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Evaluating Relative Chain Orientation of Amylose and Poly( l ‐lactide) in Inclusion Complexes Formed by Vine‐Twining Polymerization Using Primer–Guest Conjugates
Author(s) -
Tanaka Tomonari,
Sasayama Shota,
Yamamoto Kazuya,
Kimura Yoshiharu,
Kadokawa Junichi
Publication year - 2015
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.201400603
Subject(s) - polymer chemistry , polymerization , chemistry , amylose , lactide , gel permeation chromatography , copolymer , polymer , organic chemistry , starch
The relative chain orientation of amylose and poly( l ‐lactide) (PLLA) in inclusion complexes formed by phosphorylase‐catalyzed enzymatic polymerization is made clear, by using primer–guest conjugates according to a vine‐twining polymerization manner. The conjugates, which have a maltoheptaosyl moiety at COOH‐ or OH‐terminus of poly( l ‐ and d ‐lactide)s, are synthesized by copper(I)‐catalyzed click chemistry using propargyl‐terminated polylactides (PLAs) and maltoheptaosyl azide. The cavity of amylose includes PLLA, regardless of the chain orientation, when the conjugates composed of PLLA are used on the vine‐twining polymerization. On the other hand, amylose–poly( d ‐lactide) (PDLA) diblock copolymers, which are noninclusion products, are produced when the conjugates composed of PDLA are used. X‐ray diffraction (XRD) patterns of products and gel permeation chromatography (GPC) analyses of their alkaline hydrolysates strongly support that the amylose‐PLLA inclusion supramolecular polymers are produced, probably owing to the same helical direction of amylose as that of PLLA, which is responsibly induced by its chirality, regardless of the chain orientation on complexation.