The synthesis of
novel carbohydrate-based polymers allows the structure
to be tailored at the monomer level for a specific property and expands
the range of available structures beyond those found in nature. Using
a controlled anionic polymerization, a new type of carbohydrate polymer
is synthesized in which glucose-derived monomers are joined by an
α-1,2 amide linkage to give enantiopure poly-amido-saccharides
(PASs). To investigate the effect of adding ionizable carboxylic acid
groups, such as those found in natural polysaccharides containing
glucuronic acid, the oxidation of the primary alcohol at the C6-position of the repeat unit to a carboxylic acid is reported.
TEMPO-mediated oxidation provides control over the degree of oxidation
in excellent yield. Based on circular dichroism, the oxidized polymers
possess an ordered helical secondary structure in aqueous solution.
Finally, oxidized PASs stabilize lysozyme toward dehydration and freezing
stresses better than a current, widely used protein stabilizing agent,
trehalose.
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