Inorganic-organic hydrogels based on methacrylated star polydimethylsiloxane (PDMS(star)-MA) and diacrylated poly(ethylene glycol) (PEG-DA) macromers were prepared via solvent-induced phase separation (SIPS). The macromers were combined in a dichloromethane precursor solution and sequentially photopolymerized, dried and hydrated. The chemical and physical properties of the hydrogels were further tailored by varying the number average molecular weight (M(n)) of PEG-DA (M(n)=3.4k and 6k gmol(-1)) as well as the weight percent ratio of PDMS(star)-MA (M(n)=7k gmol(-1)) to PEG-DA from 0:100 to 20:80. Compared to analogous hydrogels fabricated from aqueous precursor solutions, SIPS produced hydrogels with a macroporous morphology, a more even distribution of PDMS(star)-MA, increased modulus and enhanced degradation rates. The morphology, swelling ratio, mechanical properties, bioactivity, non-specific protein adhesion, controlled introduction of cell adhesion, and cytocompatibility of the hydrogels were characterized. As a result of their tunable properties, this library of hydrogels is useful to study material-guided cell behavior and ultimate tissue regeneration.

Amphiphilic silicones were prepared by the covalent incorporation of branched polyethylene oxide (PEO) via a siloxane tether. This was achieved by using six novel branched PEO-silanes with varying siloxane tether lengths and PEO molecular weight (M n ). Each PEO-silane was crosslinked via acid-catalyzed sol-gel condensation with a,x-bis(Si-OH) polydimethylsiloxane (PDMS) (M n ¼ 3000 g/mol) to yield six amphiphilic silicone films. Film surface hydrophilicity increased with siloxane tether length, particularly after exposure to an aqueous environment, indicating that the PEO segments were more readily driven to the surface. This effect was more pronounced for films prepared with PEO-silanes containing lower M n PEO segments. AFM was used to study surface reconstruction of films upon exposure to an aqueous environment. Adsorption of bovine serum albumin (BSA) and human fibrinogen (HF) proteins decreased with siloxane tether length, particularly after first exposing films to an aqueous environment. For a given siloxane tether length, relatively less BSA adsorbed onto films prepared with PEO-silanes with lower M n PEO segments whereas less HF adsorbed onto films prepared with PEO-silanes with higher M n PEO segments. V C 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4108-4119, 2010

Poly(ethylene glycol) diacrylate (PEG-DA) hydrogels are widely utilized to probe cell-material interactions and ultimately for a material-guided approach to tissue regeneration. In this study, PEG-DA hydrogels were fabricated via solvent-induced phase separation (SIPS) to obtain hydrogels with a broader range of tunable physical properties including morphology (e.g. porosity), swelling and modulus (G′). In contrast to conventional PEG-DA hydrogels prepared from an aqueous precursor solution, the reported SIPS protocol utilized a dichloromethane (DCM) precursor solution which was sequentially photopolymerized, dried and hydrated. Physical properties were further tailored by varying the PEG-DA wt% concentration (5 wt%–25 wt%) and Mn (3.4k and 6k g mol −1). SIPS produced PEG-DA hydrogels with a macroporous morphology as well as increased G′ values versus the corresponding conventional PEG-DA hydrogels. Notably, since the total swelling was not significantly changed versus the corresponding conventional PEG-DA hydrogels, pairs or series of hydrogels represent scaffolds in which morphology and hydration or G′ and hydration are uncoupled. In addition, PEG-DA hydrogels prepared via SIPS exhibited enhanced degradation rates.

In tissue engineering, the physical and chemical properties of the scaffold mediates cell behavior including regeneration. Thus, a strategy that permits rapid screening of cell-scaffold interactions is critical. Herein, we have prepared eight “hybrid” hydrogel scaffolds in the form of continuous gradients such that a single scaffold contains spatially varied properties. These scaffolds are based on combining an inorganic macromer [methacrylated star polydimethylsiloxane, PDMSstar-MA] and organic macromer [poly(ethylene glycol)diacrylate, PEG-DA] as well both aqueous and organic fabrication solvents. Having previously demonstrated its bioactivity and osteoinductivity, PDMSstar-MA is a particularly powerful component to incorporate into instructive gradient scaffolds based on PEG-DA. The following parameters were varied to produce the different gradients or gradual transitions in: (1) the wt% ratio of PDMSstar-MA to PEG-DA macromers, (2) the total wt% macromer concentration, (3) the number average molecular weight (Mn) of PEG-DA and (4) the Mn of PDMSstar-MA. Upon dividing each scaffold into four “zones” perpendicular to the gradient, we were able to demonstrate the spatial variation in morphology, bioactivity, swelling and modulus. Among these gradient scaffolds are those in which swelling and modulus are conveniently decoupled. In addition to rapid screening of cell-material interactions, these scaffolds are well-suited for regeneration of interfacial tissues (e.g. osteochondral tissues) that transition from one tissue type to another.

The goal of the research described herein is the fabrication and assessment of electrically conductive partially-cured epoxy coatings which, upon cracking, autonomously restore barrier, mechanical and electrical properties via a microcapsule based healing mechanism. Upon cracking, microcapsules in the crack path release the 'healing' solvent ethyl phenyl acetate (EPA), which locally swells the matrix, promoting crack closure and enabling the diffusion and subsequent reaction of the residual hardener in the vicinity of the crack. Two different self-healing coatings and two controls based on an electrically conductive epoxy resin with approximately 20% carbon nanotubes (CNTs) were fabricated. Electrochemical impedance spectroscopy was employed to evaluate the potential of the CNT and non-CNT containing encapsulated systems to restore relatively large cracks and thus restore the barrier function. An in-situ electro-tensile test in a microscope revealed that electrical conductivity and mechanical properties were restored to 64% (± 23) and 81% (± 39) respectively, which correlated to crack closure. Under appropriate testing conditions the system showed successive damage-heal events in terms of electrical conductivity.