Infrared and Raman spectroscopy and quantum chemistry calculation studies of C–H⋯O hydrogen bondings and thermal behavior of biodegradable polyhydroxyalkanoate

This review paper reports infrared (IR) and Raman spectroscopy and quantum chemistry calculation studies of C–H⋯O hydrogen bondings and thermal behavior of biodegradable polyhydroxyalkanoates. IR and Raman spectra were measured for poly(3-hydroxybutyrate) (PHB) and a new type of bacterial copolyester, poly(3-hydroxybutyrate-co−3-hydroxyhexanoate), P(HB-co-HHx) (HHx=12 mol%) over a temperature range of 20 °C to higher temperatures (PHB, 200 °C; HHx=12 mol%, 140 °C) to explore their structure and thermal behavior. One of bands due to the CH3 asymmetric stretching modes appears near 3010 cm−1 in the IR and Raman spectra of PHB and P(HB-co-HHx) at 20 °C. These frequencies of IR and Raman CH3 asymmetric stretching bands are much higher than usual. These anomalous frequencies of the CH3 asymmetric stretching bands together with the X-ray crystallographic structure of PHB have suggested that there is an inter- or intra-molecular C–H⋯O hydrogen bond between the C6-point double bond; length half of m-dashO group in one helical structure and the CH3 group in the other helical structure in PHB and P(HB-co-HHx). The quantum chemical calculation of model compounds of PHB also has suggested the existence of C–H⋯O hydrogen bonds in PHB and P(HB-co-HHx). It is very likely that a chain of C–H⋯O hydrogen bond pairs link two parallel helical structures in the crystalline parts. The temperature-dependent IR and Raman spectral variations have revealed that the crystallinity of P(HB-co-HHx) (HHx=12 mol%) decreases gradually from a fairly low temperature (about 60 °C), while the crystallinity of PHB remains almost unchanged until just below its melting temperature. It has also been found from the IR and Raman studies that for both PHB and P(HB-co-HHx) the weakening of the C–H⋯O hydrogen bonds starts from just above room temperature, but the deformation of helical structures occurs after the weakening of the C–H⋯O hydrogen bonds advances to some extent.