In this study, uracil has been introduced as the nucleating agent (NA) for bacterially synthesized poly[(3-hydroxybutyrate)-co-(3-hydroxyhexanoate)] (PHBHHx) copolymers with HHx content of 5, 10, 18 mol-%, and poly(3-hydroxybutyrate) (PHB) homopolymer for the first time. Its effect was compared with the conventional NA of PHB, that is, boron nitride (BN), and two other naturally occurring pyrimidine derivatives, i.e., thymine and cytosine. The effects of uracil on the crystallization kinetics, melting behavior, spherulite morphology, and crystalline structure of PHBHHx and PHB were investigated by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and wide-angle X-ray diffraction (WAXD). Uracil and BN exhibit the comparable nucleation efficiency on the crystallization of PHB, whereas uracil shows much more effective nucleation ability than BN for PHBHHx copolymers. With incorporation of 1 wt.-% uracil, PHBHHx with 0-10 mol-% HHx units can finish crystallization upon cooling at 10 degrees C x min(-1). The crystallization half-times (t(1/2)) of all the PHB and PHBHHx samples decrease significantly with presence of uracil. The crystallization rate of polymers further enhances with increase in uracil concentration. With addition of 1 wt.-% uracil, the t(1/2) value of PHBHHx with 10 mol-% HHx units melt-crystallizing at 80 degrees C decreases to approximately 4.0% of the neat polymer, and the nucleation density increases by 3-4 orders of magnitude. The incorporation of uracil has no discernable effect on the crystalline structure of PHBHHx, as evidenced by WAXD results. It was proposed that the nucleation mechanism of the uracil/PHBHHx (or PHB) system might be the epitaxial nucleation.
The kinetics of crystallization induced by orotic acid (OA) and boron nitride (BN) as nucleating agents were investigated for bacterial poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)s (P(HB-co-HH)s) containing from 0 to 18% HH monomer units. The nucleation efficiency of these two chemicals was investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). It was found that both orotic acid and boron nitride are able to nucleate the crystallization of PHB. In the case of P(HB-co-HH) copolymers, orotic acid showed an outstanding nucleating effect. The comparison of half-crystallization times shows that for P(HB-co-10% HH), the crystallization initiated by orotic acid is more than three time faster than the one induced by boron nitride (t 1/2BN /t 1/2OA (60 C) ¼ 3.7 and t 1/2BN /t 1/2OA (90 C) ¼ 4.5). According to the fact that orotic acid is a biodegradable, biocompatible and a nontoxic chemical, this nucleating agent is a promising solution for PHAs used in medical applications such as implants.
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