Biodegradable nanocomposites were prepared by adding ZnO nanoparticles to bacterial polyester poly­(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) via solution casting technique. The morphology, thermal, mechanical, antibacterial, barrier, and migration properties of the nanocomposites were analyzed. The nanoparticles were uniformly dispersed within PHBV without the aid of coupling agents, and acted effectively as nucleating agents, raising the crystallization temperature and the level of crystallinity of the matrix while decreasing its crystallite size. A gradual rise in thermal stability was found with increasing ZnO loading, since the nanofillers hinder the diffusion of volatiles generated during the decomposition process. The nanocomposites displayed superior stiffness, strength, toughness, and glass transition temperature, whereas they displayed reduced water uptake and oxygen and water vapor permeability compared to the neat biopolymer, related to the strong matrix–nanofiller interfacial adhesion attained via hydrogen bonding interactions. At an optimal concentration of 4.0 wt % ZnO, the tensile strength and Young’s and storage moduli showed a maximum that coincided with the highest crystallinity and the best barrier properties. PHBV/ZnO films showed antibacterial activity against human pathogen bacteria, and the effect on Escherichia coli was stronger than on Staphylococcus aureus. The overall migration levels of the nanocomposites in both nonpolar and polar simulants dropped upon increasing nanoparticle content, and were well below the limits required by the current normative for food packaging materials. These sustainable nanomaterials with antimicrobial function are very promising to be used as containers for beverage and food products as well as for disposable applications like cutlery or overwrap films.

Poly(propylene fumarate) (PPF)-based nanocomposites incorporating different amounts of polyethylene glycol-functionalized graphene oxide (PEG-GO) have been prepared via sonication and thermal curing, and their surface morphology, structure, thermal stability, hydrophilicity, water absorption, biodegradation, cytotoxicity, mechanical, viscoelastic and antibacterial properties have been investigated. SEM and TEM images corroborated that the noncovalent functionalization with PEG caused the exfoliation of GO into thinner flakes. IR spectra suggested the presence of strong hydrogen-bonding interactions between the nanocomposite components. A gradual rise in the level of hydrophilicity, water uptake, biodegradation rate, surface roughness, protein absorption capability and thermal stability was found upon increasing GO concentration in the composites. Tensile tests revealed improved stiffness, strength and toughness for the composites compared to unfilled PPF, ascribed to a homogeneous GO dispersion within the matrix along with a strong PPF/PEG-GO interfacial adhesion via polar and hydrogen bonding interactions. Further, the nanocomposites retained enough stiffness and strength under a biological state to provide effective support for bone tissue formation. The antibacterial activity was investigated against Gram-positive Staphylococcus aureus and Staphylococcus epidermidis as well as Gram-negative Pseudomonas aeruginosa and Escherichia coli microorganisms, and it rose sharply upon increasing GO concentration; systematically, the biocide effect was stronger versus Gram-positive bacteria. Cell viability data demonstrated that PPF/PEG-GO composites do not induce toxicity over human dermal fibroblasts. These novel materials show great potential to be applied in the bone tissue engineering field.

Poly(3-hydroxybutyrate) (PHB)-based bionanocomposites incorporating different contents of ZnO nanoparticles were prepared via solution casting technique. The nanoparticles were dispersed within the biopolymer without the need for surfactants or coupling agents. The morphology, thermal, mechanical, barrier, migration and antibacterial properties of the nanocomposites were investigated. The nanoparticles acted as nucleating agents, increasing the crystallization temperature and the degree of crystallinity of the matrix, and as mass transport barriers, hindering the diffusion of volatiles generated during the decomposition process, leading to higher thermal stability. The Young’s modulus, tensile and impact strength of the biopolymer were enhanced by up to 43%, 32% and 26%, respectively, due to the strong matrix-nanofiller interfacial adhesion attained via hydrogen bonding interactions, as revealed by the FT-IR spectra. Moreover, the nanocomposites exhibited reduced water uptake and superior gas and vapour barrier properties compared to neat PHB. They also showed antibacterial activity against both Gram-positive and Gram-negative bacteria, which was progressively improved upon increasing ZnO concentration. The migration levels of PHB/ZnO composites in both non-polar and polar simulants decreased with increasing nanoparticle content, and were well below the current legislative limits for food packaging materials. These biodegradable nanocomposites show great potential as an alternative to synthetic plastic packaging materials especially for use in food and beverage containers and disposable applications.

Castor oil (CO), which is a readily available, relatively inexpensive, and environmentally benign nonedible oil, has been successfully used as matrix material to prepare biocompatible and biodegradable nanocomposite films filled with chitosan (CS)-modified ZnO nanoparticles. The biocomposites were synthesized via a simple and versatile solution mixing and casting method. The morphology, structure, thermal stability, water absorption, biodegradability, cytocompatibility, barrier, mechanical, viscoelastic, antibacterial, and wound healing properties of the films have been analyzed. FT-IR spectra were used to obtain information about the nanoparticle-matrix interactions. The thermal stability, hydrophilicity, degree of porosity, water absorption, water vapor transmission rate (WVTR), oxygen permeability (Dk), and biodegradability of the films increased with the CS-ZnO loading. The WVTR and Dk data obtained are within the range of values reported for commercial wound dressings. Tensile tests demonstrated that the nanocomposites displayed a good balance between elasticity, strength, and flexibility under both dry and simulated body fluid (SBF) environments. The flexibility increased in a moist atmosphere due to the plasticization effect of absorbed water. The nanocomposites also exhibited significantly enhanced dynamic mechanical performance (storage modulus and glass transition temperature) than neat CO under different humidity conditions. The antibacterial activity of the films against Escherichia coli, Staphylococcus aureus, and Micrococcus luteus bacteria was investigated in the presence and the absence of UV light. The biocide effect increased progressively with the CS-ZnO content and was systematically stronger against Gram-positive cells. Composites with nanoparticle loading ≤5.0 wt % exhibited very good in vitro cytocompatibility and enabled a faster wound healing than neat CO and control gauze, hence showing great potential to be applied as antibacterial wound dressings.

Biocompatible ternary nanocomposites based on poly(ether ether ketone) (PEEK)/poly(ether imide) (PEI) blends reinforced with bioactive titanium dioxide (TiO2) nanoparticles were fabricated via ultrasonication followed by melt-blending. The developed biomaterials were characterized using FT-IR, SEM, XRD, DSC, TGA, and DMA. Further, their water-absorption, tensile, tribological, dielectric, and antibacterial properties were evaluated. PEI acts as a coupling agent, since it can interact both with PEEK via π-π stacking and polar interactions as well as with the nanoparticles through hydrogen bonding, as corroborated by the FT-IR spectra, which resulted in a homogeneous titania dispersion within the biopolymer blend without applying any particle surface treatment or polymer functionalization. A change from promotion to retardation in the crystallization rate of the matrix was found with increasing TiO2 concentration, while its crystalline structure remained unaltered. The nanoparticles stiffened, strengthened, and toughened the matrix simultaneously, and the optimal properties were achieved at 4.0 wt % TiO2. More interesting, the tensile properties were retained after steam sterilization in an autoclave or exposure to a simulated body fluid (SBF). The nanocomposites also displayed reduced water absorption though higher thermal stability, storage modulus, glass transition temperature, dielectric constant, and dielectric loss compared to the control blend. Further, remarkable enhancements in the tribological properties under both SBF and dry environments were attained. The nanoparticles conferred antibacterial action versus Gram-positive and Gram-negative bacteria in the presence and the absence of UV light, and the highest inhibition was attained at 4.0 wt % nanoparticle concentration. These nanocomposites are expected to be used in long-term load-bearing implant applications.