Search Results (15)

In this study, poly(butylene adipate-co-terephthalate) (PBAT), starch, glycerol, and grape seed extract (GSE) were blended and extruded to fabricate PBAT/thermoplastic starch(TPS)/GSE active films by blow molding. The interaction between GSE and TPS primarily occurred through hydrogen bonding, with little interaction observed with PBAT. The oxygen barrier property of the film was improved by the incorporation of GSE into the films, whereas the mechanical properties slightly decreased. The PBAT/TPS/GSE films had excellent UV blocking properties imparted by PBAT and visible light blocking properties endowed by GSE. The films containing GSE offered antimicrobial activity against Escherichia coli and Staphylococcus aureus by delaying bacterial growth. Also, the GSE-added films exhibited antioxidant activity with strong dose dependence due to the free radical scavenging ability of polyphenolic compounds in GSE. The shelf life of peanut butter packaged with the PBAT/TPS/GSE-5 film was expected to exceed 300 days, which was approximately twice that of LDPE film packaging. The proposed active films had good material properties, functional activities, and excellent ability to prolong the shelf life of peanut butter. Full article

A chemical platform for post-polymerization methods was developed, starting from the ecodesign and enzymatic synthesis of safe and sustainable bio-based polyesters containing discrete units of itaconic acid. This unsaturated bio-based monomer enables the covalent linkage of molecules that can impart desired properties such as hydrophilicity, flexibility, permeability, or affinity for biological targets. Molecular descriptor-based computational methods, which are generally used for modeling the pharmacokinetic properties of drugs (ADME), were employed to predict in silico the hydrophobicity (LogP), permeability, and flexibility of virtual terpolymers composed of different polyols (1,4-butanediol, glycerol, 1,3-propanediol, and 1,2-ethanediol) with adipic acid and itaconic acid. Itaconic acid, with its reactive vinyl group, acts as a chemical platform for various post-polymerization functionalizations. Poly(glycerol adipate itaconate) was selected because of its higher hydrophilicity and synthetized via solvent-free enzymatic polycondensation at 50 °C to prevent the isomerization or crosslinking of itaconic acid. The ecotoxicity and marine biodegradability of the resulting oligoester were assessed experimentally in order to verify its compliance with safety and sustainability criteria. Finally, the viability of the covalent linkage of biomolecules via Michael addition to the vinyl pendant of the oligoesters was verified using four molecules bearing thiol and amine nucleophilic groups: N-acetylcysteine, N-Ac-Phe-ε-Lys-OtBu, Lys-Lys-Lys, and glucosamine. Full article

Two types of glycerol stearates, glycerol monostearate (GMS) and glycerol tristearate (GTS), were added into poly(butylene adipate-co-terephtalate) (PBAT), with the aim to improve their water vapor barrier properties. The effects of the two small molecules on microstructure, chain mobility, and surface hydrophobicity were amply assessed via both experimental and simulation methods. The incorporation of the modifiers at small loadings, 5 wt% of GMS and 1 wt% of GTS, resulted in substantial improvements in water vapor barrier properties, while a further increase in the modifier content resulted in deterioration. The optimal water vapor permeability reached values of 2.63 × 10⁻¹³ g·cm/(cm²·s·Pa) and 6.55 × 10⁻¹³ g·cm/(cm²·s·Pa), which are substantially lower than the permeability, 8.43 × 10⁻¹³ g·cm/(cm²·s·Pa), of neat PBAT. The water vapor permeability of PBAT/GMS blends was also proven to be time-dependent and dramatically decreased with time, mainly due to the migration process of small molecules, forming a waterproof layer. The barrier improvement results are assumed to be related to the hydrophobic effect of glycerol stearate and are largely dependent on the content, polarity, compatibility, and dispersion of modifiers. In addition, the incorporation of modifiers did not largely sacrifice the mechanical strength of PBAT, which is advantageous in mulch film applications. Full article

Starches plasticized with glycerol/citric acid/stearic acid and tributyl 2-acetylcitrate (ATBC), respectively, were processed with poly (butylene adipate-Co-terephthalate (PBAT) via extrusion and a film-blown process. All the composite films were determined for morphology, mechanical, thermal stability, crystalline, and optical properties. Results show that the most improved morphology was in the 30% glycerol plasticized PBAT/thermoplastic starch (TPS) composite films, characterized by the smallest and narrowest distribution of TPS particle sizes and a more uniform dispersion of TPS particles. However, the water absorption of PBAT/TPS composite films plasticized with glycerol surpassed that observed with ATBC as a plasticizer. Mechanical properties indicated insufficient plasticization of the starch crystal structure when using 10% ATBC, 20% ATBC, and 20% glycerol as plasticizers, leading to poor compatibility between PBAT and TPS. This resulted in stress concentration points under external forces, adversely affecting the mechanical properties of the composites. All PBAT/TPS composite films exhibited a negative impact on the initial thermal decomposition temperature compared to PBAT. Additionally, the haze value of PBAT/TPS composite films exceeded 96%, while pure PBAT had a haze value of 47.42%. Films plasticized with 10% ATBC, 20% ATBC, and 20% glycerol displayed lower transmittance values in the visible light region. The increased transmittance of films plasticized with 30% glycerol further demonstrated their superior plasticizing effect compared to other PBAT/TPS composite films. This study provides a simple and feasible method for preparing low-cost PBAT composites, and their extensions are expected to further replace general-purpose plastics in daily applications. Full article

Poly(butylene adipate–co–terephthalate) (PBAT) is widely used for production of biodegradable films due to its high elongation, excellent flexibility, and good processability properties. An effective way to develop more accessible PBAT-based bioplastics for wide application in packaging is blending of PBAT with thermoplastic starch (TPS) since PBAT is costly with prices approximately double or even triple the prices of traditional plastics like polyethylene. This study is focused on investigating the influence of TPS/PBAT blend ratio and montmorillonite (MMT) content on the physical and mechanical properties and molecular mobility of TPS–MMT/PBAT nanocomposites. Obtained TPS–MMT/PBAT nanocomposites through the melt blending process were characterized using tensile testing, dynamic mechanical thermal analysis (DMTA), and X-ray diffraction (XRD), as well as solid-state ¹H and ¹³C NMR spectroscopy. Mechanical properties demonstrated that the addition of TPS to PBAT leads to a substantial decrease in the tensile strength as well as in the elongation at break, while Young’s modulus is rising substantially, while the effect of the MMT addition is almost negligible on the tensile stress of the blends. DMTA results confirmed the formation of TPS domains in the PBAT matrix. With increasing TPS content, mobility of starch-rich regions of TPS domains slightly increases. However, molecular mobility in glycerol-rich regions of TPS domains in the blends was slightly restricted. Moreover, the data obtained from ¹³C CP/MAS NMR spectra indicated that the presence of TPS in the sample decreases the mobility of the PBAT chains, mainly those located at the TPS/PBAT interfaces. Full article

A biodegradable polymer packaging system for ‘Benitaka’ table grapes (Vitis vinifera L.) was developed to inhibit the development of gray mold during refrigerated storage. The system consisted of packages and sachets containing Na₂S₂O₅ to release sulfur dioxide (SO₂), both produced with biodegradable films of starch, glycerol, and poly (adipate co-butylene terephthalate) (PBAT) produced via blown extrusion. The films were characterized in terms of thickness, density, mass loss in water, water vapor permeability, sorption isotherms, and mechanical properties. The table grapes were packed with biodegradable plastic bags containing SO₂-releasing sachets inside. The experimental design was completely randomized, with four repetitions and five treatments: (a) control, without sachet containing Na₂S₂O₅ and SiO₂; (b) 2 g of Na₂S₂O₅ + 2 g of SiO₂; (c) 4 g of Na₂S₂O₅ + 1 g of SiO₂; (d) 4 g of Na₂S₂O₅ + 2 g of SiO₂; and (e) 4 g of Na₂S₂O₅ + 4 g of SiO₂. The bunches were stored in a refrigerated chamber at 1 ± 1 °C and relative humidity above 90%. The treatments were evaluated 30 and 45 days after the beginning of refrigerated storage and 3 days at room temperature. The grapes were evaluated based on the incidence of gray mold, mass loss, stem browning, shattered berries, and berry bleaching. The data were subjected to the analysis of variance, and the means were compared using Tukey’s test at 5%. The biodegradable films had good processability during the production via blown extrusion, with good physical properties to be used in the packaging of grapes and the production of SO₂-releasing sachets. The biodegradable polymer packaging system (biodegradable plastic bags + SO₂-releasing sachets) inhibited the development of gray mold on ‘Benitaka’ table grapes for 45 days at 1 °C, preserving their quality, with low mass loss, few shattered berries, and rachis freshness. Full article

This study aimed to fabricate new variations of glycerol-based polyesters by grafting poly(glycerol adipate) (PGA) with hydrophobic bioactive moieties, tocopherol (TOC), and cholesterol (CHO). Their effects on nanoparticle (NP) formation, drug release, and cellular responses in cancer and normal cells were evaluated. CHO and TOC were successfully grafted onto PGA backbones with 30% and 50% mole grafting. Increasing the percentage of mole grafting in both molecules increased the glass transition temperature and water contact angle of the final polymers but decreased the critical micelle concentration of the formulated particles. PGA-TOC NPs reduced the proliferation of MDA-MB-231 cancer cells. However, they enhanced the proliferation of primary dermal fibroblasts within a specific concentration range. PGA-CHO NPs minimally affected the growth of cancer and normal cells. Both types of NPs did not affect apoptosis or the cell cycle of cancer cells. PGA-CHO and PGA-TOC NPs were able to entrap SN-38, a hydrophobic anticancer drug, with a particle size <200 nm. PGA-CHO NPs had a higher drug loading capacity and a greater drug release than PGA-TOC NPs. However, SN-38-loaded PGA-TOC NPs showed higher toxicity than SN-38 and SN-38-loaded PGA-CHO NPs due to the combined effects of antiproliferation and higher cellular uptake. Compared with SN-38, the drug-loaded NPs more profoundly induced sub-G1 in the cell cycle analysis and apoptosis of cancer cells in a similar pattern. Therefore, PGA-CHO and PGA-TOC polymers have potential applications as delivery systems for anticancer drugs. Full article

Enzymatic one-pot synthesis procedures in a one-step and two-step monomers addition were developed to obtain poly(glycerol adipate) macromers with methacrylate end-functional groups under the presence of 1 and 3 wt% of Candida antarctica lipase B (CALB). Glycerol, divinyl adipate, and vinyl methacrylate were enzymatically reacted (vinyl methacrylate was either present from the beginning in the monomers solution or slowly dropped after 6 h of reaction) in tetrahydrofuran (THF) at 40 °C over 48 h. Macromers with a methacrylate end groups fraction of ≈52% in a simple one-pot one-step procedure were obtained with molecular weights (M_n) of ≈7500–7900 g/mol. The obtained products under the one-pot one-step and two steps synthesis procedures carried out using 1 and 3 wt% of a CALB enzymatic catalyst were profusely characterized by NMR (¹H and ¹³C), MALDI-TOF MS, and SEC. The methacrylate functional macromers obtained with the different procedures and 1 wt% of CALB were combined with an Irgacure^® 369 initiator to undergo homopolymerization under UV irradiation for 10 and 30 min, in order to test their potential to obtain amorphous networks within minutes with similar properties to those typically obtained by complex acrylation/methacrylation procedures, which need multiple purification steps and harsh reagents such as acyl chlorides. To the best of our knowledge, this is the first time that it has been demonstrated that the obtention of methacrylate-functional predominantly linear macromers based on poly(glycerol adipate) is able to be UV crosslinked in a simple one-step procedure. Full article

This study aimed to improve the anticancer effect of Cordyceps militaris herbal extract (CME) on breast cancer cells with hyaluronic acid (HYA) surface-decorated lipid polymer hybrid nanoparticles (LPNPs) and evaluate the applicability of a synthesized poly(glycerol adipate) (PGA) polymer for LPNP preparation. Firstly, cholesterol- and vitamin E-grafted PGA polymers (PGA-CH and PGA-VE, respectively) were fabricated, with and without maleimide-ended polyethylene glycol. Subsequently, CME, which contained an active cordycepin equaling 9.89% of its weight, was encapsulated in the LPNPs. The results revealed that the synthesized polymers could be used to prepare CME-loaded LPNPs. The LPNP formulations containing Mal-PEG were decorated with cysteine-grafted HYA via thiol-maleimide reactions. The HYA-decorated PGA-based LPNPs substantially enhanced the anticancer effect of CME against MDA-MB-231 and MCF-7 breast cancer cells by enhancing cellular uptake through CD44 receptor-mediated endocytosis. This study demonstrated the successful targeted delivery of CME to the CD44 receptors of tumor cells by HYA-conjugated PGA-based LPNPs and the new application of synthesized PGA-CH- and PGA-VE-based polymers in LPNP preparation. The developed LPNPs showed promising potential for the targeted delivery of herbal extracts for cancer treatment and clear potential for translation in in vivo experiments. Full article

Pneumococcal disease remains a global burden, with current conjugated vaccines offering protection against the common serotype strains. However, there are over 100 serotype strains, and serotype replacement is now being observed, which reduces the effectiveness of the current vaccines. Pneumococcal surface protein A (PspA) has been investigated as a candidate for new serotype-independent pneumococcal vaccines, but requires adjuvants and/or delivery systems to improve protection. Polymeric nanoparticles (NPs) are biocompatible and, besides the antigen, can incorporate mucoadhesive and adjuvant substances such as chitosans, which improve antigen presentation at mucosal surfaces. This work aimed to define the optimal NP formulation to deliver PspA into the lungs and protect mice against lethal challenge. We prepared poly(glycerol-adipate-co-ω-pentadecalactone) (PGA-co-PDL) and poly(lactic-co-glycolic acid) (PLGA) NPs using an emulsion/solvent evaporation method, incorporating chitosan hydrochloride (HCl-CS) or carboxymethyl chitosan (CM-CS) as hybrid NPs with encapsulated or adsorbed PspA. We investigated the physicochemical properties of NPs, together with the PspA integrity and biological activity. Furthermore, their ability to activate dendritic cells in vitro was evaluated, followed by mucosal immunization targeting mouse lungs. PGA-co-PDL/HCl-CS (291 nm) or CM-CS (281 nm) NPs produced smaller sizes compared to PLGA/HCl-CS (310 nm) or CM-CS (299 nm) NPs. Moreover, NPs formulated with HCl-CS possessed a positive charge (PGA-co-PDL +17 mV, PLGA + 13 mV) compared to those formulated with CM-CS (PGA-co-PDL −20 mV, PLGA −40 mV). PspA released from NPs formulated with HCl-CS preserved the integrity and biological activity, but CM-CS affected PspA binding to lactoferrin and antibody recognition. PspA adsorbed in PGA-co-PDL/HCl-CS NPs stimulated CD80+ and CD86+ cells, but this was lower compared to when PspA was encapsulated in PLGA/HCl-CS NPs, which also stimulated CD40+ and MHC II (I-A/I-E)+ cells. Despite no differences in IgG being observed between immunized animals, PGA-co-PDL/HCl-CS/adsorbed-PspA protected 83% of mice after lethal pneumococcal challenge, while 100% of mice immunized with PLGA/HCl-CS/encapsulated-PspA were protected. Therefore, this formulation is a promising vaccine strategy, which has beneficial properties for mucosal immunization and could potentially provide serotype-independent protection. Full article

The fabrication of affordable biodegradable plastics remains a challenging issue for both the scientific community and industries as mechanical properties and biodegradability improve at the expense of the high cost of the material. Hence, the present work deals with fabrication and characterization of biodegradable polymer with 40% rice husk waste filler and 60% polymer-containing mixture of polybutylene succinate (PBS) and poly butylenes adipate-Co-terephthalate (PBAT) to achieve good mechanical properties, 92% biodegradation in six months, and competitive pricing. The challenge in incorporating high amounts of hydrophilic nature filler material into hydrophobic PBS/PBAT was addressed by adding plasticizers such as glycerol and calcium stearate. The compatibilizers such as maleic anhydride (MA) and dicumyl peroxide (DCP) was used to improve the miscibility between hydrophobic PBS/PBAT and hydrophilic filler material. The component with the formulation of 24:36:40 (PBS/PBAT/TPRH) possessed the tensile strength of 14.27 MPa, modulus of 200.43 MPa, and elongation at break of 12.99%, which was suitable for the production of molded products such as a tray, lunch box, and straw. The obtained composite polymer achieved 92% mass loss after six months of soil burial test confirming its biodegradability. Full article

The mechanical properties and tear resistance of an ecofriendly flexible packaging film, i.e., poly(lactic acid) (PLA)/poly (butylene adipate–co–terephthalate) (PBAT) film, were investigated via a blown film extrusion process. The application of PLA and PBAT in product packaging is limited due to the high brittleness, low stiffness, and incompatibility of the materials. In this study, the effects of various plasticizers, such as adipate, adipic acid, glycerol ester, and adipic acid ester, on the plasticization of PLA and fabrication of the PLA/PBAT blown film were comprehensively evaluated. It was determined that the plasticizer containing ether and ester functionalities (i.e., adipic acid ester) improved the flexibility of PLA as well as its compatibility with PBAT. It was found that the addition of the plasticizer effectively promoted chain mobility of the PLA matrix. Moreover, the interfacial adhesion between the plasticized PLA domain and PBAT matrix was enhanced. The results of the present study demonstrated that the plasticized PLA/PBAT blown film prepared utilizing a blown film extrusion process exhibited improved tear resistance, which increased from 4.63 to 8.67 N/mm in machine direction and from 13.19 to 16.16 N/mm in the transverse direction. Full article

Biocompatible and bio-based materials are an appealing resource for the pharmaceutical industry. Poly(glycerol-adipate) (PGA) is a biocompatible and biodegradable polymer that can be used to produce self-assembled nanoparticles (NPs) able to encapsulate active ingredients, with encouraging perspectives for drug delivery purposes. Starch is a versatile, inexpensive, and abundant polysaccharide that can be effectively applied as a bio-scaffold for other molecules in order to enrich it with new appealing properties. In this work, the combination of PGA NPs and starch films proved to be a suitable biopolymeric matrix carrier for the controlled release preparation of hydrophobic drugs. Dynamic Light Scattering (DLS) was used to determine the size of drug-loaded PGA NPs, while the improvement of the apparent drug water solubility was assessed by UV-vis spectroscopy. In vitro biological assays were performed against cancer cell lines and bacteria strains to confirm that drug-loaded PGA NPs maintained the effective activity of the therapeutic agents. Dye-conjugated PGA was then exploited to track the NP release profile during the starch/PGA nanocomposite film digestion, which was assessed using digestion models mimicking physiological conditions. The collected data provide a clear indication of the suitability of our biodegradable carrier system for oral drug delivery. Full article

The enzymatically synthesized poly (glycerol adipate) (PGA) has demonstrated all the desirable key properties required from a performing biomaterial to be considered a versatile “polymeric-tool” in the broad field of drug delivery. The step-growth polymerization pathway catalyzed by lipase generates a highly functionalizable platform while avoiding tedious steps of protection and deprotection. Synthesis requires only minor purification steps and uses cheap and readily available reagents. The final polymeric material is biodegradable, biocompatible and intrinsically amphiphilic, with a good propensity to self-assemble into nanoparticles (NPs). The free hydroxyl group lends itself to a variety of chemical derivatizations via simple reaction pathways which alter its physico-chemical properties with a possibility to generate an endless number of possible active macromolecules. The present work aims to summarize the available literature about PGA synthesis, architecture alterations, chemical modifications and its application in drug and gene delivery as a versatile carrier. Following on from this, the evolution of the concept of enzymatically-degradable PGA-drug conjugation has been explored, reporting recent examples in the literature. Full article

Starch is one of the most abundant polysaccharides on the earth and it is the most important source of energy intake for humans. Thermoplastic starch (TPS) is also widely used for new bio-based materials. The blending of starch with other molecules may lead to new interesting biodegradable scaffolds to be exploited in food, medical, and pharmaceutical fields. In this work, we used native starch films as biopolymeric matrix carriers of chemo enzymatically-synthesized poly (glycerol-adipate) (PGA) nanoparticles (NPs) to produce a novel and biocompatible material. The prototype films had a crystallinity ranging from 4% to 7%. The intrinsic and thermo-mechanical properties of the composite showed that the incorporation of NPs in the starch films decreases the glass transition temperature. The utilization of these film prototypes as the basis for new biocompatible material showed promise, particularly because they have a very low or even zero cytotoxicity. Coumarin was used to monitor the distribution of the PGA NPs in the films and demonstrated a possible interaction between the two polymers. These novel hybrid nanocomposite films show great promise and could be used in the future as biodegradable and biocompatible platforms for the controlled release of amphiphilic and hydrophobic active ingredients. Full article