Investigation of the Hydrolytic Degradation Kinetics of 3D-Printed PLA Structures under a Thermally Accelerated Regime.

The application of biobased and biodegradable polymers, such as polylactide (PLA), in fused deposition modeling (FDM) 3D-printing technology creates a new prospect for rapid prototyping and other applications in the context of ecology. The popularity of the FDM method and its significance in material engineering not only creates new prospects for the development of technical sciences on an industrial scale, but also introduces new technologies into households. In this study, the kinetics of the hydrolytic degradation of samples obtained by the FDM method from commercially available PLA filaments under a thermally accelerated regime were analyzed. The investigation was conducted at the microstructural, supramolecular, and molecular levels by using methods such as micro-computed tomography (micro-CT), wide-angle X-ray diffraction (WAXD), viscosimetry, and mass erosion measurements. The obtained results clearly present the rapid structural changes in 3D-printed materials during degradation due to their amorphous initial structure. The complementary studies carried out at different scale levels allowed us to demonstrate the relationship between the observed structural changes in the samples and the hydrolytic decomposition of the polymer chains, which made it possible to scientifically understand the process and expand the knowledge on biodegradation.

Evaluation of Polysaccharide-Peptide Conjugates Containing the RGD Motif for Potential Use in Muscle Tissue Regeneration.

New scaffold materials composed of biodegradable components are of great interest in regenerative medicine. These materials should be: stable, nontoxic, and biodegrade slowly and steadily, allowing the stable release of biodegradable and biologically active substances. We analyzed peptide-polysaccharide conjugates derived from peptides containing RGD motif (H-RGDS-OH (1), H-GRGDS-NH2 (2), and cyclo(RGDfC) (3)) and polysaccharides as scaffolds to select the most appropriate biomaterials for application in regenerative medicine. Based on the results of MTT and Ki-67 assays, we can state that the conjugates containing calcium alginate and the ternary nonwoven material were the most supportive of muscle tissue regeneration. Scanning electron microscopy imaging and light microscopy studies with hematoxylin-eosin staining showed that C2C12 cells were able to interact with the tested peptide-polysaccharide conjugates. The release factor (Q) varied depending on both the peptide and the structure of the polysaccharide matrix. LDH, Alamarblue®, Ki-67, and cell cycle assays indicated that peptides 1 and 2 were characterized by the best biological properties. Conjugates containing chitosan and the ternary polysaccharide nonwoven with peptide 1 exhibited very high antibacterial activity against Staphylococcus aureus and Klebsiella pneumoniae. Overall, the results of the study suggested that polysaccharide conjugates with peptides 1 and 2 can be potentially used in regenerative medicine.

Polymer-Based Electrophoretic Deposition of Nonwovens for Medical Applications: The Effect of Carrier Structure, Solution, and Process Parameters.

Hyaluronate and alginate are non-toxic and biocompatible polymers, which can be used for surface modification and functionalization of many kinds of materials. Electrophoretic deposition (EPD) has several advantages, including its versatility, simplicity, and ability to coat substrates with complex shapes, and is used for the creation of antimicrobial or hydrophobic coatings on metallic biomaterials, among other applications. However, its utilization for applying biopolymer layers on textiles is very limited due to the more complex structure and spatial characteristics of fibrous materials. The aim of this research was to analyze the effects of selected EPD process parameters and the structural characteristics of fibrous carriers on the kinetics of the process and the microscopic characteristics of the deposited layers. The influence of solution characteristics, process parameters, and carrier structures obtained using two different techniques (melt blown and spun-bonded) were analyzed. The morphology and structure of the created deposits were analyzed using scanning electron microscopy and computed tomography, and molecular structure analysis was performed with Fourier Transform Infrared spectroscopy. The surface mass and thickness of fibrous poly (lactic acid)-based carriers were analyzed in accordance with the respective standards. This study serves as a basis for discussion and further development of this method with regard to fibrous materials for medical applications.

Investigation of the Influence of PLA Molecular and Supramolecular Structure on the Kinetics of Thermal-Supported Hydrolytic Degradation of Wet Spinning Fibres.

In this study, differences in the kinetics of the thermal-supported hydrolytic degradation of polylactide (PLA) wet spinning fibres due to material variance in the initial molecular and supramolecular structure were analysed. The investigation was carried out at the microstructural and molecular levels by using readily available methods such as scanning electron microscopy, mass erosion measurement and estimation of intrinsic viscosity. The results show a varying degree of influence of the initial structure on the degradation rate of the studied PLA fibres. The experiment shows that hydrolytic degradation at a temperature close to the cold crystallization temperature is, on a macroscopic level, definitely more rapid for the amorphous material, while on a molecular scale it is similar to a semi-crystalline material. Furthermore, for the adopted degradation temperature of 90 °C, a marginal influence of the pH of the degradation medium on the degradation kinetics was also demonstrated.

Molecular and Supramolecular Changes in Polybutylene Succinate (PBS) and Polybutylene Succinate Adipate (PBSA) Copolymer during Degradation in Various Environmental Conditions.

In this paper, the influence of the various degradation conditions, on the molecular and supramolecular structure of polybutylene succinate (PBS) and polybutylene succinate adipate (PBSA) copolymer during degradation is described. The experiment was carried out by the use of injection molded samples and normalized conditions of biodegradation in soil, composting and artificial weathering. Materials were studied by size-exclusion chromatography (SEC) coupled with multiangle laser light scattering (MALLS) detection and wide-angle X-ray diffraction (WAXD). Additionally, the physical and mechanical properties of the samples were determined. The performed experiments clearly show difference impacts of the selected degradation conditions on the macroscopic, supramolecular and molecular parameters of the studied aliphatic polyesters. The structural changes in PBS and PBSA explain the observed changes in the physical and mechanical properties of the obtained injection molded samples.

Investigation of the Influence of PLA Molecular Structure on the Crystalline Forms (α' and α) and Mechanical Properties of Wet Spinning Fibres.

In this paper, the influence of the molecular structure of polylactide (PLA)-characterised by its molar mass and content of d-lactide isomer-on the molecular ordering and α'⁻α form transition during fibre manufacturing by the wet spinning method is described. Fibres were studied by wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). Additionally, the physical and mechanical properties of the fibres were determined. This study also examines the preliminary molecular ordering and crystallisation of PLA fibres at various draw ratios. The performed experiments clearly show the dependence of the molecular ordering of PLA on the molar mass and d-lactide content during the wet spinning process. The fibres manufactured from PLA with the lowest content of d-lactide and the lowest molar mass were characterised by a higher tendency for crystallisation and a higher possibility to undergo the disorder-to-order phase transition (α' to α form). The structural changes in PLA explain the observed changes in the physical and mechanical properties of the obtained fibres.