Martinka Maksymiak Magdalena, Andrä-Żmuda Silke, Sikorska Wanda, Janeczek Henryk, Chaber Paweł, Musioł Marta, Godzierz Marcin, Kowalczuk Marek, Adamus Grazyna
Centre of Polymer and Carbon Materials, Polish Academy of Sciences, 34. M. Curie-Skłodowska St., 41-819 Zabrze, Poland.
Materials (Basel). 2024 Nov 29;17(23):5863. doi: 10.3390/ma17235863.
This study presents an in-depth molecular and structural characterization of novel biopolyesters developed under the trademark Bluepha. The primary aim was to elucidate the relationship between chemical structure, chain architecture, and material properties of these biopolyesters to define their potential applications across various sectors. Proton nuclear magnetic resonance (H NMR) analysis identified the biopolyesters as poly[()-3-hydroxybutyrate--()-3-hydroxyhexanoate] (PHBH) copolymers, containing 4% and 10% molar content of hydroxyhexanoate (HH) units, respectively. Mass spectrometry analysis of PHBH oligomers, produced via controlled thermal degradation, further confirmed the chemical structure and molecular architecture of the PHBH samples. Additionally, multistage electrospray ionization mass spectrometry (ESI-MS/MS) provided insights into the chemical homogeneity and arrangement of comonomer units within the copolyester chains, revealing a random distribution of hydroxyhexanoate (HH) and hydroxybutyrate (HB) units along the PHBH chains. X-ray diffraction (XRD) patterns demonstrated partial crystallinity in the PHBH samples. The thermal properties, including glass transition temperature (), melting temperature (), and melting enthalpy (Δ), were found to be lower in PHBH than in poly()-3-hydroxybutyrate (PHB), suggesting a broader application potential for the tested PHBH biopolyesters.
本研究对以Bluepha商标开发的新型生物聚酯进行了深入的分子和结构表征。主要目的是阐明这些生物聚酯的化学结构、链结构与材料性能之间的关系,以确定其在各个领域的潜在应用。质子核磁共振(H NMR)分析确定这些生物聚酯为聚[(R)-3-羟基丁酸-(R)-3-羟基己酸](PHBH)共聚物,分别含有4%和10%摩尔含量的羟基己酸(HH)单元。通过控制热降解制备的PHBH低聚物的质谱分析进一步证实了PHBH样品的化学结构和分子结构。此外,多级电喷雾电离质谱(ESI-MS/MS)深入了解了共聚酯链内共聚单体单元的化学均匀性和排列,揭示了羟基己酸(HH)和羟基丁酸(HB)单元在PHBH链上的随机分布。X射线衍射(XRD)图谱表明PHBH样品具有部分结晶性。发现PHBH的热性能,包括玻璃化转变温度()、熔点()和熔化焓(Δ)低于聚(R)-3-羟基丁酸(PHB),这表明测试的PHBH生物聚酯具有更广泛的应用潜力。