The first method consisted of the mixing of PVA, CS, and glycerol by a one‐step extrusion process to obtain PVA/CS 1S blends, and the second method involved the plasticization and processing of PVA and CS, each one with glycerol separately, and then they were extruded again to obtain PVA/CS 2S blends. CS content was varied at 30, 40, 50, 60, and 70 wt‐3%. Finally, PVA/CS blends were processed by blown extrusion to produce films. The effect of the extrusion method and CS content on the thermal, morphological, rheological, and mechanical properties of PVA/CS blends was studied. Crystallization and melt temperatures (DSC) decreased with higher CS content. The degradation temperature increased from 210°C to 270°C and 295°C for one‐step and two‐step processes, respectively, indicating that CS acted as a plasticizer and disrupted PVA crystallinity. One‐step extrusion had viscosities closer to PVA, while two‐step extrusion resembled CS, resulting in complete starch granule plasticization. The Young's modulus increased by 168% and 146% for one and two‐step blends, respectively. Although incorporating 30 wt‐% starch via a two‐step process leads to a higher disintegration rate (83.8%) and method‐dependent property improvements, the one‐step extrusion method holds greater industrial promise. Its advantages include lower costs by skipping pre‐plasticization, reduced drying requirements, and the ability to use more glycerol.
In this study, poly-DL-lactic acid (PDLLA) was synthesized via ring-opening polymerization (ROP) to develop a biomedical scaffold for tissue engineering. A rotary evaporator with a two-stage vacuum pump under an 
 In this study, poly-DL-lactic acid (PDLLA) was synthesized via ring-opening polymerization (ROP) to develop a biomedical scaffold for tissue engineering. A rotary evaporator with a two-stage vacuum pump under an inert atmosphere and constant stirring was used. A factorial design with three factors (oligomerization time, ROP time, and catalyst concentration) at two levels was applied. Polymers were characterized by FTIR, capillary viscometry, 1H-NMR, DSC, and TGA. The kinetic study revealed a first-order model, indicating that the polymerization rate depends linearly on monomer concentration. The activation energy (70.5 kJ/mol) suggests a moderate energy requirement, consistent with ring-opening polymerization, while the high pre-exponential factor (6.93 × 106 min-1) reflects a significant frequency of molecular collisions. The scaffold was fabricated via extrusion and 3D printing, and its morphology, porosity, mechanical properties, and contact angle were studied. The highest molecular weight PDLLA was obtained with 6 h of oligomerization, 4 h of ROP, and 1% catalyst concentration. The samples exhibited thermal stability below 40 °C, while the scaffold reached 71.6% porosity, an 85.97° contact angle, and a compressive strength of 4.24 MPa with an elastic modulus of 51.7 MPa. These findings demonstrate the scaffold's potential for biomedical applications.
ABSTRACT Polylactides (PLA) are insoluble in acetone under normal conditions. Upon heating, the PLA solubility in acetone increases sharply up to complete dissolution. The PLA transition from the solid semi‐crystalline 
 ABSTRACT Polylactides (PLA) are insoluble in acetone under normal conditions. Upon heating, the PLA solubility in acetone increases sharply up to complete dissolution. The PLA transition from the solid semi‐crystalline state to the soluble one is first studied by the high‐sensitivity differential scanning calorimetry. The PLA dissolution thermograms are obtained. Thermodynamic characteristics of the dissolution, the transition temperature, and enthalpy ( T t = 51.0 ± 0.3 °C and 22 ± 2 J g −1 ), are shown to be independent of the polymer content in the system (1–7 mg mL −1 ). The dissolution thermograms are transformed to the temperature dependences of the relative PLA solubility (0 ≀ α( T ) ≀ 1). These dependences are well approximated by the model of phase equilibrium between the solid polymer and its ideal solution (correlation coefficient of 0.999). The parameters of the model, the apparent transition enthalpy and the apparent transition temperature, do not depend on the PLA concentration: Δ m h * = 420 ± 50 kJ mol −1 , and 324.9 ± 0.2 K. As a result of the consistent thermodynamic analysis of the calorimetric data, the PLA crystallization degree (20%) and the average molecular weight of the crystalline domains of PLA macromolecules (4000 Da) are estimated.
ABSTRACT Incorporating nanoparticles can meaningfully alter the stereocomplexation of polylactide systems. In the current study, the stereocomplex crystallization behavior, microstructure, electrical conductivity, wettability, and thermal stability performance of stereocomplexed‐polylactide nanocomposites 
 ABSTRACT Incorporating nanoparticles can meaningfully alter the stereocomplexation of polylactide systems. In the current study, the stereocomplex crystallization behavior, microstructure, electrical conductivity, wettability, and thermal stability performance of stereocomplexed‐polylactide nanocomposites loaded with graphene oxide, carbon nanotubes, and their nanohybrid system (1:1) from an interface‐geometry combinational point of view was systematically investigated. After the nanocomposites were analyzed via transmission electron microscopy, electrical conductivity test, differential scanning calorimetry, thermogravimetric analysis, contact angle measurements, and surface energy calculations, it was concluded that two factors, thermodynamic (dispersion/filler–polymer interaction) and nanofiller geometry, are determinant in modulating the degree of stereocomplexation and thermal stability. By introducing only 0.25 wt.% graphene oxide, 33.0% stereocomplex crystals with a melting temperature 14 K higher than that of the neat stereocomplexed‐polylactide and an 11 K higher thermal degradation temperature were obtained, which was attributed to the simultaneous presence of stereocomplex crystals and graphenic platelets. For the first time, a mechanism for the stereocomplexation of polylactide enantiomeric chains on the surface of graphenic platelets and carbon nanotubes in their hybrid system was proposed. Our results pave the way toward a feasible engineering of the interface to control the stereocomplexation for the desired application of stereocomplexed‐polylactide‐filled hybrid nanocomposites.
ABSTRACT In tissue engineering and regenerative medicine, biodegradable PLCL polymers are highly valued. This is because their mechanical properties can be finely adjusted, and they are compatible with biological tissues. 
 ABSTRACT In tissue engineering and regenerative medicine, biodegradable PLCL polymers are highly valued. This is because their mechanical properties can be finely adjusted, and they are compatible with biological tissues. However, precise control over their degradation rate remains a challenge for biomedical applications. In this study, magnesium oxide (MgO) nanoparticles were incorporated into PLCL matrices to systematically modulate both mechanical properties and degradation behavior. To determine the microstructure and thermal robustness of the PLCL/MgO composites, a battery of tests was conducted. These tests included scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), rheometry, and thermogravimetric analysis (TGA). The results revealed that MgO nanoparticles significantly enhanced the ultimate tensile strength and modulus of elasticity of PLCL while simultaneously accelerating its hydrolytic degradation. This was attributed to MgO's dual role: (1) stabilizing the local pH by neutralizing acidic degradation byproducts, thereby mitigating autocatalytic degradation of the PLCL matrix, and (2) acting as an alkaline catalyst to facilitate ester bond hydrolysis. Notably, the degradation rate increased in a MgO concentration‐dependent manner, with minimal impact on the polymer's biocompatibility. This study demonstrates that MgO can effectively modulate the degradation process, thereby enabling the creation of bioresorbable PLCL‐based materials with tailored lifespans. This advancement holds great promise for advanced biomedical applications.
The demands of the green economy necessitate modern polymer materials that are not only environmentally friendly but also durable and capable of long service life. Bio-based polylactide (PLA) polyesters have 
 The demands of the green economy necessitate modern polymer materials that are not only environmentally friendly but also durable and capable of long service life. Bio-based polylactide (PLA) polyesters have gained significant traction in various industrial markets; however, their application in specialized sectors is hindered by high brittleness. This study extensively examines the effects of 1-5% of synthetically obtained tetracyclosiloxane (CS) and octaspherosilicate (OSS) derivatives with methacrylate (MA) and trimethoxysilyl (TMOS) groups as functional modifiers for PLA. The research provides a detailed characterization of PLA/CS and PLA/OSS materials, including a comparative analysis of mechanical properties such as tensile, flexural, and dynamic resistance. Notably, incorporating 5% CS-2MA-2TMOS into PLA resulted in a remarkable 104% increase in impact resistance. The study further evaluates the influence of these modifications on thermal properties (DSC, TGA), heat deflection temperature (HDT), and surface character (WCA). The miscibility between the organosilicon additives and PLA was assessed using oscillatory rheometry and SEM-EDS analysis. The melt-rheology analysis explained the mechanisms behind the interaction between the CS and OSS additives with the PLA matrix, highlighting their lubricating effects on the melt flow behavior. The study was complemented by XRD structural analysis and verification of the structure of PLA-based materials by optical microscopy and SEM analysis, demonstrating a plasticizing effect and uniform distribution of the modifiers. The findings strongly suggest that, even at low concentrations, organosilicon additives serve as effective impact modifiers for PLA.