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January 27, 2006

Protein-Polymer Conjugates in Solution and on Surfaces
Heather D. Maynard, Howard Reiss Career Development Chair
Department of Chemistry and Biochemistry & California NanoSystems Institute
University of California, Los Angeles

Proteins are naturally evolved to achieve high activity and specificity in signaling and
recognition. Conjugating polymer chains to proteins can be very beneficial in the context
of biomedicine, leading to enhanced materials functional in targeted drug delivery,
diagnostics, and as therapeutics. Resultant properties depend on the identity of the
polymer chain, the polymer molecular weight distribution, number of chains, and points
of attachment. We have developed general strategies to prepare protein-polymer
conjugates. For example, we have synthesized initiators for atom transfer radical
polymerization (ATRP) that also react with specific amino acid side chains and
demonstrated controlled polymerization to form semi-telechelic polymers. The resulting
polymers conjugate directly to proteins without the need for post-polymerization
modification of the chain ends. In another example, we use the protein as a
macroinitiator for polymerization, forming the polymer bioconjugate in situ. This and
other synthetic strategies to form protein-polymer conjugates in solution and on surfaces
will be discussed.
Relevant Papers:
(1) Bontempo, D.; Heredia, K. L.; Fish, B. A.; Maynard, H. D., “Cysteine-Reactive
Polymers Synthesized by Atom Transfer Radical Polymerization for Conjugation
to Proteins,” J. Am. Chem. Soc., 2004, 126, 15372-15373.
(2) Bontempo, D.; Maynard, H. D., “Streptavidin as a Macroinitiator for
Polymerization: In Situ Protein-Polymer Conjugate Formation,” J. Am. Chem.
Soc., 2005, 127, 6508-6509
(3) Christman, K. L.; Maynard, H. D., “Protein Micropatterns Using a pHResponsive
Polymer and Light,” Langmuir, 2005, 21, 8389-8393.
(4) Bontempo, D.; Li, R. C.; Ly, T.; Brubaker, C. E.; Maynard, H. D., “One-Step
Synthesis of Low Polydispersity, Biotinylated Poly(N-isopropylacrylamide) by
ATRP,” Chem. Commun., 2005, (37), 4702-4704.
(5) Heredia, K. L.; Bontempo, D.; Ly, T.; Byers, J. T.; Halstenberg, S.; Maynard, H.
D., “In-Situ Preparation of Protein-‘Smart’ Polymer Conjugates with Retention of
Bioactivity,” J. Am. Chem. Soc., 2005, 127, 16955-16960.