Crystallization Behavior and Electrical Properties of Nanoparticle-Reinforced Poly(lactic Acid)-Based Films

Graphene oxide (GO) and multiwalled carbon nanotubes with silver particles (MWNT-Ag) of different concentrations were used as nanofillers to prepare poly(lactic acid) (PLA) nanoparticle films through the solvent casting method. In this study, the effects of nanoparticles on the crystallization behavior, relationships between the dispersion and electrical properties, and hydrolytic degradation behaviors were investigated for the PLA/MWNT-Ag and PLA/rGO films. Differential scanning calorimetry was used to evaluate the crystallization behaviors of the PLA/MWNT-Ag and PLA/reduced GO (rGO) films. Electron probe microanalysis was performed to characterize the dispersion of MWNT-Ag, and X-ray diffraction and Raman spectroscopy were used to determine the degree of dispersion of rGO in the PLA matrix. The results showed that nanoparticles enhanced the crystallization kinetics of PLA as well as the hydrolytic degradation rate. From the measurement of electrical properties, the electrical conductivity of PLA/MWNT-Ag 1.0 wt% was much higher than that of the pure PLA and PLA/rGO films, showing that MANT and Ag nanoparticles contribute greatly to enhancing the electrical conductivity of the PLA/MWNT-Ag films.

Degradation-Dependent Stress Relaxing Semi-Interpenetrating Networks of Hydroxyethyl Cellulose in Gelatin-PEG Hydrogel with Good Mechanical Stability and Reversibility

The mechanical milieu of the extracellular matrix (ECM) plays a key role in modulating the cellular responses. The native ECM exhibits viscoelasticity with stress relaxation behavior. Here, we reported the preparation of degradation-mediated stress relaxing semi-interpenetrating (semi-IPN) polymeric networks of hydroxyethyl cellulose in the crosslinked gelatin-polyethylene glycol (PEG) architecture, leveraging a newly developed synthesis protocol which successively includes one-pot gelation under physiological conditions, freeze-drying and a post-curing process. Fourier transform infrared (FTIR) confirmed the formation of the semi-IPN blend mixture. A surface morphology analysis revealed an open pore porous structure with a compact skin on the surface. The hydrogel showed a high water-absorption ability (720.00 ± 32.0%) indicating the ability of retaining a hydrophilic nature even after covalent crosslinking with functionalized PEG. Detailed mechanical properties such as tensile, compressive, cyclic compression and stress relaxation tests were conducted at different intervals over 28 days of hydrolytic degradation. Overall, the collective mechanical properties of the hydrogel resembled the mechanics of cartilage tissue. The rate of stress relaxation gradually increased with an increasing swelling ratio. Hydrolytic degradation led to a marked increase in the percentage dissipation energy and stress relaxation response, indicating the degradation-dependent viscoelasticity of the hydrogel. Strikingly, the hydrogel maintained the structural stability even after degrading two-thirds of its initial mass after a month-long hydrolytic degradation. This study demonstrates that this semi-IPN G-PEG-HEC hydrogel possesses bright prospects as a potential scaffolding material in tissue engineering.

Modular Paradigm for Composites: Modeling Hydrothermal Degradation of Glass Fibers

Fiber-reinforced composite materials are often used in structural applications in humid, marine, and offshore environments. Superior mechanical properties are compromised by environmental ageing and hydrolytic degradation. Glass fibers are the most broadly used type of fiber reinforcement to date. However, they are also most severely affected by environmental degradation. The glass fiber degradation rates depend on: (1) glass formulation; (2) environmental factors: pH, T, stress; (3) sizing; (4) matrix polymer; (5) fiber orientation and composite layup. In this short review (communication), seven modules within the Modular Paradigm are reviewed and systematized. These modeling tools, encompassing both trivial and advanced formulas, enable the prediction of the environmental ageing of glass fibers, including the kinetics of mass loss, fiber radius reduction, environmental crack growth and loss of strength. The modeling toolbox is of use for both industry and academia, and the Modular Paradigm could become a valuable tool for such scenarios as lifetime prediction and the accelerated testing of fiber-reinforced composite materials.

Hydrolytic Degradation of Polylactic Acid Fibers as a Function of pH and Exposure Time

Polylactic acid (PLA) is a widely used bioresorbable polymer in medical devices owing to its biocompatibility, bioresorbability, and biodegradability. It is also considered a sustainable solution for a wide variety of other applications, including packaging. Because of its widespread use, there have been many studies evaluating this polymer. However, gaps still exist in our understanding of the hydrolytic degradation in extreme pH environments and its impact on physical and mechanical properties, especially in fibrous materials. The goal of this work is to explore the hydrolytic degradation of PLA fibers as a function of a wide range of pH values and exposure times. To complement the experimental measurements, molecular-level details were obtained using both molecular dynamics (MD) simulations with ReaxFF and density functional theory (DFT) calculations. The hydrolytic degradation of PLA fibers from both experiments and simulations was observed to have a faster rate of degradation in alkaline conditions, with 40% of strength loss of the fibers in just 25 days together with an increase in the percent crystallinity of the degraded samples. Additionally, surface erosion was observed in these PLA fibers, especially in extreme alkaline environments, in contrast to bulk erosion observed in molded PLA grafts and other materials, which is attributed to the increased crystallinity induced during the fiber spinning process. These results indicate that spun PLA fibers function in a predictable manner as a bioresorbable medical device when totally degraded at end-of-life in more alkaline conditions.

Changes in Crystal Structure and Accelerated Hydrolytic Degradation of Polylactic Acid in High Humidity

Highly crystallized polylactic acid (PLA) is suitable for industrial applications due to its stiffness, heat resistance, and dimensional stability. However, crystal lamellae in PLA products might delay PLA decomposition in the environment. This study clarifies how the initial crystal structure influences the hydrolytic degradation of PLA under accelerated conditions. Crystallized PLA was prepared by annealing amorphous PLA at a specific temperature under reduced pressure. Specimens with varied crystal structure were kept at 70 °C and in a relative humidity (RH) of 95% for a specific time. Changes in crystal structure were analyzed using differential calorimetry and wide-angle X-lay diffraction. The molecular weight (MW) was measured with gel permeation chromatography. The crystallinity of the amorphous PLA became the same as that of the initially annealed PLA within one hour at 70 °C and 95% RH. The MW of the amorphous PLA decreased faster even though the crystallinity was similar during the accelerated degradation. The low MW chains of the amorphous PLA tended to decrease faster, although changes in the MW distribution suggested random scission of the molecular chains for initially crystallized PLA. The concentrations of chain ends and impurities, which catalyze hydrolysis, in the amorphous region were considered to be different in the initial crystallization. The crystallinity alone does not determine the speed of hydrolysis.

Amniotic Epithelial Stem Cells Counteract Acidic Degradation By-Products of Electrospun PLGA Scaffold by Improving Their Immunomodulatory Profile In Vitro

Electrospun poly(lactic-co-glycolic acid) (PLGA) scaffolds with highly aligned fibers (ha-PLGA) represent promising materials in the field of tendon tissue engineering (TE) due to their characteristics in mimicking fibrous extracellular matrix (ECM) of tendon native tissue. Among these properties, scaffold biodegradability must be controlled allowing its replacement by a neo-formed native tendon tissue in a controlled manner. In this study, ha-PLGA were subjected to hydrolytic degradation up to 20 weeks, under di-H2O and PBS conditions according to ISO 10993-13:2010. These were then characterized for their physical, morphological, and mechanical features. In vitro cytotoxicity tests were conducted on ovine amniotic epithelial stem cells (oAECs), up to 7 days, to assess the effect of non-buffered and buffered PLGA by-products at different concentrations on cell viability and their stimuli on oAECs’ immunomodulatory properties. The ha-PLGA scaffolds degraded slowly as evidenced by a slight decrease in mass loss (14%) and average molecular weight (35%), with estimated degradation half-time of about 40 weeks under di-H2O. The ultrastructure morphology of the scaffolds showed no significant fiber degradation even after 20 weeks, but alteration of fiber alignment was already evident at week 1. Moreover, mechanical properties decreased throughout the degradation times under wet as well as dry PBS conditions. The influence of acid degradation media on oAECs was dose-dependent, with a considerable effect at 7 days’ culture point. This effect was notably reduced by using buffered media. To a certain level, cells were able to compensate the generated inflammation-like microenvironment by upregulating IL-10 gene expression and favoring an anti-inflammatory rather than pro-inflammatory response. These in vitro results are essential to better understand the degradation behavior of ha-PLGA in vivo and the effect of their degradation by-products on affecting cell performance. Indeed, buffering the degradation milieu could represent a promising strategy to balance scaffold degradation. These findings give good hope with reference to the in vivo condition characterized by physiological buffering systems.

Structural Analysis of the Ancestral Haloalkane Dehalogenase AncLinB-DmbA

Haloalkane dehalogenases (EC 3.8.1.5) play an important role in hydrolytic degradation of halogenated compounds, resulting in a halide ion, a proton, and an alcohol. They are used in biocatalysis, bioremediation, and biosensing of environmental pollutants and also for molecular tagging in cell biology. The method of ancestral sequence reconstruction leads to prediction of sequences of ancestral enzymes allowing their experimental characterization. Based on the sequences of modern haloalkane dehalogenases from the subfamily II, the most common ancestor of thoroughly characterized enzymes LinB from Sphingobium japonicum UT26 and DmbA from Mycobacterium bovis 5033/66 was in silico predicted, recombinantly produced and structurally characterized. The ancestral enzyme AncLinB-DmbA was crystallized using the sitting-drop vapor-diffusion method, yielding rod-like crystals that diffracted X-rays to 1.5 Å resolution. Structural comparison of AncLinB-DmbA with their closely related descendants LinB and DmbA revealed some differences in overall structure and tunnel architecture. Newly prepared AncLinB-DmbA has the highest active site cavity volume and the biggest entrance radius on the main tunnel in comparison to descendant enzymes. Ancestral sequence reconstruction is a powerful technique to study molecular evolution and design robust proteins for enzyme technologies.