An experimental investigation into the physical, thermal and mechanical degradation of a polymeric bioresorbable scaffold.

This study presents a comprehensive evaluation of the mechanical, micro-mechanical and physical properties of Reva Medical Fantom Encore Bioresorbable Scaffolds (BRS) subjected to a thermally-accelerated degradation protocol. The Fantom Encore BRS were immersed in phosphate buffered saline solution at 50 °C for 112 days with radial compression testing, nanoindentation, differential scanning calorimetry, gel permeation chromatography and mass loss characterisation performed at consecutive time points. In the initial stages of degradation (Days 0-21), the Fantom Encore BRS showed increases in radial strength and stiffness, despite a substantial reduction in in molecular weight, with a slight increase in the melt temperature also observed. In the second phase (Days 35-54), the radial strength of the BRS samples were maintained despite a continued loss in molecular weight. However, during this phase, the ductility of the stent showed a reduction, with stent fracture occurring earlier in the crimp process and with lower amounts of plastic deformation evident under visual examination post-fracture. In the final phase (Days 63-112), the load-bearing capacity of the Fantom Encore BRS showed continued reduction, with decreases in radial stiffness and strength, and drastic reduction in the work-to-fracture of the devices. Throughout each phase, there was a steady increase in the relative crystallinity, with limited mass loss until day 112 and only minor changes in glass transition and melt temperatures. Limited changes were observed in nano-mechanical properties, with measured local elastic moduli and hardness values remaining largely similar throughout degradation. Given that the thermally-accelerated in vitro conditions represented a four-fold acceleration of physiological conditions, these results suggest that the BRS scaffolds could exhibit substantially brittle behaviour after âˆ¼ one year of implantation.

Parametric Finite Element Model and Mechanical Characterisation of Electrospun Materials for Biomedical Applications.

Electrospun materials, due to their unique properties, have found many applications in the biomedical field. Exploiting their porous nanofibrous structure, they are often used as scaffolds in tissue engineering which closely resemble a native cellular environment. The structural and mechanical properties of the substrates need to be carefully optimised to mimic cues used by the extracellular matrix to guide cells' behaviour and improve existing scaffolds. Optimisation of these parameters is enabled by using the finite element model of electrospun structures proposed in this study. First, a fully parametric three-dimensional microscopic model of electrospun material with a random fibrous network was developed. Experimental results were obtained by testing electrospun poly(ethylene) oxide materials. Parameters of single fibres were determined by atomic force microscopy nanoindentations and used as input data for the model. The validation was performed by comparing model output data with tensile test results obtained for electrospun mats. We performed extensive analysis of model parameters correlations to understand the crucial factors and enable extrapolation of a simplified model. We found good agreement between the simulation and the experimental data. The proposed model is a potent tool in the optimisation of electrospun structures and scaffolds for enhanced regenerative therapies.

Physical and mechanical degradation behaviour of semi-crystalline PLLA for bioresorbable stent applications.

This study presents a systematic evaluation of the physical, thermal and mechanical performance of medical-grade semi-crystalline PLLA undergoing thermally-accelerated degradation. Samples were immersed in phosphate-buffered saline solution at 50 °C for 112 days and mass loss, molecular weight, thermal properties, degree of crystallinity, FTIR and Raman spectra, tensile elastic modulus, yield stress and failure stress/strain were evaluated at consecutive time points. Samples showed a consistent reduction in molecular weight and melting temperature, a consistent increase in percent crystallinity and limited changes in glass transition temperature and mass loss. At day 49, a drastic reduction in tensile failure strain was observed, despite the fact that elastic modulus, yield and tensile strength of samples were maintained. Brittleness increase was followed by rapid increase in degradation rate. Beyond day 70, samples became too brittle to test indicating substantial deterioration of their load-bearing capacity. This study also presents a computational micromechanics framework that demonstrates that the elastic modulus of a semi-crystalline polymer undergoing degradation can be maintained, despite a reducing molecular weight through compensatory increases in percent crystallinity. This study presents novel insight into the relationship between physical properties and mechanical performance of medical-grade PLLA during degradation and could have important implications for design and development of bioresorbable stents for vascular applications.

Solvent Sorption-Induced Actuation of Composites Based on a Polymer of Intrinsic Microporosity.

Materials that are capable of actuation in response to a variety of external stimuli are of significant interest for applications in sensors, soft robotics, and biomedical devices. Here, we present a class of actuators using composites based on a polymer of intrinsic microporosity (PIM). By adding an activated carbon (AX21) filler to a PIM, the composite exhibits repeatable actuation upon solvent evaporation and wetting and it is possible to achieve highly controlled three-dimensional actuation. Curled composite actuators are shown to open upon exposure to a solvent and close as a result of solvent evaporation. The degree of curling and actuation is controlled by adjusting the amount of filler and evaporation rate of the solvent casting process, while the actuation speed is controlled by adjusting the type of solvent. The range of forces and actuation speed produced by the composite is demonstrated using acetone, ethanol, and dimethyl sulfoxide as the solvent. The maximum contractile stress produced upon solvent desorption in the pure PIM polymer reached 12 MPa, with an ultimate force over 20 000 times the weight of a sample. This form of the composite actuator is insensitive to humidity and water, which makes it applicable in an aqueous environment, and can survive a wide range of temperatures. These characteristics make it a promising actuator for the diverse range of operating conditions in robotic and medical applications. The mechanism of actuation is discussed, which is based on the asymmetric distribution of the carbon filler particles that leads to a bilayer structure and the individual layers expand and contract differently in response to solvent wetting and evaporation, respectively. Finally, we demonstrate the application of the actuator as a potential drug delivery vehicle, with capacity for encapsulating two kinds of drugs and reduced drug leakage in comparison to existing technologies.

The denticulate ligament - Tensile characterisation and finite element micro-scale model of the structure stabilising spinal cord.

BACKGROUND: Damage to the spinal cord is one of the most debilitating pathologies with considerable health, economic and social impact. Improved prevention, treatment and rehabilitation after spinal cord injury (SCI) requires the complex biomechanics of the spinal cord with all its structural elements and the injury mechanism to be understood. This comprehensive understanding will also allow development of models and tools enabling better diagnosis, surgical treatment with increased safety and efficacy and possible development of regenerative therapies. The denticulate ligaments play an important role in stabilising spinal cord within the spinal canal. They participate in spinal cord movements and play a role in determining the stress distribution during physiological but also traumatic loading. We present detailed tensile characterisation of the denticulate ligaments and a Finite Element micro-scale model of the ligament relating its structure with the distribution of stress under physiological loading. METHOD: Denticulate ligaments were dissected from cervical spinal levels from 6 porcine cervical specimens with fragments of the pia and dura mater and characterised in terms of their geometry and response to uniaxial tensile loading. The stress-strain characteristics were recorded until rupture of the ligament, ultimate parameters and Young's moduli were determined. The parametric micro-structural Finite Element model was constructed based on literature microscope and histological images of a denticulate ligament as a phenomenological representation of the complex microstructure of a soft tissue. The model was validated against the experimental data. RESULTS: Stress-strain characteristics obtained in tensile test were typical for a soft tissue behaviour. No statistically relevant differences in ultimate strength, strain and Young's moduli were observed between the ligaments harvested from different vertebral levels. Average ultimate tensile stress was 1.26 ±â€¯0.20 MPa at strain 0.51 ±â€¯0.00, rupturing force (1.01 ±â€¯0.21 N) was in agreement with results obtained previously. The Finite Element model accurately predicted the extension-load behaviour of the denticulate ligament in elastic regime. The micro-scale structural representation enabled capturing deformation modes representative of the experimentally observed behaviour. CONCLUSIONS: The presented stress-strain characteristics of the denticulate ligaments add valuable data to the understanding of the biomechanics of the spinal cord and enable development of more accurate models. The developed micro-scale model was capable of capturing biomechanical response of collagenous tissue under tensile loading, it can be applied for the prediction of other soft tissues behaviours. The denticulate ligament model should be included into future spinal cord models to fully represent the complex system's biomechanics and enable development of surgical aid tools to improve patient outcomes and future regenerative therapies.

Mechanical characterisation of polymer of intrinsic microporosity PIM-1 for hydrogen storage applications.

Polymers of intrinsic microporosity (PIMs) are currently attracting interest due to their unusual combination of high surface areas and capability to be processed into free-standing films. However, there has been little published work with regards to their physical and mechanical properties. In this paper, detailed characterisation of PIM-1 was performed by considering its chemical, gas adsorption and mechanical properties. The polymer was cast into films, and characterised in terms of their hydrogen adsorption at -196 °C up to much higher pressures (17 MPa) than previously reported (2 MPa), demonstrating the maximum excess adsorbed capacity of the material and its uptake behaviour in higher pressure regimes. The measured tensile strength of the polymer film was 31 MPa with a Young's modulus of 1.26 GPa, whereas the average storage modulus exceeded 960 MPa. The failure strain of the material was 4.4%. It was found that the film is thermally stable at low temperatures, down to -150 °C, and decomposition of the material occurs at 350 °C. These results suggest that PIM-1 has sufficient elasticity to withstand the elastic deformations occurring within state-of-the-art high-pressure hydrogen storage tanks and sufficient thermal stability to be applied at the range of temperatures necessary for gas storage applications.