Polycarbonates are a class of degradable polymers used in biomedical applications including vehicles for drug-delivery and sca olds for tissue engineering. They can be classi ed into two groups i.e. aliphatic and aromatic polycarbonates, each with distinctive mechanical properties and degradation mechanisms. Aliphatic polycarbonates are soft and flexible materials most suitable for cartilage or blood vessel repair. Aromatic polycarbonates are strong and stiff , useful for hard tissue applications such as bone regeneration. While aliphatic polycarbonates may undergo a surface erosion process mediated by biological activity, aromatic polycarbonates as for example tyrosine-derived compositions undergo hydrolytic degradation and slow mass erosion. In this thesis, aromatic-aliphatic polycarbonates from natural (hydroxyalkyl)phenols such as tyrosol were explored with the rationale of combining the advantages of both classes of polycarbonates. Copolymers of tyrosol and homovanillyl alcohol had high tensile strength, and showed enzymatic surface erosion by lipase, in vitro. During erosion, mechanical properties were retained for at least 18 weeks: The wet modulus of E = 0.9 +/- 0.1GPa was retained at 65% (w/w) mass loss (rate = 0.14 +/- 0.01 mgcm−2 d−1). The aromatic-aliphatic polycarbonates from (hydroxyalkyl)phenols showed sequence isomerism of diaryl, dialkyl, and aryl alkyl carbonate bonds. In order to control the carbonate isomer sequence, a selective synthesis methodology for diaryl and dialkyl carbonate diols as pre-programmed monomers was developed. An alternating sequence (alt) of diaryl and dialkyl carbonates demonstrated dramatic changes of the phase behavior and erosion as compared to the scrambled sequence (scr): A faster erosion rate of 0.36+/-0.01 mgcm−2d−1 for amorphous alt was observed. When heated, alt readily attained a 3-dimensional crystalline order, whereas scr showed sluggish transition into a 1-dimensional mesophase. Oriented and annealed lms of alt had improved sti ness with E = 5.4 +/- 0.3GPa as compared to scr and poly(l-lactic acid) with E = 3.8+/- 0.2 GPa and E = 3.8 +/- 0.3 GPa, respectively. The in vivo subcutaneous implantation of polymer discs resulted in slow mass loss after 3 months. However, the surface morphology appeared strikingly similar to in vitro samples. Further investigation into implant location and specimen dimensions may help to identify conditions for the in vivo resorbability.
Subject (authority = RUETD)
Topic
Chemistry and Chemical Biology
Subject (authority = ETD-LCSH)
Topic
Polycarbonates
Subject (authority = ETD-LCSH)
Topic
Polymers in medicine--Mechanical properties
RelatedItem (type = host)
TitleInfo
Title
Rutgers University Electronic Theses and Dissertations
Identifier (type = RULIB)
ETD
Identifier
ETD_6008
PhysicalDescription
Form (authority = gmd)
electronic resource
InternetMediaType
application/pdf
InternetMediaType
text/xml
Extent
1 online resource (xxi, 163 p. : ill.)
Note (type = degree)
Ph.D.
Note (type = bibliography)
Includes bibliographical references
Note (type = statement of responsibility)
by Sven Daniel Sommerfeld
RelatedItem (type = host)
TitleInfo
Title
Graduate School - New Brunswick Electronic Theses and Dissertations
Identifier (type = local)
rucore19991600001
Location
PhysicalLocation (authority = marcorg); (displayLabel = Rutgers, The State University of New Jersey)
Rutgers University. Graduate School - New Brunswick
AssociatedObject
Type
License
Name
Author Agreement License
Detail
I hereby grant to the Rutgers University Libraries and to my school the non-exclusive right to archive, reproduce and distribute my thesis or dissertation, in whole or in part, and/or my abstract, in whole or in part, in and from an electronic format, subject to the release date subsequently stipulated in this submittal form and approved by my school. I represent and stipulate that the thesis or dissertation and its abstract are my original work, that they do not infringe or violate any rights of others, and that I make these grants as the sole owner of the rights to my thesis or dissertation and its abstract. I represent that I have obtained written permissions, when necessary, from the owner(s) of each third party copyrighted matter to be included in my thesis or dissertation and will supply copies of such upon request by my school. I acknowledge that RU ETD and my school will not distribute my thesis or dissertation or its abstract if, in their reasonable judgment, they believe all such rights have not been secured. I acknowledge that I retain ownership rights to the copyright of my work. I also retain the right to use all or part of this thesis or dissertation in future works, such as articles or books.