Search

As new ultra-soft materials are being developed for medical devices and biomedical applications, the comprehensive characterization of their physical and mechanical properties is both critical and challenging. To characterize the very low surface modulus of the novel biomimetic lehfilcon A silicone hydrogel contact lens coated with a layer of a branched polymer brush structure, an improved atomic force microscopy (AFM) nanoindentation method has been applied. This technique allows for precise contact-point determination without the effects of viscous squeeze-out upon approaching the branched polymer. Additionally, it allows individual brush elements to be mechanically characterized in the absence of poroelastic effects. This was accomplished by selecting an AFM probe with a design (tip size, geometry, and spring constant) that was especially suited to measuring the properties of soft materials and biological samples. The enhanced sensitivity and accuracy of this method allows for the precise measurement of the very soft lehfilcon A material, which has an extremely low elastic modulus in the surface region (as low as 2 kPa) and extremely high elasticity (nearly 100%) in an aqueous environment. The surface-characterization results not only reveal the ultra-soft nature of the lehfilcon A lens surface but also demonstrate that the elastic modulus exhibits a 30 kPa/200 nm gradient with depth due to the disparity between the modulus of the branched polymer brushes and the SiHy substrate. This surface-characterization methodology may be applied to other ultra-soft materials and medical devices.

Materials taking advantage of the characteristics of biological tissues are strongly sought after in medical science and bioscience. On the natural corneal tissue surface, the highly soft and lubricated surface is maintained by composite structures composed of hydrophilic biomolecules and substrates. To mimic this structure, the surface of a silicone hydrogel contact lens was modified with a biomimetic phospholipid polymer, poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC), and the nanoscaled morphology and mechanical properties of the surface were confirmed with advanced surface characterization and imaging techniques under an aqueous medium. Concavities and convexities on the nanometer order were recognized on the surface. The surface was completely covered with a PMPC layer and remained intact even after 30 days of clinical use in a human ocular environment. The mechanical properties of the natural corneal tissue and the PMPC-modified surface were similar in the living environment, that is, low modulus and frictional properties comparable to natural tissues. These results show the validity of material preparation by biomimetic methods. The methodologies developed in this study may contribute to future development of human-friendly medical devices.

A silicone hydrogel contact lens material, with a unique chemical and physical structure has been designed for long-term ocular performance. Enhancement of this silicone hydrogel contact lens material was achieved through surface modification using a cross-linkable bioinspired 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer, which creates a soft surface gel layer on the silicone hydrogel base material. The surface properties of this MPC polymer-modified lens were characterized under hydrated condition revealing, inter alia, its unique polymer structure, excellent hydrophilicity, lubricity, and flexibility. Analysis of the MPC polymer layer in a hydrated state was performed using a combination of a high-resolution environmental scanning electron microscopy and atomic force microscopy. Compared to the silicone hydrogel base material, this surface had a higher captive bubble contact angle, which corresponds to higher hydrophilicity of the surface. In addition, the hydrated MPC polymer layer exhibited an extremely soft surface and reduced the coefficient of friction by more than 80 %. These characteristics were attributed to the hydration state of the MPC polymer layer on the surface of the silicone hydrogel base material. Also, interaction force of protein deposition was lowered on the surface. Such superior surface properties are anticipated to contribute to excellent ocular performance.

Injectable nanocomposites made of biodegradable poly(propylene fumarate) and the crosslinking agent propylene fumarate-diacrylate as well as each of three forms of single-walled carbon nanotubes (SWNTs) were evaluated for their in vitro cytotoxicity. Unreacted components, crosslinked networks, and degradation products of the nanocomposites were investigated for their effects on cell viability using a fibroblast cell line in vitro. The results did not reveal any in vitro cytotoxicity for purified SWNTs, SWNTs functionalized with 4-tert-butylphenylene, and ultra-short SWNTs at 1- 100 microg/mL concentrations. Moreover, nearly 100% cell viability was observed on all crosslinked nanocomposites and cell attachment on their surfaces was comparable with that on tissue culture polystyrene. The degradation products of the nanocomposites displayed a dose-dependent adverse effect on cells, which was partially due to increased osmolarity by the conditions of accelerated degradation and could be overcome at diluted concentrations. These results demonstrate that all three tested nanocomposites have favorable cytocompatibility for potential use as scaffolds for bone tissue engineering applications.

We investigated the fabrication of highly porous scaffolds made of three different materials [poly(propylene fumarate) (PPF) polymer, an ultra-short single-walled carbon nanotube (US-tube) nanocomposite, and a dodecylated US-tube (F-US-tube) nanocomposite] in order to evaluate the effects of material composition and porosity on scaffold pore structure, mechanical properties, and marrow stromal cell culture. All scaffolds were produced by a thermal-crosslinking particulate-leaching technique at specific porogen contents of 75, 80, 85, and 90 vol%. Scanning electron microcopy, microcomputed tomography, and mercury intrusion porosimetry were used to analyze the pore structures of scaffolds. The porogen content was found to dictate the porosity of scaffolds. There was no significant difference in porosity, pore size, and interconnectivity among the different materials for the same porogen fraction. Nearly 100% of the pore volume was interconnected through 20microm or larger connections for all scaffolds. While interconnectivity through larger connections improved with higher porosity, compressive mechanical properties of scaffolds declined at the same time. However, the compressive modulus, offset yield strength, and compressive strength of F-US-tube nanocomposites were higher than or similar to the corresponding properties for the PPF polymer and US-tube nanocomposites for all the porosities examined. As for in vitro osteoconductivity, marrow stromal cells demonstrated equally good cell attachment and proliferation on all scaffolds made of different materials at each porosity. These results indicate that functionalized ultra-short single-walled carbon nanotube nanocomposite scaffolds with tunable porosity and mechanical properties hold great promise for bone tissue engineering applications.

This study investigates the effects of nanostructure size and surface area on the rheological properties of un-cross-linked poly(propylene fumarate) (PPF) nanocomposites and the mechanical properties of cross-linked nanocomposites as a function of the nanostructure loading. Three model carbon nanostructures were examined, C(60) fullerenes, ultra-short single-walled carbon nanotubes (US-tubes) and single-walled carbon nanotubes (SWNTs). Rheological measurements showed that C60 and US-tube un-cross-linked nanocomposites exhibited viscous-like characteristics with the complex viscosity independent of frequency for nanostructure concentrations up to 1 wt%. Compressive and flexural mechanical testing demonstrated significant mechanical reinforcement of US-tube and SWNT nanocomposites as compared to cross-linked polymer alone, with an up to twofold increase in the mechanical properties. Scanning electron microscopy examination of the fracture surface of cross-linked US-tube nanocomposite revealed lack of aggregation of US-tubes. Although sol fraction studies did not provide any evidence of additional cross-linking, due to the presence of US-tubes in the nanocomposites, transmission electron microscopy studies suggested the crystallization of PPF on the surface of US-tubes which can contribute to the mechanical reinforcement of the US-tube nanocomposites. These results demonstrate that the rheological properties of un-cross-linked nanocomposites depend mainly on the carbon nanostructure size, whereas the mechanical properties of the cross-linked nanocomposites are dependent on the carbon nanostructure surface area. The data also suggest that US-tube nanocomposites are suitable for further consideration as injectable scaffolds for bone tissue engineering applications.

Bone tissue engineering could provide an alternative to conventional treatments for fracture nonunion, spinal fusion, joint replacement, and pathological loss of bone. However, this approach will require a biocompatible matrix to allow progenitor cell delivery and support tissue invasion. The construct must also support physiological loads as it degrades to allow the regenerated tissue to bear an increasing load. To meet these complex requirements, we have employed topology-optimized design and solid free-form fabrication to manufacture biodegradable poly(propylene fumarate)/beta-tricalcium phosphate composites. These scaffolds were seeded with primary human fibroblasts transduced with an adenovirus expressing bone morphogenetic protein-7 and implanted subcutaneously in mice. Specimens were evaluated by microcomputed tomography, compressive testing, and histological staining. New bone was localized on the scaffold surface and closely followed its designed contours. Furthermore, the total stiffness of the constructs was retained for up to 12 weeks after implantation, as scaffold degradation and tissue invasion took place.

Contains fulltext : 69781.pdf (Publisher’s version ) (Closed access) Scaffolds play a pivotal role in the tissue engineering paradigm by providing temporary structural support, guiding cells to grow, assisting the transport of essential nutrients and waste products, and facilitating the formation of functional tissues and organs. Single-walled carbon nanotubes (SWNTs), especially ultra-short SWNTs (US-tubes), have proven useful for reinforcing synthetic polymeric scaffold materials. In this article, we report on the in vivo biocompatibility of US-tube reinforced porous biodegradable scaffolds in a rabbit model. US-tube nanocomposite scaffolds and control polymer scaffolds were implanted in rabbit femoral condyles and in subcutaneous pockets. The hard and soft tissue response was analyzed with micro-computed tomography (micro CT), histology, and histomorphometry at 4 and 12 weeks after implantation. The porous US-tube nanocomposite scaffolds exhibited favorable hard and soft tissue responses at both time points. At 12 weeks, a three-fold greater bone tissue ingrowth was seen in defects containing US-tube nanocomposite scaffolds compared to control polymer scaffolds. Additionally, the 12 week samples showed reduced inflammatory cell density and increased connective tissue organization. No significant quantitative difference in polymer degradation was observed among the various groups; qualitative differences between the two time points were consistent with expected degradation due to the progression of time. Although no conclusions can be drawn from the present study concerning the osteoinductivity of US-tube nanocomposite scaffolds, the results suggest that the presence of US-tubes may render nanocomposite scaffolds bioactive assisting osteogenesis.

We have investigated the dispersion of single-walled carbon nanotubes (SWNTs) and functionalized SWNTs (F-SWNTs) in the unsaturated, biodegradable polymer poly(propylene fumarate) (PPF) and examined the rheological properties of un-cross-linked nanocomposite formulations as well as the electrical and mechanical properties of cross-linked nanocomposites. F-SWNTs were produced from individual SWNTs by a diazonium-based method and dispersed better than unmodified SWNTs in both un-cross-linked and cross-linked PPF matrix. Cross-linked nanocomposites with F-SWNTs were superior to those with unmodified SWNTs in terms of their mechanical properties. Specifically, nanocomposites with 0.1 wt % F-SWNTs loading resulted in a 3-fold increase in both compressive modulus and flexural modulus and a 2-fold increase in both compressive offset yield strength and flexural strength when compared to pure PPF networks, whereas the use of 0.1 wt % SWNTs gained less than 37% mechanical reinforcement. These extraordinary mechanical enhancements considered together with Raman scattering and sol fraction measurements indicate strong SWNT-PPF interactions and increased cross-linking densities resulting in effective load transfer. With enhanced mechanical properties and capabilities of in situ injection and cross-linking, these SWNT/polymer nanocomposites hold significant implications for the fabrication of bone tissue engineering scaffolds.