Articles

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

  • XU Guang-yong ,
  • DONG Man-yuan ,
  • MA Jian-feng ,
  • ZHANG Li-min
Expand
  • 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 date: 2019-03-06

  Online published: 2019-04-03

Supported by

the National Natural Science Foundation of China (21577169).

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) 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., Ea 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.

Cite this article

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 . DOI: 10.11938/cjmr20192718

References

[1] ANJUM A, ZUBER M, ZIA K M, et al. Microbial production of polyhydroxyalkanoates (PHAs) and its copolymers:A review of recent advancements[J]. Int J Biol Macromol, 2016(89):161-174.
[2] POLTRONIERI P, KUMAR P. Polyhydroxyalkanoates (PHAs) in industrial applications[M]//MARTÍNEZ L, KHARISSOVA O, KHARISOV B. Handbook of ecomaterials. Springer, Cham, 2018:1-30.
[3] CHANPRATEEP S. Current trends in biodegradable polyhydroxyalkanoates[J]. J Biosci Bioeng, 2010, 110(6):621-632.
[4] NERKAR M, RAMSAY J A, RAMSAY B A, et al. Improvements in the melt and solid-state properties of poly(lactic acid), poly-3-hydroxyoctanoate and their blends through reactive modification[J]. Polymer, 2015(64):51-61.
[5] LI L, HUANG W, WANG B, et al. Properties and structure of polylactide/poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PLA/PHBV) blend fibers[J]. Polymer, 2015(68):183-194.
[6] BASNETT P, CHING K Y, STOLZ M, et al. Novel poly(3-hydroxyoctanoate)/poly(3-hydroxybutyrate) blends for medical applications[J]. Reactive and Functional Polymers, 2013, 73(10):1340-1348.
[7] CORRE Y M, BRUZAUD S, GROHENS Y. Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and poly(propylene carbonate) blends:an efficient method to finely adjust properties of functional materials[J]. Macromol Mater Eng, 2013, 298(11):1176-1183.
[8] ABDELWAHAB M A, FLYNN A, CHIOU B S, et al. Thermal, mechanical and morphological characterization of plasticized PLA-PHB blends[J]. Polym Degrad Stabil, 2012, 97(9):1822-1828.
[9] WANG Q, YANG P, XIAN M, et al. Production of block copolymer poly(3-hydroxybutyrate)-block-poly(3-hydroxypropionate) with adjustable structure from an inexpensive carbon source[J]. ACS Macro Lett, 2013, 2(11):996-1000.
[10] TRIPATHI L, WU L P, MENG D, et al. Biosynthesis and characterization of diblock copolymer of p(3-hydroxypropionate)-block-p(4-hydroxybutyrate) from recombinant Escherichia coli[J]. Biomacromolecules, 2013, 14(3):862-870.
[11] LI S Y, DONG C L, WANG S Y, et al. Microbial production of polyhydroxyalkanoate block copolymer by recombinant Pseudomonas putida[J]. Appl Microbiol Biotechnol, 2011, 90(2):659-669.
[12] LEE W H, LOO C Y, NOMURA C T, et al. Biosynthesis of polyhydroxyalkanoate copolymers from mixtures of plant oils and 3-hydroxyvalerate precursors[J]. Bioresour Technol, 2008, 99(15):6844-6851.
[13] KOLLER M, BONA R, CHIELLINI E, et al. Polyhydroxyalkanoate production from whey by Pseudomonas hydrogenovora[J]. Bioresour Technol, 2008, 99(11):4854-4863.
[14] PHUKON P, SAIKIA J P, KONWAR B K. Bio-plastic (P-3HB-co-3HV) from Bacillus circulans (MTCC 8167) and its biodegradation[J]. Colloids Surf B Biointerfaces, 2012(92):30-34.
[15] RAO U, SRIDHAR R, SEHGAL P K. Biosynthesis and biocompatibility of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) produced by Cupriavidus necator from spent palm oil[J]. Biochem Eng J, 2010, 49(1):13-20.
[16] MENG D C, SHI Z Y, WU L P, et al. Production and characterization of poly(3-hydroxypropionate-co-4-hydroxybutyrate) with fully controllable structures by recombinant Escherichia coli containing an engineered pathway[J]. Metab Eng, 2012, 14(4):317-324.
[17] CHANPRATEEP S, BUASRI K, MUANGWONG A, et al. Biosynthesis and biocompatibility of biodegradable poly(3-hydroxybutyrate-co-4-hydroxybutyrate)[J]. Polym Degrad Stabil, 2010, 95(10):2003-2012.
[18] FUKUI T, SUZUKI M, TSUGE T, et al. Microbial synthesis of poly((r)-3-hydroxybutyrate-co-3-hydroxypropionate) from unrelated carbon sources by engineered cupriavidus necator[J]. Biomacromolecules, 2009, 10(4):700-706.
[19] WANG Q, YANG P, XIAN M, et al. Biosynthesis of poly(3-hydroxypropionate-co-3-hydroxybutyrate) with fully controllable structures from glycerol[J]. Bioresour Technol, 2013(142):741-744.
[20] OBRUCA S, BENESOVA P, PETRIK S, et al. Production of polyhydroxyalkanoates using hydrolysate of spent coffee grounds[J]. Process Biochemistry, 2014, 49(9):1409-1414.
[21] WONG Y M, BRIGHAM C J, RHA C, et al. Biosynthesis and characterization of polyhydroxyalkanoate containing high 3-hydroxyhexanoate monomer fraction from crude palm kernel oil by recombinant Cupriavidus necator[J]. Bioresour Technol, 2012(121):320-327.
[22] SIMON-COLIN C, GOUIN C, LEMECHKO P, et al. Biosynthesis and characterization of polyhydroxyalkanoates by Pseudomonas guezennei from alkanoates and glucose[J]. Int J Biol Macromol, 2012, 51(5):1063-1069.
[23] DE LIMA J A, FELISBERTI M I. Poly(hydroxybutyrate) and epichlorohydrin elastomers blends:Phase behavior and morphology[J]. Eur Polym J, 2006, 42(3):602-614.
[24] ALTHURI A, MATHEW J, SINDHU R, et al. Microbial synthesis of poly-3-hydroxybutyrate and its application as targeted drug delivery vehicle[J]. Bioresour Technol, 2013(145):290-296.
[25] MASOOD F, HASAN F, AHMED S, et al. Biosynthesis and characterization of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) from Bacillus cereus FA11 isolated from TNT-contaminated soil[J]. Ann Microbiol, 2011, 62(4):1377-1384.
[26] CERRONE F, S NCHEZ-PEINADO M D M, RODR GUEZ-D AZ M, et al. PHAs production by strains belonging to Massilia genus from starch[J]. Starch, 2011, 63(4):236-240.
[27] SHAFEE E E. The influence of semicrystalline morphology on the dielectric relaxation properties of poly(3-hydroxybutyrate)[J]. Eur Polym J, 2001, 37(8):1677-1684.
[28] NOZIROV F, SZCZESNIAK E, FOJUD Z, et al. H-1 and C-13 NMR studies of molecular dynamics in the biocopolymer of glycolide and epsilon-caprolactone[J]. Solid State Nucl Mag, 2002, 22(1):19-28.
[29] ZHANG L M, TANG H R, HOU G J, et al. The domain structure and mobility of semi-crystalline poly(3-hydroxybutyrate) and poly(3-hydroxybutyrateco-3-hydroxyvalerate):A solid-state NMR study[J]. Polymer, 2007, 48(10):2928-2938.
[30] ABRAGAM A. The principles of nuclear magnetism[M]. Oxford University Press, 1961:120.
[31] NOZIROV F, FOJUD Z, KLINOWSKI J, et al. High-resolution solid-state C-13 NMR studies of poly (R)-3-hydroxybutyric acid[J]. Solid State Nucl Mag, 2002, 21(3/4):197-203.
[32] NOZIROV F, NAZIROV A, JURGA S, et al. Molecular dynamics of poly(L-lactide) biopolymer studied by wide-line solid-state H-1 and H-2 NMR spectroscopy[J]. Solid State Nucl Mag, 2006, 29(4):258-266.
[33] ARRIETA M P, L PEZ J, HERN NDEZ A, et al. Ternary PLA-PHB-Limonene blends intended for biodegradable food packaging applications[J]. Eur Polym J, 2014(50):255-270.
[34] ZEMBOUAI I, KACI M, BRUZAUD S, et al. A study of morphological, thermal, rheological and barrier properties of Poly(3-hydroxybutyrate-Co-3-Hydroxyvalerate)/polylactide blends prepared by melt mixing[J]. Polym Test, 2013, 32(5):842-851.
[35] TANG H R, BELTON P S. Molecular motions of D-alpha-galacturonic acid (GA) and methyl-D-alpha-galacturonic acid methyl ester (MGAM) in the solid state-A proton NMR study[J]. Solid State Nucl Mag, 1998, 12(1):21-30.
[36] WANG Y L, TANG H R, BELTON P S. Solid state NMR studies of the molecular motions in the polycrystalline alpha-L-fucopyranose and methyl alpha-L-fucopyranoside[J]. J Phys Chem B, 2002, 106(49):12834-12840.
[37] BECKMANN P A, BURBANK K S, LAU M M W, et al. Solid state proton spin-lattice relaxation in four structurally related organic molecules[J]. Chem Phys, 2003, 290(2/3):241-250.
[38] MCCALL D W, DOUGLASS D C. Molecular motion in polyethylene.V. (NMR-coparison with dielectric results-20 degrees-130 degreesc-e)[J]. Appl Phys Lett, 1965, 7(1):12-14.
[39] BECKMANN P A, BURBANK K S, CLEMO K M, et al. H-1 nuclear magnetic resonance spin-lattice relaxation, C-13 magic-angle-spinning nuclear magnetic resonance spectroscopy, differential scanning calorimetry, and x-ray diffraction of two polymorphs of 2,6-di-tert-butylnaphthalene[J]. J Chem Phys, 2000, 113(5):1958-1965.
[40] PACANSKY J, YOSHIMINE M. Theoretical-studies of the barriers for internal-rotation of methyl-groups in the tert-butyl radical[J]. J Phys Chem, 1986, 90(9):1980-1983.
Outlines

/