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comonomer is carried out to produce the maltooligosaccharide-
grafted polymer (iv), and then the phosphorylase-catalyzed
enzymatic polymerization of Glc-1-P from the resulting graft
copolymer is performed to yield the amylose-grafted polymer
(vi). As another synthetic route for macromonomer method, after
the phosphorylase-catalyzed enzymatic polymerization of Glc-
1-P from the maltooligosaccharide-containing monomer, which is
obtained by the aforementioned chemical reaction (ii), is conducted
to obtain the amylose-containing monomer (macromonomer) (v),
(co)polymerization of this macromonomer is performed to produce
the amylose-grafted polymer (vii). However, the synthetic route for
polymer reaction method is that polymerization of the monomer
is first performed (i), the maltooligosaccharide primer reacts with
the resulting polymer backbone to obtain the maltooligosaccharide-
grafted polymer (iii), and then the phosphorylase-catalyzed
enzymatic polymerization of Glc-1-P is carried out as described
earlier (vi). In the chemoenzymatic method, the length of amylose
graft chain can be controlled by changing the feed ratio of Glc-1-P
to the primer on the enzymatic polymerization (v and vi), whereas
the number of amylose graft chain can be controlled by changing the
feed ratio of the maltooligosaccharide-containing monomer to the
comonomer (iv), amylose-containing monomer to the comonomer
(vii), and the maltooligosaccharide to the unit number of the polymer
main chain (iii).
5.2
General Chemical Reactions to Link
Maltooligosaccharide to Polymer
Backbones or Polymerizable Groups
Representative three chemical reactions to link the
maltooligosaccharides to polymer backbones or polymerizable
groups are described in Fig. 5.2.
The reducing end of a maltooligosaccharide can be easily con-
verted to the corresponding aldonic acid by oxidation, which
spontaneously leads to an aldonolactone by dryness. The aldonol-
actone reacts with the amino group to obtain the corresponding
aldonamide without protection of hydroxy groups on the maltoo-
ligosaccharide (Fig. 5.2a) [8]. Use of amine-functionalized polymer
