Duncan J. Maitland

Biomedical applications of thermally activated shape memory polymers

Shape memory polymers (SMPs) are smart materials that can remember a primary shape and can return to this primary shape from a deformed secondary shape when given an appropriate stimulus. This property allows them to be delivered in a compact form via minimally invasive surgeries in humans, and deployed to achieve complex final shapes. Here we review the various biomedical applications of SMPs and the challenges they face with respect to actuation and biocompatibility. While shape memory behavior has been demonstrated with heat, light and chemical environment, here we focus our discussion on thermally stimulated SMPs.

A pH-responsive supramolecular polymer gel as an enteric elastomer for use in gastric devices

Devices resident in the stomach -- which are used for a variety of clinical applications including nutritional modulation for bariatrics, ingestible electronics for diagnosis and monitoring, and gastric retentive dosage forms for prolonged drug delivery -- typically incorporate elastic polymers to compress the devices during delivery through the esophagus and other narrow orifices in the digestive system. However, in the event of accidental device fracture or migration, the non-degradable nature of these materials risks intestinal obstruction. Here, we show that an elastic, pH-responsive supramolecular gel remains stable and elastic in the acidic environment of the stomach but can be dissolved in the neutral-pH environment of the small and large intestines. In a large animal model, prototype devices with these materials as the key component demonstrated prolonged gastric retention and safe passage. These enteric elastomers should increase the safety profile for a wide range of gastric retentive devices.

Opacification of Shape Memory Polymer Foam Designed for Treatment of Intracranial Aneurysms

Shape memory polymer (SMP) foam possesses structural and mechanical characteristics that make them very promising as an alternative treatment for intracranial aneurysms. Our SMP foams have low densities, with porosities as high as 98.8%; favorable for catheter delivery and aneurysm filling, but unfavorable for attenuating X-rays. This lack of contrast impedes the progression of this material becoming a viable medical device. This paper reports on increasing radio-opacity by incorporating a high-Z element, tungsten particulate filler to attenuate X-rays, while conserving similar physical properties of the original non-opacified SMP foams. The minimal amount of tungsten for visibility was determined and subsequently incorporated into SMP foams, which were then fabricated into samples of increasing thicknesses. These samples were imaged through a pig’s skull to demonstrate radio-opacity in situ. Quantification of the increase in image contrast was performed via image processing methods and standard curves were made for varying concentrations of tungsten doped solid and foam SMP. 4% by volume loading of tungsten incorporated into our SMP foams has proven to be an effective method for improving radio-opacity of this material while maintaining the mechanical, physical and chemical properties of the original formulation.

Porous Shape-Memory Polymers

Porous shape memory polymers (SMPs) include foams, scaffolds, meshes, and other polymeric substrates that possess porous three-dimensional macrostructures. Porous SMPs exhibit active structural and volumetric transformations and have driven investigations in fields ranging from biomedical engineering to aerospace engineering to the clothing industry. The present review article examines recent developments in porous SMPs, with focus given to structural and chemical classification, methods of characterization, and applications. We conclude that the current body of literature presents porous SMPs as highly interesting smart materials with potential for industrial use.

The effect of moisture absorption on the physical properties of polyurethane shape memory polymer foams

The effect of moisture absorption on the glass transition temperature (T(g)) and stress/strain behavior of network polyurethane shape memory polymer (SMP) foams has been investigated. With our ultimate goal of engineering polyurethane SMP foams for use in blood contacting environments, we have investigated the effects of moisture exposure on the physical properties of polyurethane foams. To our best knowledge, this study is the first to investigate the effects of moisture absorption at varying humidity levels (non-immersion and immersion) on the physical properties of polyurethane SMP foams. The SMP foams were exposed to differing humidity levels for varying lengths of time, and they exhibited a maximum water uptake of 8.0% (by mass) after exposure to 100% relative humidity for 96 h. Differential scanning calorimetry results demonstrated that water absorption significantly decreased the T(g) of the foam, with a maximum water uptake shifting the T(g) from 67 °C to 5 °C. Samples that were immersed in water for 96 h and immediately subjected to tensile testing exhibited 100% increases in failure strains and 500% decreases in failure stresses; however, in all cases of time and humidity exposure, the plasticization effect was reversible upon placing moisture-saturated samples in 40% humidity environments for 24 h.

In vivo response to an implanted shape memory polyurethane foam in a porcine aneurysm model

Cerebral aneurysms treated by traditional endovascular methods using platinum coils have a tendency to be unstable, either due to chronic inflammation, compaction of coils, or growth of the aneurysm. We propose to use alternate filling methods for the treatment of intracranial aneurysms using polyurethane-based shape memory polymer (SMP) foams. SMP polyurethane foams were surgically implanted in a porcine aneurysm model to determine biocompatibility, localized thrombogenicity, and their ability to serve as a stable filler material within an aneurysm. The degree of healing was evaluated via gross observation, histopathology, and low vacuum scanning electron microscopy imaging after 0, 30, and 90 days. Clotting was initiated within the SMP foam at time 0 (<1 h exposure to blood before euthanization), partial healing was observed at 30 days, and almost complete healing had occurred at 90 days in vivo, with minimal inflammatory response.

Thermomechanical Properties, Collapse Pressure, and Expansion of Shape Memory Polymer Neurovascular Stent Prototypes

Shape memory polymer stent prototypes were fabricated from thermoplastic polyurethane. Commercial stents are generally made of stainless steel or other alloys. These alloys are too stiff and prevent most stent designs from being able to navigate small and tortuous vessels to reach intracranial lesions. A solid tubular model and a high flexibility laser etched model are presented. The stents were tested for collapse in a pressure chamber. At 37 degrees C, the full collapse pressure was comparable to that of commercially available stents, and higher than the estimated maximum pressure exerted by intracranial arteries. However, there is a potential for onset of collapse, which needs further study. The stents were crimped and expanded, the laser-etched stent showed full recovery with an expansion ratio of 2.7 and a 1% axial shortening.

Characterizing and modeling the free recovery and constrained recovery behavior of a polyurethane shape memory polymer.

In this work, tensile tests and one-dimensional constitutive modeling are performed on a high recovery force polyurethane shape memory polymer that is being considered for biomedical applications. The tensile tests investigate the free recovery (zero load) response as well as the constrained displacement recovery (stress recovery) response at extension values up to 25%, and two consecutive cycles are performed during each test. The material is observed to recover 100% of the applied deformation when heated at zero load in the second thermomechanical cycle, and a stress recovery of 1.5 MPa to 4.2 MPa is observed for the constrained displacement recovery experiments.After performing the experiments, the Chen and Lagoudas model is used to simulate and predict the experimental results. The material properties used in the constitutive model - namely the coefficients of thermal expansion, shear moduli, and frozen volume fraction - are calibrated from a single 10% extension free recovery experiment. The model is then used to predict the material response for the remaining free recovery and constrained displacement recovery experiments. The model predictions match well with the experimental data.

A High‐Performance Recycling Solution for Polystyrene Achieved by the Synthesis of Renewable Poly(thioether) Networks Derived from d‐Limonene

Nanocomposite polymers are prepared using a new sustainable materials synthesis process in which d-Limonene functions simultaneously both as a solvent for recycling polystyrene (PS) waste and as a monomer that undergoes UV-catalyzed thiol-ene polymerization reactions with polythiol comonomers to afford polymeric products composed of precipitated PS phases dispersed throughout elastomeric poly(thioether) networks. These blended networks exhibit mechanical properties that greatly exceed those of either polystyrene or the poly(thioether) network homopolymers alone.

Virtual Treatment of Basilar Aneurysms Using Shape Memory Polymer Foam

Numerical simulations are performed on patient-specific basilar aneurysms that are treated with shape memory polymer (SMP) foam. In order to assess the post-treatment hemodynamics, two modeling approaches are employed. In the first, the foam geometry is obtained from a micro-CT scan and the pulsatile blood flow within the foam is simulated for both Newtonian and non-Newtonian viscosity models. In the second, the foam is represented as a porous media continuum, which has permeability properties that are determined by computing the pressure gradient through the foam geometry over a range of flow speeds comparable to those of in vivo conditions. Virtual angiography and additional post-processing demonstrate that the SMP foam significantly reduces the blood flow speed within the treated aneurysms, while eliminating the high-frequency velocity fluctuations that are present within the pre-treatment aneurysms. An estimation of the initial locations of thrombus formation throughout the SMP foam is obtained by means of a low fidelity thrombosis model that is based upon the residence time and shear rate of blood. The Newtonian viscosity model and the porous media model capture similar qualitative trends, though both yield a smaller volume of thrombus within the SMP foam.