Evaluation of Stability of Amylose Inclusion Complexes Depending on Guest Polymers and Their Application to Supramolecular Polymeric Materials

Abstract

This paper describes the evaluation of the stability of amylose–polymer inclusion complexes under solution state in dimethyl sulfoxide (DMSO) depending on guest polymers. The three complexes were prepared by the vine-twining polymerization method using polytetrahydrofuran (PTHF), poly(ε-caprolactone) (PCL), and poly(l-lactide) (PLLA) as guest polymers. The stability investigation was conducted at desired temperatures (25, 30, 40, 60 °C) in DMSO solutions of the complexes. Consequently, the amylose–PTHF inclusion complex was dissociated at 25 °C, while the other complexes were stable under the same conditions. When the temperatures were elevated, the amylose–PCL and amylose–PLLA complexes were dissociated at 40 and 60 °C, respectively. We also found that amylose inclusion supramolecular polymers which were prepared by the vine-twining polymerization using primer-guest conjugates formed films by the acetylation of amylose segments. The film from acetylated amylose–PLLA supramolecular polymer had higher storage modulus than that from acetylated amylose–PTHF supramolecular polymer, as a function of temperature.

Mechanically cartilage-mimicking poly(PCL-PTHF urethane)/collagen nanofibers induce chondrogenesis by blocking NF–kappa B signaling pathway

“…By adjusting the solution parameters and spinning conditions, electrospinning can easily control the fiber properties, including the diameter, structure, surface and mechanical properties of the fibers for constructing scaffolds to facilitate the differentiation of stem cells into different types of cells including osteoblasts [17], neuronal cells [18], chondrocytes [19], and cardiomyocytes [20]. PCL can be easily synthesized with polytetrahydrofuran (PTHF) to form PCL-PTHF copolymers [21]. Other components such as 1,4-butanediol (1,4-BD) [22] and 2-ureido-4 [1H]-pyrimidinone (UPy) [23] were incorporated into PCL-PTHF.…”

Difference in Macroscopic Morphologies of Amylosic Supramolecular Networks Depending on Guest Polymers in Vine-Twining Polymerization

“…The inclusion complexes with the relatively low molecular weight guest polymers ( M n values = 1200–2200) act as cross-linking points to construct small network structures. Because the complexation with PCL and PLLA are stronger than that with PTHF under solution state, as we have previously reported [34], the robust inclusion complexes with PCL and PLLA remain intact during the further enzymatic polymerization, producing macroscopic aggregates from the small supramolecular networks in the reaction mixtures. Owing to the difference in stabilities of the complexes from PCL and PLLA, macroscopic network sizes of the aggregates are slightly different as observed in the SEM images (Figure 3).…”

“…In the following investigations, we evaluated the stability of amylose–polymer inclusion complexes with the different guest polymers under solution state in dimethyl sulfoxide (DMSO). The analytical results of the investigation indicated that stability in the DMSO solutions increased in accordance with the bulkiness of the guest polymers as follows: PTHF < PCL < PLLA [34].…”

Preparation of Amylose-Oligo[(R)-3-hydroxybutyrate] Inclusion Complex by Vine-Twining Polymerization

“…The considerable difference in these peaks is because of the non-crystalline nature of ORHB in the product, indicating that the inclusion of amylose prevents the formation of a crystalline structure in the product. Dissociation of the inclusion complex was carried out by the treatment with DMSO at elevated temperatures according to our reported procedure [ 28 ]. The degree of polymerization (DP) and MW of the dissociated amylose were determined from the λ max value in the UV–Vis spectra of the violet solution of a complex with iodine to be 62.3 and 10,100, respectively [ 29 , 30 ].…”