固体核磁共振研究半晶聚-3-羟基丁酸酯和聚羟基丁酸戊酸酯的分子动力学

doi:10.11938/cjmr20192718

波谱学杂志 ›› 2019, Vol. 36 ›› Issue (4): 544-554.doi: 10.11938/cjmr20192718

固体核磁共振研究半晶聚-3-羟基丁酸酯和聚羟基丁酸戊酸酯的分子动力学

徐广永^1,2, 董满园², 马建锋¹, 张利民²

1. 常州大学环境与安全工程学院, 江苏常州 213164;
2. 中国科学院生物磁共振分析重点实验室, 波谱与原子分子物理国家重点实验室, 武汉磁共振中心(中国科学院武汉物理与数学研究所), 湖北武汉 430071

收稿日期:2019-03-06 出版日期:2019-12-05 发布日期:2019-04-03
通讯作者: 马建锋, 张利民 E-mail:jma@zju.edu.cn;zhanglm@wipm.ac.cn
基金资助:
the National Natural Science Foundation of China (21577169).

Molecular Dynamics of Semi-Crystalline Poly(3-Hydroxybutyrate) and Poly(3-Hydroxybutyrate-Co-3-Hydroxyvalerate) Studies by Solid-State NMR Spectroscopy

XU Guang-yong^1,2, DONG Man-yuan², MA Jian-feng¹, ZHANG Li-min²

1. School of Environmental and Safety Engineering, Changzhou University, Changzhou 213164, China;
2. CAS Key Laboratory of Magnetic Resonance in Biological Systems, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan(Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences), Wuhan 430071, China

Received:2019-03-06 Online:2019-12-05 Published:2019-04-03
Supported by:
the National Natural Science Foundation of China (21577169).

摘要/Abstract

摘要： 本文在150~370 K温度范围内，采用固体核磁共振（NMR）测定了半晶聚-3-羟基丁酸酯（PHB），以及3-羟基戊酸酯单体质量分数分别为5%（PHBV5）和12%（PHBV12）的聚羟基丁酸戊酸酯共聚物在实验室坐标系和旋转坐标系条件下质子的自旋-晶格弛豫时间T₁和T_1ρ.通过弛豫时间随温度变化的理论拟合，分别获得上述半晶聚合物晶区和结晶区的分子动力学参数（包括E_a和τ₀）.这些结果从分子水平上阐述了PHB结构修饰和增强的原因.

关键词: 固体核磁共振, 分子动力学, 聚-3-羟基丁酸酯, 聚羟基丁酸戊酸酯

Abstract: Molecular dynamics of semi-crystalline poly(3-hydroxybutyrate) (PHB) and copolymers poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) containing 5 wt.% (PHBV5) and 12 wt.% (PHBV12) 3-hydroxyvalerate monomer was studied with solid-state NMR spectroscopy. Proton spin-lattice relaxation times in the laboratory frame (T₁) and rotating frame (T_1ρ) were measured over the temperature range of 150~370 K. Kubo-Tomita expression fitting to the changes of relaxation times with temperature was used to obtain the molecular dynamics parameters (i.e., E_a and τ₀) in the crystalline and amorphous regions of PHB, PHBV5 and PHBV12. These results yielded molecular-level insights into the structural modification and enhancement of the PHB.

Key words: solid-state NMR, molecular dynamics, poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

中图分类号:

O482.53

徐广永, 董满园, 马建锋, 张利民. 固体核磁共振研究半晶聚-3-羟基丁酸酯和聚羟基丁酸戊酸酯的分子动力学[J]. 波谱学杂志, 2019, 36(4): 544-554.

XU Guang-yong, DONG Man-yuan, MA Jian-feng, ZHANG Li-min. Molecular Dynamics of Semi-Crystalline Poly(3-Hydroxybutyrate) and Poly(3-Hydroxybutyrate-Co-3-Hydroxyvalerate) Studies by Solid-State NMR Spectroscopy[J]. Chinese Journal of Magnetic Resonance, 2019, 36(4): 544-554.

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固体核磁共振研究半晶聚-3-羟基丁酸酯和聚羟基丁酸戊酸酯的分子动力学

Molecular Dynamics of Semi-Crystalline Poly(3-Hydroxybutyrate) and Poly(3-Hydroxybutyrate-Co-3-Hydroxyvalerate) Studies by Solid-State NMR Spectroscopy

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