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“Self-fitting” shape memory polymer (SMP) scaffolds prepared as semi-interpenetrating networks (semi-IPNs) with crosslinked linear-poly(ε-caprolactone)-diacrylate (PCL-DA, M(n) ~10 kg/mol) and linear-poly(L-lactic acid) (PLLA, M(n) ~15 kg/mol) [75/25 wt%] exhibited robust mechanical properties and accelerated degradation rates versus a PCL-DA scaffold control. However, their potential to treat irregular craniomaxillofacial (CMF) bone defects is limited by their relatively high fitting temperature (T(fit) ~55 °C; related to the T(m) of PCL) required for shape recovery (i.e. expansion) and subsequent shape fixation during press fitting of the scaffold, which can be harmful to surrounding tissue. Additionally, the viscosity of the solvent-based precursor solutions, cast over a fused salt template during fabrication, can limit scaffold size. Thus, in this work, analogous semi-IPN SMP scaffolds were also formed with a 4-arm star-PCL-tetracryalate (star-PCL-TA) (M(n) ~10 kg/mol) and star-PLLA (M(n) ~15 kg/mol). To assess the impact of a star-polymer architecture, four semi-IPN compositions were prepared: linear-PCL-DA/linear-PLLA (L/L), linear-PCL-DA/star-PLLA (L/S), star-PCL-TA/linear-PLLA (S/L) and star-PCL-TA/star-PLLA (S/S). Two PCL controls were also prepared: LPCL (i.e. 100% linear-PCL-DA) and SPCL (i.e. 100% star-PCL-TA). The S/S semi-IPN scaffold exhibited particularly desirable properties. In addition to achieving a lower, tissue-safe T(fit) (~45 °C), it exhibited the fastest rate of degradation which is anticipated to more favourably permit neotissue infiltration. The radial expansion pressure exerted by the S/S semi-IPN scaffold at T(fit) was greater than that of LPCL, which is expected to enhance osseointegration and mechanical stability. The intrinsic viscosity of the S/S semi-IPN macromer solution was also reduced such that larger scaffold specimens could be prepared.

Shape memory polymer (SMP) foams are a promising material for hemostatic dressings due to their biocompatibility, high surface area, excellent shape recovery, and ability to quickly initiate blood clotting. Biodegradable SMP foams could eliminate the need for a secondary removal procedure of hemostatic material from the patients’ wound, further facilitating wound healing. In this study, we developed hydrolytically and oxidatively biodegradable SMP foams by reacting polyols (triethanolamine or glycerol) with 6-aminocaproic acid or glycine to generate foaming monomers with degradable ester bonds. These monomers were used in foam synthesis to provide highly crosslinked SMP foam structures. The ester-containing foams showed clinically relevant thermal properties that were comparable to controls and excellent shape recovery within eight min. Triethanolamine-based ester-containing foams showed interconnected porous structure along with increased mechanical strength. Faster hydrolytic and oxidative biodegradation rates were achieved in ester-containing foams in comparison to controls. These biodegradable SMP foams with clinically applicable thermal properties possess great potential as an effective hemostatic device for use in hospitals or on battlefields.

To prevent aneurysmal rupture, intracranial aneurysms are often treated with endovascular metal coils that fill the aneurysm sac and stimulate thrombus formation, thereby isolating the aneurysm from the arterial flow. Despite its widespread use, this method can result in suboptimal outcomes leading to aneurysm recurrence. Recently, shape memory polymer foam has been proposed as an alternative aneurysm filler. In this work, a computational thrombus model is used to predict the clotting response within idealized 2D aneurysms virtually treated with foam. The results are compared to previously reported clot formation predictions in identical 2D aneurysm geometries filled with simplified endovascular metal coil shapes. Each of the foam-filled aneurysms reached at least 94% thrombus occlusion regardless of foam pore size or orientation, whereas the final thrombus occlusion within the coil-filled aneurysms varied from 80.8 to 92.2% with many of the cases leaving large areas in the aneurysm neck unfilled. Based on the simulations presented here, shape memory polymer foams may be able to produce more predictable, uniform, and complete clotting results than bare metal coils, independent of foam geometry or orientation.

Shape memory polymer (SMP) foams are porous materials with high surface area and large volumetric expansion capabilities that are well suited for endovascular occlusion applications, including brain aneurysm embolization. However, many polyurethane SMP foams are inherently radiolucent when X-ray visibility is required to ensure the safe delivery of the foam to the targeted aneurysm site using fluoroscopy. Here, highly radio-dense tantalum microparticles were added to a previously reported triiodobenzene-containing SMP foam (ATIPA foam) premix to fabricate ATIPA foam-tantalum composites (AT_T). The AT_T foams showed comparable glass transition temperatures, faster expansion profiles, increased X-ray visibility, good cytocompatibility, and faster oxidative degradation compared to the control ATIPA foam without tantalum. The mechanical properties were improved up to 4 vol% tantalum and the X-ray visibility was most appropriate for the 2 vol% (AT_2%T) and 4 vol% (AT_4%T) tantalum foams. E-beam sterilization did not impair the critical properties of the ATIPA foams. Overall, AT_2%T was the optimal foam composition for neurovascular prototypes due to its high oxidative stability in vitro compared to previous low-density SMP foams. The AT_T foams are very promising materials with high toughness and sufficient X-ray visibility for use as neurovascular embolization devices.

Shape memory polymer foams have been used in a wide range of medical applications, including, but not limited to, vessel occlusion and aneurysm treatment. This unique polymer system has been proven to shape-fill a void, which makes it useful for occlusion applications. While the shape memory polymer foam has superior performance and healing outcomes compared to its leading competitors, some device applications may benefit from longer material degradation times, or degradation-resistant formulations with increased fibrous encapsulation. In this study, biostable shape memory polymer foams were synthesized, and their physical and chemical properties were characterized as an initial evaluation of feasibility for vascular occlusion applications. After characterizing their shape memory behavior in an aqueous environment, degradation of this polymer system was studied in vitro using accelerated oxidative and hydrolytic solutions. Results indicated that the foams did not lose mass under oxidative or hydrolytic conditions, and they maintained high shape recovery in aqueous in vitro models. These degradation-resistant systems have potential for use in vascular occlusion and other wound healing applications that benefit from permanent, space-filling shape memory behavior.

The goal of this work was to develop a shape memory polymer (SMP) foam with visibility under both X-ray and magnetic resonance imaging (MRI) modalities. A porous polymeric material with these properties is desirable in medical device development for applications requiring thermoresponsive tissue scaffolds with clinical imaging capabilities. Dual modality visibility was achieved by chemically incorporating monomers with X-ray visible iodine-motifs and MRI visible monomers with gadolinium content. Physical and thermomechanical characterization showed the effect of increased gadopentetic acid (GPA) on shape memory behavior. Multiple compositions showed brightening effects in pilot, T1-weighted MR imaging. There was a correlation between the polymeric density and X-ray visibility on expanded and compressed SMP foams. Additionally, extractions and indirect cytocompatibility studies were performed to address toxicity concerns of gadolinium-based contrast agents (GBCAs). This material platform has the potential to be used in a variety of medical devices.

Current vascular aneurysm treatments often require either highly invasive strategy to surgically occlude an aneurysm or endovascular occlusion via metal coils. While endovascular coils are safer, they have limited efficacy. Endovascular coils that are integrated with shape memory polymer (SMP) foams have the potential to improve occlusion and reduce coil risks; however, the mechanical performance and limited homogeneity of SMP foams can hinder their effective use. To address this issue, SMP foams are synthesized using the monomer diethanolamine (DEA) in place of triethanolamine (TEA) to provide improved mechanical properties for medical device applications. Mechanical testing and micro-fracture analysis were performed on DEA and TEA foams. DEA foams show improved toughness and reduced micro-fractures compared to the control. This work presents the utility of DEA in SMP synthesis to enable the potential production of safer aneurysm treatment.

Various types of embolization devices have been developed for the treatment of cerebral aneurysms. However, it is challenging to properly evaluate device performance and train medical personnel for device deployment without the aid of functionally relevant models. Current in vitro aneurysm models suffer from a lack of key functional and morphological features of brain vasculature that limit their applicability for these purposes. These features include the physiologically relevant mechanical properties and the dynamic cellular environment of blood vessels subjected to constant fluid flow. Herein, we developed three-dimensionally (3D) printed aneurysm-bearing vascularized tissue structures using gelatin-fibrin hydrogel of which the inner vessel walls were seeded with human cerebral microvascular endothelial cells (hCMECs). The hCMECs readily exhibited cellular attachment, spreading, and confluency all around the vessel walls, including the aneurysm walls. Additionally, the in vitro platform was directly amenable to flow measurements via particle image velocimetry, enabling the direct assessment of the vascular flow dynamics for comparison to a 3D computational fluid dynamics model. Detachable coils were delivered into the printed aneurysm sac through the vessel using a microcatheter and static blood plasma clotting was monitored inside the aneurysm sac and around the coils. This biomimetic in vitro aneurysm model is a promising method for examining the biocompatibility and hemostatic efficiency of embolization devices and for providing hemodynamic information which would aid in predicting aneurysm rupture or healing response after treatment.

Shape memory polymers (SMPs) have been found to be promising biomaterials for a variety of medical applications; however, the clinical translation of such technology is dependent on tailorable properties such as gravimetric changes in degradation environments. For SMPs synthesized from amino-alcohols, oxidation resulting in rapid mass loss may be problematic in terms of loss of material functionality as well as toxicity and cytocompatibility concerns. Control of gravimetric changes was achieved through the incorporation of small molecule antioxidants, either directly into the polymer matrix or included in microparticles to form a SMP composite material. With direct incorporation of small molecule phenolic antioxidant 2,2′-methylenebis(6-tert-butyl)-methylphenol (Methyl), SMPs displayed reduce strain recovery by more than 50% (Methyl) and increase elastic modulus from approximately 1.4 to 2.3 MPa, at the expense of the strain to failure being reduced from 45% to 32%. Importantly, such changes could not ensure retention of the antioxidants and therefore did not increase oxidative stability beyond 15 days in accelerated oxidative conditions (equivalent to approximately 800 days in porcine aneurysms) in all cases except for the inclusion of a hindered amine that capped network growth, which also resulted in shape memory reduction (only 80% recoverable strain achieved). However, the inclusion of antioxidants in microparticles was found to produce materials with similar thermomechanical (T(g) migration below 1.0 °C) and shape recovery of 100%, while increasing oxidative resistance compared to controls (oxidation onset was delayed by 3 days and material lifespan increased to approximately 20–22 days in accelerated oxidative solution or beyond 1000 days in the porcine aneurysm). The microparticle composite SMPs also act as a platform for environmental sensing, such as pH-dependent fluorescence shifts and payload release, as demonstrated by fluorescent dye studies using phloxine B and nile blue chloride and the release of antioxidants over a 3 week period. The use of polyurethane-urea microparticles in porous SMPs is demonstrated to increase biostability of the materials, by approximately 25%, and ultimately extend their lifespan for use in aneurysm occlusion as determined through calculated in vivo degradation rates corresponding to a porcine aneurysm environment.

Despite a number of clinically available hemostats, uncontrolled bleeding is the primary cause of trauma-related death. Shape-memory polymer (SMP) foams have a number of desirable properties for use as hemostats, including shape recovery to enable delivery into bleed sites, biocompatibility, and rapid blood clotting. To expand upon this material system, the current work aims to incorporate phenolic acids, which are honey-based antimicrobial agents, into SMP foams. We showed that cinnamic acid (CA) can be utilized as a monomer in SMP synthesis to provide foams with comparable pore structure and retained cytocompatibility. The addition of CA enabled tuning of thermal and shape-memory properties within clinically relevant ranges. Furthermore, the modified foams demonstrated initial and sustained antimicrobial effects against gram-positive and gram-negative bacteria. These multifunctional scaffolds demonstrate potential for use as hemostats to improve upon current hemorrhage treatments and provide a new tool in tuning the biological and material properties of SMP foams.

Intracranial saccular aneurysm treatment using endovascular embolization devices are limited by aneurysm recurrence that can lead to aneurysm rupture. A shape memory polymer (SMP) foam-coated coil (FCC) embolization device was designed to increase packing density and improve tissue healing compared to current commercial devices. FCC devices were fabricated and tested using in vitro models to assess feasibility for clinical treatment of intracranial saccular aneurysms. FCC devices demonstrated smooth delivery through tortuous pathways similar to control devices as well as greater than 10 min working time for clinical repositioning during deployment. Furthermore, the devices passed pilot verification tests for particulates, chemical leachables, and cytocompatibility. Finally, devices were successfully implanted in an in vitro saccular aneurysm model with large packing density. Though improvements and future studies evaluating device stiffness were identified as a necessity, the FCC device demonstrates effective delivery and packing performance that provides great promise for clinical application of the device in treatment of intracranial saccular aneurysms.

Patent ductus arteriosus (PDA) is a congenital cardiovascular defect in which a fetal connection between the aorta and pulmonary artery does not spontaneously close shortly after birth. If left uncorrected serious complications and even death can occur. Surgical ligation is the traditional treatment method; however, it is an invasive procedure, that motivates development of a minimally invasive option. Shape memory polymer (SMP) foams are unique materials that hold promise in the field of minimally invasive occlusion devices. In this work, a prototype nitinol foam cage (NFC) incorporating SMP foams has been designed and evaluated in multiple mechanical and in vitro verification tests. The NFC demonstrated acceptable fatigue resistance in a preliminary strut integrity test, withstanding one million cycles without complete strut fracture. Radial force analysis of both thick- and thin-walled prototype variations generated less vessel distension and wall tension in a vessel mimic compared to a commercial device. The NFCs exhibited negligible in vitro migration, comparable to that of a commercial device, using simplified, ideal models of PDA. Deployment characteristics of the prototypes were evaluated and compared to that of a commercial device when delivered into physiological models of PDA. During mock deployments, a veterinary cardiologist noted that, while deliverable, the thin-walled NFC prototype exhibited poor deployment characteristics, however the thick-walled NFC had deployment characteristics comparable to that of a commercial device. The promising results of this study warrant further investigation of the NFC device for canine PDA closure.

Recent studies utilizing shape memory polymer foams to coat embolizing coils have shown potential benefits over current aneurysm treatments. In the current study utilizing a rabbit-elastase aneurysm model, the performance of test article (foam-coated coil [FCC]) and control (bare platinum coils [BPCs]) devices were compared at 30, 90, and 180 days using micro-CT and histological assessments. The host response was measured by identifying the cells regionally present within the aneurysm, and assessing the degree of residual debris and connective tissue. The 3D reconstructions of aneurysms provided context for histologic findings, and aided in the overall aneurysm assessment. At all time points, >75% of the cells categorized in each aneurysm were associated with a bioactive yet biocompatible host response (vs. the remainder of cells that were associated with acute inflammation). The extracellular matrix exhibited a transition from residual fibrin at 30 days to a greater degree of connective tissue at 90 and 180 days. Although the control BPC-treated aneurysms exhibited a greater degree of connective tissue at the earliest time point examined (30 days), by 180 days, the FCC-treated aneurysms had more connective tissue and less debris overall than the control aneurysms. When considering cell types and extracellular matrix composition, the overall host response scores were significantly better in FCC-treated aneurysms at the later time point. Based on the results of these metrics, the FCC device may lead to an advanced tissue remodeling response over BPC occlusion devices.

Shape memory polymers (SMPs) are highly attractive materials for medical devices. Specifically, SMP foams are currently being used as embolic devices in peripheral and cerebral vascular applications. To ensure the proper function and safety of these materials in their intended applications, it is important to understand how processing treatments, such as aging, sterilization, and foam composition can influence their degradation. Here, SMP foams were treated with industry relevant processing parameters, and the influence on degradation was observed via gravimetric, chemical, and morphological studies. Accelerated thermal aging was shown to have an influence on material degradation rate in real time oxidative studies. Sterilization was performed via Electron beam (E-beam) irradiation at the high and low dosages commonly used in industry and had no significant influence on foam degradation profiles. These findings help inform appropriate treatment of SMP foam embolic devices to ensure their safety and efficacy.

Shape memory polymers (SMPs) are promising for non-invasive medical devices and tissue scaffolds, but are limited by a lack of visibility under clinical imaging. Fluorescent dyes are an alternative to radiocontrast agents in medical applications, they can be utilized in chemical sensors and monitors and may be anti-microbial agents. Thus, a fluorescent SMP could be a highly valuable biomaterial system. Here, we show that four fluorescent dyes (phloxine B (PhB), eosin Y (Eos), indocyanine green (IcG), and calcein (Cal)) can be crosslinked into the polymer backbone to enhance material optical properties without alteration of shape memory and thermomechanical properties. Examinations of the emission wavelengths of the materials compared with the dye solutions showed a slight red shift in the peak emissions, indicative of crosslinking of the material. Quantitative analysis revealed that PhB enabled visibility through 1 cm of blood and through soft tissue. We also demonstrate the utility of these methods in combination with radio-opaque microparticle additives and the use of laser-induced shape recovery to allow for rapid shape recovery below the glass transition temperature. The crosslinking of fluorescent dyes into the SMP enables tuning of physical properties and shape memory and independently of the fluorescence functionality. This fluorescent SMP biomaterial system allows for use of multiple imaging modalities with potential application in minimally invasive medical devices.

The endovascular delivery of platinum alloy bare metal coils has been widely adapted to treat intracranial aneurysms. Despite the widespread clinical use of this technique, numerous suboptimal outcomes are possible. These may include chronic inflammation, low volume filling, coil compaction, and recanalization, all of which can lead to aneurysm recurrence, need for retreatment, and/or potential rupture. This study evaluates a treatment alternative in which polyurethane shape memory polymer (SMP) foam is used as an embolic aneurysm filler. The performance of this treatment method was compared to that of bare metal coils in a head-to-head in vivo study utilizing a porcine vein pouch aneurysm model. After 90 and 180 days post-treatment, gross and histological observations were used to assess aneurysm healing. At 90 days, the foam-treated aneurysms were at an advanced stage of healing compared to the coil-treated aneurysms and showed no signs of chronic inflammation. At 180 days, the foam-treated aneurysms exhibited an 89-93% reduction in cross-sectional area; whereas coiled aneurysms displayed an 18-34% area reduction. The superior healing in the foam-treated aneurysms at earlier stages suggests that SMP foam may be a viable alternative to current treatment methods. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 1892-1905, 2017.

Host response to an implanted biomaterial is a complex process involving microscopic changes in extracellular matrix (ECM) composition. Reliable pathology analysis is imperative for accurate assessment of the tissue response to an implanted device. Plastic histology is commonly used for histology evaluation of medical devices to assess the device-tissue interface; however, this technique is prone to variable staining that can confound histology interpretation. Appropriately, we propose using transmission electron microscopy (TEM) to confirm histologic ECM findings in order to provide sufficient host-response data. Tissue response to an absorbable shape memory polymer intravascular occlusion device with a nitinol wire backbone was evaluated. Representative plastic-embedded, micro-ground sections from 30-day, 60-day, and 90-day timepoints were analyzed. ECM regions were selected, and ultrathin sections were created for TEM evaluation. Histological changes in ECM composition were compared for light microscopy (LM) and TEM findings; specifically, TEM fibrillary patterns for collagen and fibrin were used to confirm LM results. Throughout this study, LM reveals inconsistent staining in plastic-embedded sections. TEM, on the other hand, provides clear insight into the tissue response by morphologically discerning distinct fibrillary patterns within ECM structures; loose to dense collagen surrounds the implant as fibrin degrades, demonstrating progression of postimplant ECM maturation. Moreover, TEM serves as a definitive method for confirming tissue substrate morphology when LM findings prove ambiguous.

Shape memory polymer (SMP) foam-coated coils (FCCs) are new embolic coils coated with porous SMP designed to expand for increased volume filling and enhanced healing after implantation. The purpose of this study was to compare chronic aneurysm healing after treatment with SMP FCCs to bare platinum coil (BPC) controls in the rabbit elastase aneurysm model. BPCs or SMP FCCs were implanted in rabbit elastase-induced aneurysms for follow-up at 30 days (n = 10), 90 days (n = 5), and 180 days (n = 12 for BPCs; n = 14 for SMP FCCs). Aneurysm occlusion and histologic healing, including a qualitative healing score, neointima thickness, collagen deposition, and inflammation were compared between the two groups. The mean neointima thickness was significantly greater in groups treated with SMP FCCs for all three time points. Histologic healing scores and collagen deposition quantification suggested that aneurysms treated with SMP FCCs experience more complete healing of the dome by 90 days, but the differences were not statistically significant. More progressive occlusion and recanalization were observed in aneurysms treated with SMP FCCs, but neither difference was statistically significant. Additionally, the SMP foam used in the FCCs was found to degrade faster in the rabbit elastase model than expected based on previous studies in a porcine sidewall aneurysm model. This study suggests that SMP FCCs can promote neointima formation along the aneurysm neck, and may lead to more complete healing of the dome and neck. These findings indicate potential benefits of this device for aneurysm occlusion procedures. © 2019 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 107B:2466-2475, 2019.

We employ a concentric sphere Mie scattering model to describe light scattering by pulmonary alveoli and the airway surface liquid (ASL). Using this layered sphere model, we compare alveolar scattering at different points along the respiratory cycle and observe the effect of ASL thickness on light scattering in the lung. We have also extrapolated the model to investigate alveolar scattering in various animal models of pulmonary disease. This model of pulmonary light scattering can estimate in vivo optical properties for normal and pathological states, potentially aiding the design of optical systems for diagnosis and investigation of pulmonary pathologies.

The rapid development of new optical imaging techniques is dependent on the availability of low-cost, customizable, and easily reproducible standards. By replicating the imaging environment, costly animal experiments to validate a technique may be circumvented. Predicting and optimizing the performance of in vivo and ex vivo imaging techniques requires testing on samples that are optically similar to tissues of interest. Tissue-mimicking optical phantoms provide a standard for evaluation, characterization, or calibration of an optical system. Homogenous polymer optical tissue phantoms are widely used to mimic the optical properties of a specific tissue type within a narrow spectral range. Layered tissues, such as the epidermis and dermis, can be mimicked by simply stacking these homogenous slab phantoms. However, many in vivo imaging techniques are applied to more spatially complex tissue where three dimensional structures, such as blood vessels, airways, or tissue defects, can affect the performance of the imaging system. This protocol describes the fabrication of a tissue-mimicking phantom that incorporates three-dimensional structural complexity using material with optical properties of tissue. Look-up tables provide India ink and titanium dioxide recipes for optical absorption and scattering targets. Methods to characterize and tune the material optical properties are described. The phantom fabrication detailed in this article has an internal branching mock airway void; however, the technique can be broadly applied to other tissue or organ structures.

Porous shape memory polymers (SMPs) exhibit geometric and volumetric shape change when actuated by an external stimulus and can be fabricated as foams, scaffolds, meshes, and other polymeric substrates that possess porous three-dimensional macrostructures. These materials have applications in multiple industries such as textiles, biomedical devices, tissue engineering, and aerospace. This review article examines recent developments in porous SMPs, with a focus on fabrication methods, methods of characterization, modes of actuation, and applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 1300–1318

The rapid synthesis of an optically-transparent, flexible elastomer was performed utilizing the naturally-derived source, isosorbide. A novel monomer based on isosorbide (isosorbide dialloc, IDA) was prepared by installing carbonate functionalities along with external olefins for use in thiol–ene click chemistry. Cross-linked networks were created using the commercially-available cross-linker, trimethylolpropane tris(3-mercaptopropionate) (TMPTMP) and resulted in IDA-co-TMPTMP, an optically-transparent elastomer. Systematically, IDA-co-TMPTMP networks were synthesized using a photoinitiator, a UV cure time of one minute and varied post cure times (0–24 h, 125 mm Hg) at 100 °C to observe effects on mechanical, thermal and surface alterations. The mechanical properties also had limited changes with post cure time, including a modulus at 25 °C of 1.9–2.8 MPa and an elongation of 220–344%. The thermal decomposition temperatures of the networks were consistent, ca. 320 °C, while the glass transition temperature remained below room temperature for all samples. A cell viability assay and fluorescence imaging with adherent cells are also reported in this study to show the potential of the material as a biomedical substrate. A degradation study for 60 days resulted in 8.3 ± 3.5% and 97.7 ± 0.3% mass remaining under accelerated (1 M NaOH, 60 °C) and biological conditions (pH 7.4 PBS at 37 °C), respectively. This quickly-synthesized material has the potential to hydrolytically degrade into biologically-benign and environmentally-friendly by-products and may be utilized in renewable plastics and/or bioelastomer applications.

Shape memory polymer (SMP) foams were synthesized with three different nanoparticles (tungsten, silicon dioxide, and aluminum oxide) for embolization of cerebral aneurysms. Ultra-low density SMP foams have previously been utilized for aneurysm occlusion, resulting in a rapid, stable thrombus. However, the small cross section of foam struts can potentially lead to fracture and particulate generation, which would be a serious adverse event for an embolic device. The goal of this study was to improve the mechanical properties of the system by physically incorporating fillers into the SMP matrix. Thermal and mechanical characterization suggested minimal changes in thermal transition of the SMP nanocomposites and improved mechanical strength and toughness for systems with low filler content. Actuation profiles of the three polymer systems were tuned with filler type and content, resulting in faster SMP foam actuation for nanocomposites containing higher filler content. Additionally, thermal stability of the SMP nanocomposites improved with increasing filler concentration, and particulate count remained well below accepted standard limits for all systems. Extraction studies demonstrated little release of silicon dioxide and aluminum oxide from the bulk over 16 days. Tungstun release increased over the 16 day examination period, with a maximum measured concentration of approxiately 2.87 μg/mL. The SMP nanocomposites developed through this research have the potential for use in medical devices due to their tailorable mechanical properties, thermal resisitivity, and actuation profiles.

Shape memory polymer (SMP) foams have been developed for use in neurovascular occlusion applications. These materials are predominantly polyurethanes that are known for their biocompatibility and tunable properties. However, these polymers inherently lack X-ray visibility, which is a significant challenge for their use as implantable materials. Herein, low density, highly porous shape memory polyurethane foams were developed with tungsten nanoparticles dispersed into the foam matrix, at increasing concentrations, to serve as a radiopaque agent. Utilizing X-ray fluoroscopy sufficient visibility of the foams at small geometries was observed. Thermal characterization of the foams indicated altered thermal response and delayed foam actuation with increasing nanoparticle loading (because of restricted network mobility). Mechanical testing indicated decreased toughness and strength for higher loading because of disruption of the SMP matrix. Overall, filler addition imparted x-ray visibility to the SMP foams and allowed for tuned control of the transition temperature and actuation kinetics for the material. Copyright © 2015 John Wiley & Sons, Ltd.

Current endovascular therapies for intracranial saccular aneurysms result in high recurrence rates due to poor tissue healing, coil compaction, and aneurysm growth. We propose treatment of saccular aneurysms using shape memory polymer (SMP) foam to improve clinical outcomes. SMP foam-over-wire (FOW) embolization devices were delivered to in vitro and in vivo porcine saccular aneurysm models to evaluate device efficacy, aneurysm occlusion, and acute clotting. FOW devices demonstrated effective delivery and stable implantation in vitro. In vivo porcine aneurysms were successfully occluded using FOW devices with theoretical volume occlusion values greater than 72% and rapid, stable thrombus formation. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 1407-1415, 2016.

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.

Polyurethane shape memory polymers (SMPs) with tunable thermomechanical properties and advanced processing capabilities are synthesized, characterized, and implemented in the design of a microactuator medical device prototype. The ability to manipulate glass transition temperature (Tg ) and crosslink density in low-molecular weight aliphatic thermoplastic polyurethane SMPs is demonstrated using a synthetic approach that employs UV catalyzed thiol-ene "click" reactions to achieve postpolymerization crosslinking. Polyurethanes containing varying C=C functionalization are synthesized, solution blended with polythiol crosslinking agents and photoinitiator and subjected to UV irradiation, and the effects of number of synthetic parameters on crosslink density are reported. Thermomechanical properties are highly tunable, including glass transitions tailorable between 30 and 105 °C and rubbery moduli tailorable between 0.4 and 20 MPa. This new SMP system exhibits high toughness for many formulations, especially in the case of low crosslink density materials, for which toughness exceeds 90 MJ m(-3) at select straining temperatures. To demonstrate the advanced processing capability and synthetic versatility of this new SMP system, a laser-actuated SMP microgripper device for minimally invasive delivery of endovascular devices is fabricated, shown to exhibit an average gripping force of 1.43 ± 0.37 N and successfully deployed in an in vitro experimental setup under simulated physiological conditions.

Cardiovascular implantable devices alter the biofluid dynamics and biochemistry of the blood in which they are placed. These perturbations can lead to thrombus formation which may or may not be desired, depending on the application. In this work, a computational model is developed that couples biofluid dynamics and biochemistry to predict the clotting response of blood to such devices. The model consists of 28 advection–diffusion–reaction partial differential equations to track proteins in the blood involved in clotting and utilizes boundary flux terms to model the initiation of the intrinsic clotting pathway at thrombogenic device surfaces. We use this model to simulate the transient clot growth within a 2D idealized bifurcation aneurysm filled with various distributions of bare metal coils with similar packing densities. The clot model predicts initial clot formation to occur in areas along coil surfaces where flow is minimal and where time-averaged shear rates are the smallest. Among the six coil-filled aneurysm cases simulated, maximum thrombus occlusion ranged between 80.8 and 92.2% of the post-treatment aneurysm volume and was achieved 325–450 s after treatment. With further refinement and validation, the computational clotting model will be a valuable engineering tool for evaluating and comparing the relative performance of cardiovascular implantable devices.

The synthesis of thermoset shape memory polymer (SMP) polyurethanes from symmetric, aliphatic alcohols and diisocyanates has previously demonstrated excellent biocompatibility in short term in vitro and in vivo studies, although long term stability has not been investigated. Here we demonstrate that while rapid oxidation occurs in these thermoset SMPs, facilitated by the incorporation of multi-functional, branching amino groups, byproduct analysis does not indicate toxicological concern for these materials. Through complex multi-step chemical reactions, chain scission begins from the amines in the monomeric repeat units, and results, ultimately, in the formation of carboxylic acids, secondary and primary amines; the degradation rate and product concentrations were confirmed using liquid chromatography mass spectrometry, in model compound studies, yielding a previously unexamined degradation mechanism for these biomaterials. The rate of degradation is dependent on the hydrogen peroxide concentration, and comparison of explanted samples reveals a much slower rate in vivo compared to the widely accepted literature in vitro real-time equivalent of 3% HThis paper presents an in-depth analysis on the degradation of porous, shape memory polyurethanes (SMPs), including traditional surface characterization as well as model degradation compounds with absolute quantification. This combination of techniques allows for determination of rates of degradation as well as accumulation of individual degradation products. These behaviors are used for in vivo-in vitro comparisons for determination of real time degradation rates. Previous studies have primarily been limited to surface characterization without examination of degradation products and accumulation rates. To our knowledge, our work presents a unique example where a range of material scales (atomistic-scale model compounds along with macroscopic porous SMPs) are used in conjunction with ex planted samples for calculation of degradation rates and toxicological risk.

An estimated 6 million people in the United States have an unruptured cerebral aneurysm [1]. If left untreated, these aneurysms can rupture and to lead to severe brain function impairment or even death. Shape memory polymer (SMP) foams have been proposed for use to optimize endovascular embolization in place of current embolization devices [2,3]. SMPs are capable of actuating from a programmed secondary geometry to their expanded primary geometry in response to a stimulus, such as body temperature [4]. The expanded foam geometry provides an interface for embolization of the aneurysm to occur, however, treatment with these devices has limited visibility under fluoroscopy. Previous work by Hasan et al. increased radiopacity through the incorporation of tungsten (W) nanoparticles. These composite foams showed successful x-ray visibility, but aggregate disruption of the SMP matrix led to decreased mechanical properties [5]. This work addresses limitations of composite SMP foams, namely toughness, by chemically incorporating x-ray visible monomers, such as the triodobenzene containing monomer, 5-Amino-2,4,6-triiodoisophthalic acid (AT), into the material composition. These materials enable contrast agent loading without disrupting the polymer matrix. This polymer foam system was characterized to determine the clinical relevance of the improved radiopaque SMP foam for occlusion devices.

Predominantly closed-cell low density shape memory polymer (SMP) foam was recently reported to be an effective aneurysm filling device in a porcine model (Rodriguez et al., Journal of Biomedical Materials Research Part A 2013: (http://dx.doi.org/10.1002/jbm.a.34782)). Because healing involves blood clotting and cell migration throughout the foam volume, a more open-cell structure may further enhance the healing response. This research sought to develop a non-destructive reticulation process for this SMP foam to disrupt the membranes between pore cells. Non-destructive mechanical reticulation was achieved using a gravity-driven floating nitinol pin array coupled with vibratory agitation of the foam and supplemental chemical etching. Reticulation resulted in a reduced elastic modulus and increased permeability, but did not impede the shape memory behavior. Reticulated foams were capable of achieving rapid vascular occlusion in an in vivo porcine model.

Previously developed shape-memory polymer foams display fast actuation in water due to plasticization of the polymer network. The actuation presents itself as a depression in the glass-transition temperature when moving from dry to aqueous conditions; this effect limits the working time of the foam to 10 min when used in a transcatheter embolic device. Reproducible foams are developed by altering the chemical backbone, which can achieve working times of greater than 20 min. This is accomplished by incorporating isophorone diisocyanate into the foam, resulting in increased hydrophobicity, glass transitions, and actuation time. This delayed actuation, when compared with previous systems, allows for more optimal working time in clinical applications.

The rupture of an intracranial aneurysm, which can result in severe mental disabilities or death, affects approximately 30,000 people in the United States annually. The traditional surgical method of treating these arterial malformations involves a full craniotomy procedure, wherein a clip is placed around the aneurysm neck. In recent decades, research and device development have focused on new endovascular treatment methods to occlude the aneurysm void space. These methods, some of which are currently in clinical use, utilize metal, polymeric, or hybrid devices delivered via catheter to the aneurysm site. In this review, we present several such devices, including those that have been approved for clinical use, and some that are currently in development. We present several design requirements for a successful aneurysm filling device and discuss the success or failure of current and past technologies. We also present novel polymeric-based aneurysm filling methods that are currently being tested in animal models that could result in superior healing.

Injury caused by trauma, burns, surgery, or disease often results in soft tissue loss leading to impaired function and permanent disfiguration. Tissue engineering aims to overcome the lack of viable donor tissue by fabricating synthetic scaffolds with the requisite properties and bioactive cues to regenerate these tissues. Biomaterial scaffolds designed to match soft tissue modulus and strength should also retain the elastomeric and fatigue-resistant properties of the tissue. Of particular design importance is the interconnected porous structure of the scaffold needed to support tissue growth by facilitating mass transport. Adequate mass transport is especially true for newly implanted scaffolds that lack vasculature to provide nutrient flux. Common scaffold fabrication strategies often utilize toxic solvents and high temperatures or pressures to achieve the desired porosity. In this study, a polymerized medium internal phase emulsion (polyMIPE) is used to generate an injectable graft that cures to a porous foam at body temperature without toxic solvents. These poly(ester urethane urea) scaffolds possess elastomeric properties with tunable compressive moduli (20-200 kPa) and strengths (4-60 kPa) as well as high recovery after the first conditioning cycle (97-99%). The resultant pore architecture was highly interconnected with large voids (0.5-2 mm) from carbon dioxide generation surrounded by water-templated pores (50-300 μm). The ability to modulate both scaffold pore architecture and mechanical properties by altering emulsion chemistry was demonstrated. Permeability and form factor were experimentally measured to determine the effects of polyMIPE composition on pore interconnectivity. Finally, initial human mesenchymal stem cell (hMSC) cytocompatibility testing supported the use of these candidate scaffolds in regenerative applications. Overall, these injectable polyMIPE foams show strong promise as a biomaterial scaffold for soft tissue repair.

Neural interfaces provide an electrical connection between computers and the nervous system: current penetrating devices are orders-of-magnitude stiffer than surrounding tissue. In this work, recent efforts in softening electronics and utilize thiol-ene and thiol-epoxy “click” reactions are built upon to incorporate fluid-sensitive hydrogen bonding into smart substrates for high electrode density neural interfaces. The modulus of these substrates drops more than two orders of magnitude in response to physiological conditions, despite fluid uptake of less than 6%, and can be tuned by the covalent crosslink density and degree of hydrogen bonding in the polymer network. Intracortical and intrafascicular electrode arrays are fabricated and characterized with impedance spectroscopy and cyclic voltammetry.

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 (

Highly porous, open-celled shape memory polymer (SMP) foams are being developed for a number of vascular occlusion devices. Applications include abdominal aortic and neurovascular aneurysm or peripheral vascular occlusion. A major concern with implanting these high surface area materials in the vasculature is the potential to generate unacceptable particulate burden, in terms of number, size, and composition. This study demonstrates that particulate numbers and sizes in SMP foams are in compliance with limits stated by the most relevant standard and guidance documents. Particulates were quantified in SMP foams as made, postreticulation, and after incorporating nanoparticles intended to increase material toughness and improve radiopacity. When concentrated particulate treatments were administered to fibroblasts, they exhibited high cell viability (100%). These results demonstrate that the SMP foams do not induce an unacceptable level of risk to potential vascular occlusion devices due to particulate generation.

Currently, monitoring of minimally invasive medical devices is performed using fluoroscopy. The risks associated with fluoroscopy, including increased risk of cancer, make this method especially unsuitable for pediatric device delivery and follow-up procedures. A more suitable method is magnetic resonance (MR) imaging, which makes use of harmless magnetic fields rather than ionizing radiation when imaging the patient; this method is safer for both the patient and the performing technicians. Unfortunately, there is a lack of research available on bulk polymeric materials to enhance MR-visibility for use in medical devices. Here we show the incorporation of both physical and chemical modifying agents for the enhancement of both MR and X-ray visibility. Through the incorporation of these additives, we are able to control shape recovery of the polymer without sacrificing the thermal transition temperatures or the mechanical properties. For long-term implantation, these MR-visible materials do not have altered degradation profiles, and the release of additives is well below significant thresholds for daily dosages of MR-visible compounds. We anticipate our materials to be a starting point for safer, MR-visible medical devices incorporating polymeric components. Statement of Significance Shape memory polymers (SMPs) are polymeric materials with unique shape recovery abilities that are being considered for use in biomedical and medical device applications. This paper presents a methodology for the development of MR and X-ray visible SMPs using either a chemically loaded or physical loaded method during polymer synthesis. Such knowledge is imperative for the development and clinical application of SMPs for biomedical devices, specifically for minimally-invasive vascular occlusion treatments, and while there are studies pertaining to the visibility of polymeric particles, little work has been performed on the utility of biomaterials intended for medical devices and the impact of how adding multiple functionalities, such as imaging, may impact material safety and degradation.

Uncontrolled hemorrhage accounts for more than 30% of trauma deaths worldwide. Current hemostatic devices focus primarily on time to hemostasis, but prevention of bacterial infection is also critical for improving survival rates. In this study, we sought to improve on current devices used for hemorrhage control by combining the large volume-filling capabilities and rapid clotting of shape memory polymer (SMP) foams with the swelling capacity of hydrogels. In addition, a hydrogel composition was selected that readily complexes with elemental iodine to impart bactericidal properties to the device. The focus of this work was to verify that the advantages of each respective material (SMP foam and hydrogel) are retained when combined in a composite device. The iodine-doped hydrogel demonstrated an 80% reduction in bacteria viability when cultured with a high bioburden of Staphylococcus aureus. Hydrogel coating of the SMP foam increased fluid uptake by 19× over the uncoated SMP foam. The composite device retained the shape memory behavior of the foam with more than 15× volume expansion after being submerged in 37 °C water for 15 min. Finally, the expansion force of the composite was tested to assess potential tissue damage within the wound during device expansion. Expansion forces did not exceed 0.6 N, making tissue damage during device expansion unlikely, even when the expanded device diameter is substantially larger than the target wound site. Overall, the enhanced fluid uptake and bactericidal properties of the shape memory foam composite indicate its strong potential as a hemostatic agent to treat non-compressible wounds. Statement of Significance No hemostatic device currently used in civilian and combat trauma situations satisfies all the desired criteria for an optimal hemostatic wound dressing. The research presented here sought to improve on current devices by combining the large volume-filling capabilities and rapid clotting of shape memory polymer (SMP) foams with the swelling capacity of hydrogels. In addition, a hydrogel composition was selected that readily complexes with elemental iodine to impart bactericidal properties to the device. The focus of this work was to verify that the advantages of each respective material are retained when combined into a composite device. This research opens the door to generating novel composites with a focus on both hemostasis, as well as wound healing and microbial prevention.

Polyurethane shape memory polymer (SMP) foams have been developed for various embolic medical devices due to their unique properties in minimally invasive biomedical applications. These polyurethane materials can be stored in a secondary shape, from which they can recover their primary shape after exposure to an external stimulus, such as heat and water exposure. Tailored actuation temperatures of SMPs provide benefits for minimally invasive biomedical applications, but incur significant challenges for SMP-based medical device sterilization. Most sterilization methods require high temperatures or high humidity to effectively reduce the bioburden of the device, but the environment must be tightly controlled after device fabrication. Here, two probable sterilization methods (nontraditional ethylene oxide (ntEtO) gas sterilization and electron beam irradiation) are investigated for SMP medical devices. Thermal characterization of the sterilized foams indicated that ntEtO gas sterilization significantly decreased the glass transition temperature. Further material characterization was undertaken on the electron beam (ebeam) sterilized samples, which indicated minimal changes to the thermomechanical integrity of the bulk foam and to the device functionality.

Shape memory polymer foams have been previously investigated for their safety and efficacy in treating a porcine aneurysm model. Their biocompatibility, rapid thrombus formation, and ability for endovascular catheter-based delivery to a variety of vascular beds makes these foams ideal candidates for use in numerous embolic applications, particularly within the peripheral vasculature. This study sought to investigate the material properties, safety, and efficacy of a shape memory polymer peripheral embolization device in vitro. The material characteristics of the device were analyzed to show tunability of the glass transition temperature (Tg) and the expansion rate of the polymer to ensure adequate time to deliver the device through a catheter prior to excessive foam expansion. Mechanical analysis and flow migration studies were performed to ensure minimal risk of vessel perforation and undesired thromboembolism upon device deployment. The efficacy of the device was verified by performing blood flow studies that established affinity for thrombus formation and blood penetration throughout the foam and by delivery of the device in an ultrasound phantom that demonstrated flow stagnation and diversion of flow to collateral pathways.

Polyurethane shape memory polymer (SMP) foams are proposed for use as thrombogenic scaffolds to improve the treatment of vascular defects, such as cerebral aneurysms. However, gas blown SMP foams inherently have membranes between pores, which can limit their performance as embolic tissue scaffolds. Reticulation, or the removal of membranes between adjacent foam pores, is advantageous for improving device performance by increasing blood permeability and cellular infiltration. This work characterizes the effects of cold gas plasma reticulation processes on bulk polyurethane SMP films and foams. Plasma-induced changes on material properties are characterized using scanning electron microscopy, uniaxial tensile testing, goniometry, and free strain recovery experiments. Device specific performance is characterized in terms of permeability, platelet attachment, and cell–material interactions. Overall, plasma reticulated SMP scaffolds show promise as embolic tissue scaffolds due to increased bulk permeability, retained thrombogenicity, and favorable cell–material interactions.

Planar electronics processing methods have enabled neural interfaces to become more precise and deliver more information. However, this processing paradigm is inherently 2D and rigid. The resulting mechanical and geometrical mismatch at the biotic–abiotic interface can elicit an immune response that prevents effective stimulation. In this work, a thiol–ene/acrylate shape memory polymer is utilized to create 3D softening substrates for stimulation electrodes. This substrate system is shown to soften in vivo from more than 600 to 6 MPa. A nerve cuff electrode that coils around the vagus nerve in a rat and that drives neural activity is demonstrated.

SMPs have been shown to actuate below their dry glass transition temperatures in the presence of moisture due to plasticization. This behavior has been proposed as a self-actuating mechanism of SMPs in water/physiological media. However, control over the SMP actuation rate, a critical factor for in vivo transcatheter device delivery applications, has not been previously reported. Here, a series of polyurethane SMPs with systematically varied hydrophobicity is described that permits control of the time for their complete shape recovery in water from under 2 min to more than 24 h. This control over the SMP actuation rate can potentially provide significant improvement in their delivery under conditions, which may expose them to high-moisture environments prior to actuation.

To investigate whether or not a successful aneurysm treatment procedure can subject a parent artery to harmful hemodynamic stresses, computational fluid dynamics simulations are performed on a patient-specific basilar aneurysm and bifurcation before and after a virtual endovascular treatment. Prior to treatment, the aneurysm at systole is filled with a periodic train of vortex tubes, which form at the aneurysm neck and advect upwards into the dome. Following the treatment procedure however, the motion of the vortex train is inhibited by the aneurysm filling material, which confines the vortex tubes to the region beneath the aneurysm neck. Analysis of the post-treatment flow field indicates that the impingement of the basilar artery flow upon the treated aneurysm neck and the close proximity of a vortex tube to the parent artery wall increase the maximum wall shear stresses to values approximately equal to 50 Pa at systole. Calculation of the time-averaged wall shear stresses indicates that there is a 1.4 x 10(-7) m(2) area on the parent artery exposed to wall shear stresses greater than 37.9 Pa, a value shown by Fry [Circ. Res. 22(2):165-197, 1968] to cause severe damage to the endothelial cells that line the artery wall. The results of this study demonstrate that it is possible for a treatment procedure, which successfully isolates the aneurysm from the circulation and leaves no aneurysm neck remnant, to elevate the hemodynamic stresses to levels that are injurious to the artery wall.

Polyurethane shape memory polymers (SMPs) have found a variety of uses in the medical industry in the form of self-tightening sutures, suture anchors, ligament fixation devices, vascular stents, and thrombectomy devices. New formulations of polyurethane SMP scaffolds are gaining significant interest for use in vascular embolization procedures. These scaffolds have demonstrated rapid time to occlusion, improved healing, and favorable biocompatibility, and they eliminate the need to implant multiple devices to achieve stable occlusion, significantly reducing procedure times and the total cost of treatment. Described here are various methods used to fabricate SMP scaffolds, indications for SMP scaffold embolization, advantages of using these scaffolds in embolization procedures, results seen in animal studies that made use of SMP scaffolds, and future directions for SMP scaffolds that will propel the technology to significant use beyond vessel occlusion.

Aliphatic urethane polymers have been synthesized and characterized, using monomers with high molecular symmetry, in order to form amorphous networks with very uniform supermolecular structures which can be used as photo-thermally actuable shape memory polymers (SMPs). The monomers used include hexamethylene diisocyanate (HDI), trimethylhexamethylenediamine (TMHDI), N,N,N{prime},N{prime}-tetrakis(hydroxypropyl)ethylenediamine (HPED), triethanolamine (TEA), and 1,3-butanediol (BD). The new polymers were characterized by solvent extraction, NMR, XPS, UV/VIS, DSC, DMTA, and tensile testing. The resulting polymers were found to be single phase amorphous networks with very high gel fraction, excellent optical clarity, and extremely sharp single glass transitions in the range of 34 to 153 C. Thermomechanical testing of these materials confirms their excellent shape memory behavior, high recovery force, and low mechanical hysteresis (especially on multiple cycles), effectively behaving as ideal elastomers above T{sub g}. We believe these materials represent a new and potentially important class of SMPs, and should be especially useful in applications such as biomedical microdevices.

Shape memory polymer (SMP) containing medical implants that are delivered through catheters require controlled expansion times to prevent the device from binding in the delivery catheter. Delayed expansion can be accomplished using body temperature and moisture plasticization from the aqueous environment of the blood. Although bulk material approaches are effective at delaying the expansion rate, they often compromise the ultimate expansion volume, or necessitate temperatures above body temperature for actuation. These factors motivate material refinement beyond bulk chemistry changes to achieve nonlinear passive actuation profiles. In this work, plasma deposited hydrocarbon diffusion barriers enable a second degree of material expansion control, facilitating extended catheter delivery times for endovascular medical devices. Hydrocarbon plasma films polymerized from mixtures of acetylene, ethylene and propylene were deposited on silicon wafers and characterized using ellipsometry, static water contact angles, and x-ray photoelectron spectroscopy. Selected plasma processes were applied to polyurethane SMP foams and material performance was characterized using differential scanning calorimetry and unconstrained foam expansion in 37 °C water. These plasma films were found to increase surface hydrophobicity and delay the moisture plasticization rate of shape memory polymer embolic foams without altering bulk thermo-mechanical properties.