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Molecular Structure and Crystallization Dynamics of Poly(3-hydroxyl alkanoate) with Medium-Chain Length Biosynthesized from Pseudomonas putida

Nakaoki, Takahiko, Miura, Takahiro
Journal of polymers and the environment 2018 v.26 no.10 pp. 4124-4130
Pseudomonas putida, X-ray diffraction, carbon, crystal structure, crystallization, glycerol, hydrogen bonding, melting point, pelargonic acid, polymers, thermal analysis
The molecular structure of poly(3-hydroxyalkanoate) (P3HA) with medium-chain length, biosynthesized from Psuedomonas putida (P. putida), was investigated by thermal analysis, X-ray diffraction, and infrared spectrum. Cultivation in a medium of nonanoic acid and a mixed substrate of nonanoic acid and glycerin as carbon sources provided P3HA with monomer units of 7 and 9 carbons (P3HAₙ) and 5, 6, 7, 8, 9, and 10 carbons (P3HAₘᵢₓ). Since these P3HA has comparatively long side chains, the crystallinity was as low as about 10%. It was suggested that the hydrogen bonding plays an important role in constructing the crystal. The lamellar thickness was 1.20 nm, estimated from the melting temperature depression. This lamellar thickness corresponds to two repeating units. Crystallinity depending on time was observed by the CO stretching mode in the infrared spectrum, and then Avrami’s theory was applied to analyze the crystallization mechanism. The crystallization rate of P3HAₙ was very low, on the order of a few hours. An Avrami exponent of 1.45 was estimated from the slope of the Avrami plot. This shows that the conformational arrangement is presumably promoted along the chain axis. The slow crystallization is attributed to the long side chain, which prevents aggregation of the polymer chains.