Synthesis and characterization of a POSS-PEG macromonomer and POSS-PEG-PLA hydrogels for periodontal applications.

A novel water-soluble macromonomer based on octavinyl silsesquioxane has been synthesized and contains vinyl-terminated PEG 400 in each of the eight arms to promote water solubility. The macromonomer was characterized by NMR and FTIR and its aqueous solution properties examined. In water it exhibits an LCST with a cloud point at 23 °C for a 10 wt % aqueous solution. It is surface active with a CMC of 1.5 × 10(-5) M in water and in 20:80 v/v acetone/water the CMC is 7.1 × 10(-5) M, and TEM images showed spherical 22 nm aggregates in aqueous solution above the CMC. The macromonomer was copolymerized in a 20:80 v/v acetone/water mixture with a vinyl-terminated, triblock copolymer of lactide-PEG-lactide to form a library of cross-linked hydrogels that were designed for use as scaffolds for alveolar bone repair. The cross-linked copolymer networks were shown to contain a range of nm-µm sized pores and their swelling properties in water and PBS at pH 7.4 were examined. At pH 7.4 the hydrogel networks undergo a slow hydrolysis with the release of principally PEG and lactic acid fragments. The hydrogels were shown to be noncytotoxic toward fibroblast cultures at pH 7.4, both initially (days 1-5) and after significant hydrolysis had taken place (days 23-28).

Cross-linked poly(trimethylene carbonate-co-L-lactide) as a biodegradable, elastomeric scaffold for vascular engineering applications.

A series of copolymers of trimethylene carbonate (TMC) and L-lactide (LLA) were synthesized and evaluated as scaffolds for the production of artificial blood vessels. The polymers were end-functionalized with acrylate, cast into films, and cross-linked using UV light. The mechanical, degradation, and biocompatibility properties were evaluated. High TMC polymers showed mechanical properties comparable to human arteries (Young's moduli of 1.2-1.8 MPa and high elasticity with repeated cycling at 10% strain). Over 84 days degradation in PBS, the modulus and material strength decreased gradually. The polymers were nontoxic and showed good cell adhesion and proliferation over 7 days using human mesenchymal stem cells. When implanted into the rat peritoneal cavity, the polymers elicited formation of tissue capsules composed of myofibroblasts, resembling immature vascular smooth muscle cells. Thus, these polymers showed properties which were tunable and favorable for vascular tissue engineering, specifically, the growth of artificial blood vessels in vivo.

Synthesis and evaluation of partly fluorinated block copolymers as MRI imaging agents.

A series of well-defined diblock copolymers of acrylic acid with partially fluorinated acrylate and methacrylate monomers were synthesized using ATRP as potential 19F MRI imaging agents. The diblock copolymers could undergo spontaneous self-assembly in mixed and aqueous solvents to form stable micelles with a diameter from approximately 20-45 nm, having a fluorine-rich core that provides a strong signal for MRI examinations. The observed MRI image intensities were related to the NMR longitudinal and transverse relaxation times, and were found to depend on polymer structure and method of micellization. Two distinct T2 relaxation times were measured; on comparison of expected MRI image intensities with those observed experimentally, it was found that methacrylate polymers show systematically lower signal intensity than acrylate polymers. This is related to the presence of a population of nuclear spins having very short T2 relaxation times that cannot be detected under high-resolution NMR and MRI conditions.

Synthesis and characterization of POSS-(PAA)8 star copolymers and GICs for dental applications.

OBJECTIVE: To investigate the application of a new type of multiarm polymer resins in the formulation of Glass Ionic Cements. METHODS: A series of star copolymers of t-butyl acrylate has been prepared by ATRP using a multiarm POSS-Br8 initiator. The resulting POSS-co-t-butyl acrylate star copolymers with eight arms were subsequently hydrolysed by trifluoroacetic acid to produce the corresponding POSS-co-acrylic acid star copolymers. All of the copolymers have been characterized by (1)H and (13)C NMR and FTIR spectroscopies and TGA/DSC. The as-prepared star copolymers were mixed with the glass powder from Fuji IX GP to produce the GIC samples for compression testing. RESULTS: The new type of multiarm polymer resins have been shown to have narrow molecular weight distributions and thermal properties of the acrylic acid copolymers are similar to that of poly(acrylic acid), with a two stage degradation profile involving transitions at ≈140°C and 250°C, corresponding to anhydride formation and loss of carbon dioxide, respectively. In aqueous solution the POSS-co-acrylic acid copolymers form aggregates with ≈33nm dimensions. When aqueous solutions of POSS-(PAA)8 are mixed with a glass powder, a rigid glass ionomer cement, GIC, is formed with a maximum compressive stress significantly greater than that for a linear PAA GIC of a comparable polymer molecular weight. SIGNIFICANCE: Therefore, these POSS-(PAA)8 copolymers demonstrate the potential for the application of well characterized star copolymers in the future development of new GICs as dental materials.

Electrospinning and crosslinking of low-molecular-weight poly(trimethylene carbonate-co-(L)-lactide) as an elastomeric scaffold for vascular engineering.

The growth of suitable tissue to replace natural blood vessels requires a degradable scaffold material that is processable into porous structures with appropriate mechanical and cell growth properties. This study investigates the fabrication of degradable, crosslinkable prepolymers of l-lactide-co-trimethylene carbonate into porous scaffolds by electrospinning. After crosslinking by γ-radiation, dimensionally stable scaffolds were obtained with up to 56% trimethylene carbonate incorporation. The fibrous mats showed Young's moduli closely matching human arteries (0.4-0.8MPa). Repeated cyclic extension yielded negligible change in mechanical properties, demonstrating the potential for use under dynamic physiological conditions. The scaffolds remained elastic and resilient at 30% strain after 84days of degradation in phosphate buffer, while the modulus and ultimate stress and strain progressively decreased. The electrospun mats are mechanically superior to solid films of the same materials. In vitro, human mesenchymal stem cells adhered to and readily proliferated on the three-dimensional fiber network, demonstrating that these polymers may find use in growing artificial blood vessels in vivo.