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Degradation of Natural and Artificial Poly[(R)-3-hydroxyalkanoate]s: From Biodegradation to Hydrolysis

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Plastics from Bacteria

Part of the book series: Microbiology Monographs ((MICROMONO,volume 14))

Abstract

Biodegradability of polymers has drawn much attention as a solution to problems concerning the global environment and biomedical technologies. Poly[(R)-3-hydroxybutyrate] and its copolymers are representative biodegradable polyesters which can be degraded in natural environments such as soil, sludge, freshwater, and seawater where many microorganisms utilize the degraded products as a carbon source. The ability to degrade poly[(R)-3-hydroxyalkanoate]s (PHAs) is widely distributed among fungi and bacteria and depends on the extracellular PHA depolymerases, which are carboxyesterases, and on the physical state of the polymer (amorphous or crystalline). Intracellular depolymerase systems lead to CO2 and H2O when bacteria need energy or carbon sources. All polyesters are susceptible degradation by simple hydrolysis to some extent. The degradation rate is very dependent on the chemical structure and the crystallinity of the materials. One way to obtain more hydrophilic PHAs consists in the introduction of specific functions into the macromolecular side chains. The combination of bioconversion and organic chemistry allows modulation of the physical properties of these bacterial polyesters, such as solubility, hydrophilic–hydrophobic balance, and water stability, from the perspective of biomedical applications.

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References

  • Abe H, Doi Y (1996) Enzymatic and environmental degradation of racemic poly(3-hydroxybutyric acid)s with different stereoregularities. Macromolecules 29:8683–8688

    CAS  Google Scholar 

  • Abe H, Doi Y, Aoki H, Akehata T (1998) Solid-state structures and enzymatic degradabilities for melt-crystallized films of copolymers of (R)-3-hydroxybutyric acid with different hydroxyalkanoic acids. Macromolecules 31:1791–1797

    CAS  Google Scholar 

  • Abe T, Kobayashi T, Saito T (2005) Properties of a novel intracellular poly(3-hydroxybutyrate) depolymerase with high specific activity (PhaZd) in Wautersia eutropha H16. J Bacteriol 187:6982–6990

    CAS  PubMed  Google Scholar 

  • Alper R, Lundgren DG, Marchessault RH, Cote WA (1963) Properties of poly-β-hydroxybutyrate. I. General considerations concerning the naturally occurring polymer. Biopolymers 1:545–556

    CAS  Google Scholar 

  • Aoyagi Y, Yamashita K, Doi Y (2002) Thermal degradation of poly[(R)-3-hydroxybutyrate], poly[epsilon-caprolactone], and poly[(S)-lactide]. Polym Degrad Stab 76:53–59

    CAS  Google Scholar 

  • Bear MM, Leboucher-Durand MA, Langlois V, Lenz RW, Goodwin S, Guerin P (1997) Bacterial poly-3-hydroxyalkenoates with epoxy groups in the side chains. React Funct Polym 34:65–77

    CAS  Google Scholar 

  • Bear MM, Renard E, Randriamahefa S, Langlois V, Guerin P (2001) Preparation of a bacterial polyester with carboxy groups in side chains. C R Acad Sci Paris Chim/Chemistry 4:289–293

    CAS  Google Scholar 

  • Bloembergen S, Holden DA, Hamer GK, Bluhm TL, Marchessault RH (1986) Studies of composition and crystallinity of bacterial poly(β-hydroxybutyrate-co-β-hydroxyvalerate). Macromolecules 19:2865–2871

    CAS  Google Scholar 

  • Brucato CL, Wong SS (1991) Extracellular poly(3-hydroxybutyrate) depolymerase from Penicillium funiculosum: general characteristics and active site studies. Arch Biochem Biophys 290:497–502

    CAS  PubMed  Google Scholar 

  • Bruckner S, Meille SV, Malpezzi L, Cesaro A, Navarini N, Tombolini R (1988) The structure of poly(D-(-)-beta-hydroxybutyrate): a refinement based on the Rietveld method. Macromolecules 21:967–972

    CAS  Google Scholar 

  • Cameron NS, Corbierre MK, Eisenberg A (1999) Asymmetric amphiphilic block copolymers in solution: a morphological wonderland. Can J Chem 77:1311–1326

    CAS  Google Scholar 

  • Cheng GQ, Wu Q (2005) The application of polyhydroxyalkanoates as tissue engineering materials. Biomaterials 26:6565–6578

    Google Scholar 

  • Chung DM, Choi MH, Song JJ, Yoon SC, Kang IK, Huh NE (2001) Intracellular degradation of two structurally different polyhydroxyalkanoic acids accumulated in Pseudomonas putida and Pseudomonas citronellolis from mixtures of octanoic acid and 5-phenylvaleric acid. Int J Biol Macromol 29:243–250

    CAS  PubMed  Google Scholar 

  • Cornibert J, Marchessault RH (1972) Physical properties of poly-hydroxybutyrate. IV. Conformational analysis and crystalline structure. J Mol Biol 71:735–756

    CAS  PubMed  Google Scholar 

  • Curley JM, Lenz RW, Fuller RC, Browne SE, Gabriel CB, Panday S (1997) 13C n.m.r. spectroscopy in living cells of Pseudomonas oleovorans. Polymer 38:5313–5319

    CAS  Google Scholar 

  • de Eugenio LI, García P, Luengo JM, Sanz JM, San Roman J, García JL, Prieto MA (2007) Biochemical evidence that phaZ gene encodes a specific intracellular medium chain length polyhydroxyalkanoate depolymerase in Pseudomonas putida KT2442. J Biol Chem 282:4951–4962

    Google Scholar 

  • de Eugenio LI, García JL, García P, Prieto MA, Sanz JM (2008b) Comparative analysis of the physiological and structural properties of a medium chain length polyhydroxyalkanoate depolymerase from Pseudomonas putida KT2442. Eng Life Sci 8:260–267

    Google Scholar 

  • Doi Y (1990) Microbial polyesters. VCH, New York

    Google Scholar 

  • Doi Y, Kanesawa Y, Kunioka M, Saito T (1990) Biodegradation of microbial copolyesters poly(3-hydroxybutyrate-co-3-hydroxyvalerate and poly(3-hydroxybutyrate-co-4-hydroxybutyrate). Macromolecules 23:26–31

    CAS  Google Scholar 

  • Doi Y, Kunioka M, Nakamura Y, Soga K (1988) Nuclear magnetic resonance studies on unusual bacterial copolyesters of 3-hydroxybutyrate and 4-hydroxybutyrate. Macromolecules 21:2722–2727

    CAS  Google Scholar 

  • Domenek S, Langlois V, Renard E (2007) Bacterial polyesters-graft-polyethyleneglycol: behavior in aqueous media. Polym Degrad Stab 92:1384–1392

    CAS  Google Scholar 

  • Elbanna K, Lütke-Eversloh T, Jendrossek D, Luftmann H, Steinbüchel A (2004) Studies on the biodegradability of polythioester copolymers and homopolymers by polyhydroxyalkanoate (PHA)-degrading bacteria and PHA depolymerases. Arch Microbiol 182:212–225

    CAS  PubMed  Google Scholar 

  • Feng LD, Wang Y, Inagawa Y, Kasuya K, Doi Y, Saito T (2004) Enzymatic degradation behavior of comonomer compositionally fractionated bacterial poly(3-hydroxybutyrate-co-3-hydroxyvalerate)s by poly(3-hydroxyalkanoate) depolymerases isolated from Ralstnia pickettii T1 and Acidovorax sp TP4. Polym Degrad Stab 84:95–104

    CAS  Google Scholar 

  • Foster LJR, Lenz RW, Fuller RC (1999) Intracellular depolymerase activity in isolated inclusion bodies containing polyhydroxyalkanoates with long chain alkyl and functional substituents in the side chain. Int J Biol Macromol 26:187–192

    CAS  PubMed  Google Scholar 

  • Foster LRJ, Stuart ES, Tehrani Z, Lenz RW, Fuller RC (1996) Intracellular depolymerase and polyhydroxyoctanoate granule integrity in Pseudomonas. Int J Biol Macromol 19:177–183

    CAS  PubMed  Google Scholar 

  • Foster LJR, Zervas SJ, Lenz RW, Fuller RC (1995) The biodegradation of poly-3-hydroxyalkanoates, PHAs, with long alkyl substituents by Pseudomonas maculicola. Biodegradation 6:67–73

    CAS  Google Scholar 

  • Freier T, Kunze G, Nischen C, Kramer S, Stenberg K, Sass M, Hopt UT, Schmitz KP (2002) In vitro and in vivo degradation studies for the development of a biodegradable patch based on poly(3-hydroxybutyrate). Biomaterials 8:129–137

    Google Scholar 

  • Frier T, Kunze C, Nischan C, Kramer S, Sternberg K, Sass M (2002) Biomaterials 23:2629

    Google Scholar 

  • Fritzsche K, Lenz RW, Fuller RH (1990) Production of unsaturated polyesters by Pseudomonas oleovorans. Int J Biol Macromol 12:85–91

    CAS  PubMed  Google Scholar 

  • Fukui T, Narikawa T, Miwa T, Shirakawa Y, Saito T, Tomita K (1998) Effect of limited tryptic modification of a bacterial poly(3-hydroxybutyrate) depolymerase on its catalytic activity. Biochem Biophys Acta 952:164–171

    Google Scholar 

  • Gao D, Maehara A, Yamane T, Ueda S (2001) Identification of the intracellular polyhydroxyalkanoate depolymerase gene of Paracoccus denitrificans and some properties of the gene product. FEMS Microbiol Lett 196:159–164

    CAS  PubMed  Google Scholar 

  • Grondahl L, Chandler-Temple A, Trau M (2005) Polymeric grafting of acrylic acid onto poly(3-hydroxybutyrate-co-3-hydroxyvalerate): surface functionalization for tissue engineering applications. Biomacromolecules 6:2197–2203

    CAS  PubMed  Google Scholar 

  • Handrick R, Reinhardt S, Focarete ML, Scandola M, Adamus G, Kowalczuk M, Jendrossek D (2001) A new type of thermoalkalophilic hydrolase of Paucimonas lemoignei with high specificity for amorphous polyesters of short chain-length hydroxyalkanoic acids. J Biol Chem 276:36215–36224

    CAS  PubMed  Google Scholar 

  • Handrick R, Reinhardt S, Jendrossek D (2000) Mobilization of poly(3-hydroxybutyrate) in Ralstonia eutropha. J Bacteriol 182:5916–5918

    CAS  PubMed  Google Scholar 

  • Handrick R, Reinhardt S, Schultheiss D, Reichart T, Schüler D, Jendrossek V, Jendrossek D (2004a) Unraveling the function of Rhodospirillum rubrum activator of polyhydroxybutyrate (PHB)degradation: the activator is a PHB-granule-bound protein (phasin). J Bacteriol 186:2466–2475

    CAS  PubMed  Google Scholar 

  • Handrick R, Technow U, Reichart T, Reinhardt S, Sander T, Jendrossek D (2004b) The activator of the Rhodospirillum rubrum PHB depolymerase is a polypeptide that is extremely resistant to high temperature (121°C) and other physical or chemical stresses. FEMS Microbiol Lett 230:265–274

    CAS  PubMed  Google Scholar 

  • He J, Chen S, Yu Z (2002) Determination of poly-beta-hydroxybutyric acid in Bacillus thuringiensis by capillary zone electrophoresis with indirect ultraviolet absorbance detection. J Chromatogr A 973:197–202

    CAS  PubMed  Google Scholar 

  • Hiraishi T, Hirahara Y, Doi Y, Maeda M, Taguchi S (2006) Effects of mutations in the substrate-binding domain of poly[(R)-3-hydroxybutyrate] (PHB) depolymerase from Ralstonia pickettii T1 on PHB degradation. Appl Environ Microbiol 72:7331–7338

    CAS  PubMed  Google Scholar 

  • Hiraishi T, Ohura T, Ito S, Kasuya K, Doi Y (2000) Function of the catalytic domain of poly(3-hydroxybutyrate) depolymerase from Pseudomonas stutzeri. Biomacromolecules 1:320–324

    CAS  PubMed  Google Scholar 

  • Hirt TD, Neuenschwander P, Suter UW (1996) Telechelic diols from poly[(R)-3-hydroxybutyric acid] and poly{[(R)-3-hydroxybutyric acid]-co-[(R)-3-hydroxyvaleric acid]}. Macromol Chem Phys 197:1609–1614

    CAS  Google Scholar 

  • Hisano T, Kasuya K, Kezuka Y, Ishii N, Kobayashi T, Shiraki M, Oroudjev E, Hansma H, Iwata T, Doi Y, Saito T, Miki K (2006) The crystal structure of polyhydroxybutyrate depolymerase from Penicillium funiculosum provides insights into the recognition and degradation of biopolyesters. J Mol Biol 356:993–1004

    CAS  PubMed  Google Scholar 

  • Hocking PJ, Marchessault RH, Timmins MR, Lenz RW, Fuller RC (1996) Enzymatic degradation of single crystals of bacterial and synthetic poly(β-hydroxybutyrate). Macromolecules 29:2472–2478

    CAS  Google Scholar 

  • Holland SJ, Jolly AM, Yasin M, Tighe BJ (1987) Polymers for biodegradable medical devices. Biomaterials 8:289–29

    Google Scholar 

  • Hu SG, Jou CH, Yang MC (2003) Antibacterial and biodegradable properties of polyhydroxyalkanoates grafted with chitosan and chitooligosaccharides via ozone treatment. J Appl Polym Sci 88:2797–2803

    CAS  Google Scholar 

  • Iwata T, Doi Y, Kasuya K, Inoue Y (1997a) Visualization of enzymatic degradation of poly[(R)-3-hydroxybutyrate] single crystals by an extracellular PHB depolymerase. Macomolecules 30:833–839

    CAS  Google Scholar 

  • Iwata T, Doi Y, Nakayama S, Sasatsuki H, Teramachi S (1999) Adsorption of biopolyester depolymerase on silicon wafer and poly[(R)-3-hydroxybutyric acid] single crystal revealed by real-time AFM. Int J Biol Macromol 25:41–45

    Google Scholar 

  • Iwata T, Doi Y, Tanaka T, Akehata T, Shiromo M, Teramachi S (1997b) Enzymatic degradation and adsorption on poly[(R)-3-hydroxybutyrate] single crystals with two types of extracellular PHB depolymerases from Comamonas acidovorans YM1609 and Alcaligenes faecalis T1. Macromolecules 30:5290–5296

    CAS  Google Scholar 

  • Iwata T, Doi Y (1999) Crystal structure and biodegradation of aliphatic polyster crystals, Macomol Chem Phys 200:2429–2442

    Google Scholar 

  • Iwata T, Shiromo M, Doi Y (2002) Surface structures of poly[(R)-3-hydroxybutyrate] and its copolymer single crystals before and after enzymatic degradation with an extracellular PHB depolymerase. Macromol Chem Phys 203:1309–1312

    CAS  Google Scholar 

  • Jendrossek D (1998) Microbial degradation of polyesters: a review on extracellular poly(hydroxyalkanoic acid) depolymerases. Polym Degrad Stab 59:317–325

    CAS  Google Scholar 

  • Jendrossek D (2007) Peculiarities of PHA granules preparation and PHA depolymerase activity determination. Appl Microbiol Biotechnol 74:1186–1196

    CAS  PubMed  Google Scholar 

  • Jendrossek D, Frisse A, Behrends A, Andermann M, Kratzin HD, Stanislawski T, Schlegel HG (1995) Biochemical and molecular characterization of the Pseudomonas lemoignei polyhydroxyalkanoate depolymerase system. J Bacteriol 177:596–607

    CAS  PubMed  Google Scholar 

  • Jendrossek D, Handrick R (1996) Microbial degradation of polyhydroxyalkanoates. Annu Rev Microbiol 56:403–432

    Google Scholar 

  • Jendrossek D, Handrick R (2002) Microbial degradation of polyhydroxyalkanoates. Annu Rev Microbiol 56:403–432

    CAS  PubMed  Google Scholar 

  • Jendrossek D, Schirmer A, Schlegel HG (1996) Biodegradation of polyhydroxyalkanoic acids. Appl Microbiol Biotechnol 46:451–463

    CAS  PubMed  Google Scholar 

  • Kamiya N, Sakurai M, Inoue Y, Chüjo R (1991) Isomorphic behavior of random copolymers: thermodynamic analysis of cocrystallization of poly(3-hydroxybutyrate-co-3-hydroxyvalerate). Macromolecules 24:3888–3892

    CAS  Google Scholar 

  • Kang IK, Choi SH, Shin DS, Yoon SC (2001) Surface modification of polyhydroxyalkanoate films and their interaction with human fibroblasts. Int J Biol Macromol 28:205–212

    CAS  PubMed  Google Scholar 

  • Kasuya K, Ohura T, Masuda K, Doi Y (1999) Substrate and binding specificities of bacterial polyhydroxybutyrate depolymerases. Int J Biol Macromol 24:329–336

    CAS  PubMed  Google Scholar 

  • Kasuya K, Tezuka Y, Ishii Yamagata Y, Shiraki M, Saito T, Hisano T, Iwata T, Doi Y (2007) Molecular characterization of the poly(3-hydroxybutyrate) depolymerase gene from Penicillium funiculosum. Macromol Symp 249–250:540–544

    Google Scholar 

  • Kataeva A, Seidel RD III, Shah A, West LT, Li XL, Ljungdahl LG (2002) The fibronection type 3-like repeat from the Clostridium thermocellum cellobiohydrolase CbhA promotes hydrolysis of cellulose by modifying its surface. Appl Environ Microbiol 68:4292–4300

    CAS  PubMed  Google Scholar 

  • Kawaguchi Y, Doi Y (1992) Kinetic and mechanism of synthesis and degradation of poly(3-hydroxybutyrate) in Alcaligenes eutrophus. Macromolecules 25:2324–2329

    CAS  Google Scholar 

  • Khang G, Kim SW, Cho JC, Rhee JM, Yoon SC, Lee HB (2001) Preparation and characterization of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) microspheress for the sustained release of 5-fluororacil. Biomed Mater Eng 11:89–103

    CAS  PubMed  Google Scholar 

  • Kim H, Ju HS, Kim J (2000a) Characterization of an extracellular poly(3-hydroxy-5-phenylvalerate) depolymerase from Xanthomonas sp JS02. Appl Microbiol Biotechnol 53:323–327

    CAS  PubMed  Google Scholar 

  • Kim YB, Lenz RW, Fuller (1995) Poly-3-hydroxyalkanoates containing unsaturated repeating units produced by Pseudomonas oleovorans. Polym Sci Polym Ed 33:1367–1374

    CAS  Google Scholar 

  • Kim HJ, Ryu KE, Bae KS, Rhee YH (2000b) Purification and characterization of extracellular medium-chain-length polyhydroxyalkanoate depolymerise from Pseudomonas sp. RY-1. J Biosci Bioeng 89:196–198

    CAS  PubMed  Google Scholar 

  • Kim HM, Ryu KE, Bae KS, Rhee YH (2000c) Purification and characterization of extracellular medium-chain-length polyhydroxyalkanoate depolymerase from Pseudomonas sp. RY-1. J Biosci Bioeng 90:416–421

    Google Scholar 

  • Kim DY, Nam JS, Rhee YH (2002) Characterization of an extracellular medium-chain-length poly(3-hydroxyalkanoate) depolymerase from Pseudomonas alcaligenes LB19. Biomacromolecules 3:291–296

    CAS  PubMed  Google Scholar 

  • Kim HJ, Kim DY, Nam JS, Bae KS, Rhee YH (2003) Characterization of an extracellular medium-chain-length poly(3-hydroxyalkanoate) depolymerase from Streptomyces sp. KJ-72. Antonie Van Leeuwenhoek 83:183–189

    CAS  PubMed  Google Scholar 

  • Kobayashi T, Saito T (2003) Catalytic triad of intracellular poly(3-hydroxybutyrate) depolymerase (PhaZ1) in Ralstonia eutropha H16. J Biosci Bioeng 96:487–492

    CAS  PubMed  Google Scholar 

  • Kobayashi T, Shiraki M, Abe T, Sugiyama M, Saito T (2003) Purification and properties of an intracellular 3-hydroxybutyrate-oligomer hydrolase (PhaZ2) in Ralstonia eutropha H16 and its identification as a novel intracellular poly(3-hydroxybutyrate) depolymerase. J Bacteriol 185:3485–3490

    CAS  PubMed  Google Scholar 

  • Kobayashi T, Uchino K, Abe T, Yamazaki Y, Saito T (2005) Novel intracellular 3-hydroxybutyrate-oligomer hydrolase in Wautersia eutropha H16. J Bacteriol 187:5129–5135

    CAS  PubMed  Google Scholar 

  • Koyama N, Doi Y (1997) Effects of solid state structures on the enzymatic degradability of bacterial poly(hydroxyalkanoic acids). Macromolecules 30:826–832

    CAS  Google Scholar 

  • Kunioka M, Kawaguchi Y, Doi Y (1989) Production of biodegradable copolyesters of 3-hydroxybutyrate and 4-hydroxybutyrate by Alcaligenes eutrophus. Appl Microbiol Biotechnol 30:569–573

    CAS  Google Scholar 

  • Kurth N, Renard E, Brachet F, Robic D, Guérin P, Bourbouze (2002) Poly(3-hydroxyoctanoate) containing pendant carboxylic groups for the preparation of nanoparticles aimed at drug transport and release. Polymer 43:1095–1101

    CAS  Google Scholar 

  • Lageveen RG, Huismann GW, Preusting H, Ketelaar P, Eggink G, Witholt B (1988) Formation of polyesters by pseudomonas oleovorans: effect of substrates on formation and composition of poly-(R)-3-hydroxyalkanoates and poly-(R)-3-hydroxyalkenoates. Appl Environ Microbiol 54:2924–2932

    CAS  PubMed  Google Scholar 

  • Lee MY, Park WH, Lenz RW (2000) Hydrophilic bacterial polyesters modified with pendant hydroxyl groups. Polymer 41:1703–1709

    CAS  Google Scholar 

  • Lenz RW, Marchessault RH (2005) Bacterial polyesters: biosynthesis, biodegradable plastics and biotechnology. Biomacromolecules 6:1–8

    CAS  PubMed  Google Scholar 

  • Li J, Li X, Ni X, Leong KW (2003a) Synthesis and characterization of new biodegradable amphiphilic poly(ethylene oxide)-b-poly[(R)-3-butyrate]-b-poly(ethylene oxide) triblock copolymers. Macromolecules 36:2661–2667

    CAS  Google Scholar 

  • Li J, Ni X, Li X, Tan NK, Lim CT, Ramakrishna S, Leong KW (2005b) Micellization phenomena of biodegradable amphiphilic triblock copolymers consisting of poly(β-hydroxyalkanoic acid) and poly(ethylene oxide). Langmuir 21:8681–8685

    CAS  PubMed  Google Scholar 

  • Li X, Li J, Leong KW (2003b) Preparation and characterization of inclusion complexes of biodegradable amphiphilic poly(ethylene oxide)-poly[(R)-3-hydroxybutyrate]-poly(ethylene oxide) triblock copolymers with cyclodextrins. Macromolecules 36:1209–1214

    CAS  Google Scholar 

  • Li X, Loh XJ, Wang K, He C, Li J (2005a) Poly(ester urethane)s consisting of poly[(R)-3-hydroxybutyrate] and poly(ethylene glycol) as candidate biomaterials: characterization and mechanical property studies. Biomacromolecules 6:2740–2747

    CAS  PubMed  Google Scholar 

  • Li Z, Lin H, Ishii N, Chen GQ, Inoue Y (2007) Study of enzymatic degradation of microbial copolyesters consisting of 3-hydroxybutyrate and medium-chain-length 3-hydroxyalkanoates. Polym Degrad Stab 92:1708–1714

    CAS  Google Scholar 

  • Ma Z, Gao C, Ji J, Shen J (2002) Protein immobilization on the surface of poly-L-lactic acid films for improvement of cellular interactions Eur Polym J 38:2279–2284

    Google Scholar 

  • Majid MIA (1988) The degradation of PHB and P(HB-HV) copolymers and their uses in drug delivery. PhD thesis, University of Bath

    Google Scholar 

  • Marois Y, Zhang Z, Vert M, Beaulieu L, Lenz RW, Guidoin R (1999a) In vivo biocompatibiliy and degradation studies of polyhydroxyaoctanoate in the rat: a ne sealant for the polyester arterial prosthesis. Tissue Eng 5:369–386

    CAS  PubMed  Google Scholar 

  • Marois Y, Zhang Z, Vert M, Deng X, Lenz RW, Guidoin R (1999b) Mechanism and rate of degradation polyhydroxyoctanoate film in aqueous media: a short-term in vitro study. J Biomater Sci Polym Ed 10:483–499

    CAS  PubMed  Google Scholar 

  • Marois Y, Zhang Z, Vert M, Deng X, Lenz RW, Guidoin R (2000) Mechanism and rate of degradation polyhydroxyoctanoate film in aqueous media: a long-term in vitro study. J Biomed Mater Res A 49:216–224

    CAS  Google Scholar 

  • Merrick JM, Doudoroff M (1964) Depolymerization of poly(β-hydroxybutyrate) by an intracellular system. J Bacteriol 88:61–70

    Google Scholar 

  • Mitomo H, Watanabe Y, Yoshii F, Makuuchi K (1995) Radiation effect on polyesters. Radiat Phys Chem 46:233–238

    CAS  Google Scholar 

  • Miyazaki S, Takahashi K, Shiraki M, Saito T, Tezuka Y, Kasuya K (2000) Properties of a poly(3-hydroxybutyrate) depolymerase from Penicillium funiculosum. J Polym Environ 8:175–182

    CAS  Google Scholar 

  • Mukai K, Yamada K, Doi Y (1992) Extracellular polyhydroxyalkanoate depolymerases and their inhibitor from Pseudomonas lemoignei. Int J Biol Macromol 14:235–239

    CAS  PubMed  Google Scholar 

  • Müller B, Jendrossek D (1993) Purification and properties of poly(3-hydroxyvaleric acid) depolymerase from Pseudomonas lemoignei. Appl Microbiol Biotechnol 38:487–492

    Google Scholar 

  • Murase T, Iwata T, Doi T (2001a) Direct observation of enzymatic degradation behavior of poly[(R)-3-hydroxybutyrate] lamellar single crystals by atomic force microscopy. Macro­molecules 34:5848–5853

    CAS  Google Scholar 

  • Murase T, Iwata T, Doi Y (2001b) Atomic force microscopy investigation of poly[(R)-3-hydroxybutyrate] lamellar single crystals: relationship between molecular weight and enzymatic degradation behavior. Macromol Biosci 1:275–281

    CAS  Google Scholar 

  • Murase T, Iwata T, Doi Y (2001c) Direct observation of enzymatic degradation behavior of poly[(R)-3-hydroxybutyrate] lamellar single crystals by atomic force microscopy. Macromolecules 34:5848–5853

    CAS  Google Scholar 

  • Murase T, Suzuki Y, Doi Y, Iwata T (2002a) Non hydrolytic fragmentation of a poly[(R)-3-hydroxybutyrate] single crystal revealed by use of a mutant of polyhydroxybutyrate depolymerase. Biomacromolecules 3:312–317

    CAS  PubMed  Google Scholar 

  • Murase T, Suzuki Y, Doi Y, Iwata T (2002b) Nonhydrolytic fragmentation of a poly[(R)-3-hydroxybutyrate] single crystal revealed by use of a mutant of polyhydroxybutyrate depolymerase. Biomacromolecules 3:312–317

    CAS  PubMed  Google Scholar 

  • Nguyen S (2008) Graft copolymers containing poly(3-hydroxyalkanoates) – a review on their synthesis, properties, and applications. Can J Chem 86:570–578

    CAS  Google Scholar 

  • Nobes GAR, Marchessault RH, Chanzy H, Briese BH, Jendrossek D (1996) Splintering of poly(3-hydroxybutyrate) single crystals by PHB-depolymerase A from Pseudomonas lemoignei. Macromolecules 26:8330–8333

    Google Scholar 

  • Nobes GAR, Marchessault RH, Briese BH, Jendrossek D (1998) Microscopic visualization of the enzymatic degradation of poly(3HB-co-3HV) and poly(3HV) single crystals by PHA depolymerases from Pseudomonas lemoignei. J Environ Polym Degrad 6:99–107

    CAS  Google Scholar 

  • Nojiri M, Saito T (1997) Structure and function of poly(3-hydroxybutyrate) depolymerase from Alcaligenes faeccalis T1. J Bacteriol 179:6965–6970

    CAS  PubMed  Google Scholar 

  • Numata K, Kikkawa Y, Tsuge T, Iwata T, Doi Y, Abe H (2005) Atomic force microscopy: effects enzymatic degradation processes of poly[(R)-3-hydroxybutyric acid] and poly[(R)-3-hydroxybutyric acid-co-(R)-3-hydroxyvaleric acid] single crystals revealed by of molecular weight and second-monomer composition on erosion rates. Biomacromolecules 6:2008–2016

    Google Scholar 

  • Numata K, Kikkawa Y, Tsuge T, Iwata T, Doi Y, Abe H (2006) Adsorption of biopolyester depolymerase on silicon wafer and poly[(R)-3-hydroxybutyric acid] single crystal revealed by real-time AFM. Macromol Biosci 6:41–50

    CAS  PubMed  Google Scholar 

  • Numata K, Sato S, Fujita M, Tsuge T, Iwata T, Doi Y (2007) Adsorption effects of poly(hydroxybutyric acid) depolymerase on chain-folding surface of polyester single crystals revealed by mutant enzyme and frictional force microscopy. Polym Degrad Stab 92:176–183

    CAS  Google Scholar 

  • Ohura T, Kasuya K, Doi Y (1999) Cloning and characterization of the polyhydroxybutyrate depolymerase gene of Pseudomonas stutzeri and analysis of the function of substrate-binding domains. Appl Environ Microbiol 65:189–197

    CAS  PubMed  Google Scholar 

  • Okamura R, Marchessault RH (1967) X-ray structure of poly-β-hydroxybutyrate. In: Ramachandran GN (ed) Conformation of biopolymer, vol 2. Academic, London, pp 709–720

    Google Scholar 

  • Pohlmann A, Fricke WF, Reinecke F, Kusian B, Liesegang H, Cramm H, Eitinger T, Ewering C, Potter M, Schwart Striimatter A, Voss I, Gootschalk G, Steinbüchel A, Friedrich B, Bowien (2006) Genome sequence of the bioplastic-producing “Knallglas” bacterium Ralstonia eutropha H16. Nat Biotechnol 24:1227–1229

    PubMed  Google Scholar 

  • Pouton CW, Majid MIA, Notarianni LJ (1988) Degradation of polyhydroxybutyrate and related copolymers. Proc Int Symp Control Release Bioact Mater 15:182–183

    Google Scholar 

  • Ramsay BA, Saracovan I, Ramsay JA, Marchessault RH (1994) A method for the isolation of microorganism producing extracellular long-side-chain poly(β-hydroxyalkanoate) depolymerase). J Environ Polym Degrad 2:1–7

    CAS  Google Scholar 

  • Ravenelle F, Marchessault RH (2002) One-step synthesis of amphiphilic diblock copolymers from bacterial poly([R]-3-hydroxybutyric acid). Biomacromolecules 3:1057–1064

    CAS  PubMed  Google Scholar 

  • Ravenelle F, Marchessault RH (2003) Self-assembly of poly([R]-3-hydroxybutyric acid)-block-poly(ethylene glycol) diblock copolymers. Biomacromolecules 4:856–858

    CAS  PubMed  Google Scholar 

  • Renard E, Langlois V, Guerin P (2007) Chemical modifications of bacterial polyesters: from stability to controlled degradation of resulting polymers. Corros Eng Sci Technol 42300–42310

    Google Scholar 

  • Renard E, Poux A, Timbart L, Langlois V, Guérin P (2005) Preparation of a novel artificial bacterial polyester modified with pendant hydroxyl groups. Biomacromolecules 6:891–896

    CAS  PubMed  Google Scholar 

  • Renard E, Tanguy PY, Samain E, Guerin P (2003a) Synthesis of novel polyhydroxyalkanoates. Macromol Symp 197:11–18

    CAS  Google Scholar 

  • Renard E, Ternat C, Langlois V, Guérin P (2003b) Synthesis of graft bacterial polyesters for nanoparticles preparation. Macromol Biosci 3:248–252

    CAS  Google Scholar 

  • Renard E, Walls M, Guerin P, Langlois V (2004) Hydrolytic degradation of blends of poly hydroxyalkanoates and functionalized polyhydroxyalkanoates. Polym Degrad Stab 85:779–787

    CAS  Google Scholar 

  • Rhee YA, Kim YH, Shin KS (2006) Characterization of an extracellular poly(3-hydroxyoctanoate) depolymerase from the marine isolate Pseudomonas luteola M13–4. Enzyme Microb Technol 38:529–535

    CAS  Google Scholar 

  • Saegusa H, Shiraki L, Saito T (2002) Cloning of an intracellular D(–)-3-hydroxybutyrate-oligomer hydrolase gene from Ralstonia eutropha H16 and identification of the active site serine residue by site-directed mutagenesis. J Biosci Bioeng 94:106–112

    CAS  PubMed  Google Scholar 

  • Scherer T, Fuller MRC, Goodwin S, Lenz RW (2000) Enzymatic hydrolysis of oligomeric models of poly-3-hydroxybutyrate. Biomacromolecules 1:577–583

    CAS  PubMed  Google Scholar 

  • Schirmer A, Jendrossek D, Schlegel H (1993) Degradation of poly(3-hydroxyoctanoic acid) [P(3HO)] by bacteria: purification and properties of a P(3HO) depolymerase from Pseudomonas fluorescens GK13. Appl Environ Microbiol 59:1220–1227

    CAS  PubMed  Google Scholar 

  • Schöber U, Thiel C, Jendrossek D (2000) Poly(3-hydroxyvalerate) depolymerase of Pseudomonas lemoignei. Appl Environ Microbiol 66:1385–1392

    PubMed  Google Scholar 

  • Shiraki M, Shimada T, Tatsumchi M, Saito T (1995) Purification and characterization of extracellular poly(3-hydroxybutyrate) depolymerases. J Environ Polym Degrad 3:13–21

    CAS  Google Scholar 

  • Sparks J, Scholz C (2008) Synthesis and characterization of a cationic poly(3-hydroxyalkanoate). Biomacromolecules 9(8):2091–2096

    CAS  PubMed  Google Scholar 

  • Steinbüchel A, Aerts K, Babel W, Follner C, Liebergesell M, Madkour MH, Mayer F, Pieper-Furst U, Pries A, Valentin HE et al (1995) Considerations on the structure and biochemistry of bacterial polyhydroxyalkanoic acid inclusions. Can J Microbiol 41(Suppl 1):94–105

    PubMed  Google Scholar 

  • Stuart ES, Lenz RW, Fuller RC (1995) The ordered macromolecular surface of polyester inclusion bodies in Pseudomonas oleovorans. Can J Microbiol 41(Suppl 1):84–93

    CAS  Google Scholar 

  • Stuart ES, Foster LJR, Lenz RW, Fuller RC (1996) Intracellular depolymerase functionality and location in Pseudomonas oleovorans inclusions containing polyhydroxyoctanoate. Int J Biol Macromol 19:171–176

    CAS  PubMed  Google Scholar 

  • Sudesh K, Abe H, Doi Y (2000) Synthesis, structure and properties of polyhydroxyalkanoates biological polyesters. Prog Polym Sci 25:1503–1555

    CAS  Google Scholar 

  • Sugiyama A, Shiraki M, Kobayashi T, Morikawa G, Yamamoto M, Yamaoka M, Saito T (2002) Cloning and sequencing of an intracellular D(–)-3-hydroxybutyrate oligomer hydrolase from Acidovorax sp. strain SA1 and purification of the enzyme. Curr Microbiol 45:123–127

    CAS  PubMed  Google Scholar 

  • Tagmurlu MF, Korkuzus F, Gürsel I, Korkuzus P, Örs Ü, Hasirci V (1999) Sulbactam-cefoperazone polyhydroxybutyrate-co-hydroxuvalerate (PHBV) local antibiotic delivery system: in vivo effectiveness and biocompatibility in the treatment of implant-related experimental osteomyelitis. J Biomed Mater Res 46:494–503

    Google Scholar 

  • Takaku H, Kimoto A, Kodaira S, Nashimoto M, Takagi M (2006) Isolation of a Gram-positive poly(3-hydroxybutyrate) (PHB)-degrading bacterium from compost, and cloning and characterization of a gene encoding PHB depolymerase of Bacillus megaterium N-18–25-9. FEMS Microbiol Lett 264:152–159

    CAS  PubMed  Google Scholar 

  • Tanio T, Fukui T, Shirakura Y, Saito T, Tomita K, Kaiho T, Masamune S (1982) An extracellular poly(3-hydroxybutyrate) depolymerase from Alcaligenes faecalis. Eur J Biochem 124:71–77

    CAS  PubMed  Google Scholar 

  • Tesema Y, Raghavan D, Stubbs J (2005) Bone cell viability on methacrylic acid grafted and collagen immobilized porous poly(3-hydroxybutyrate-co-3-hydroxyvalerate). J Appl Polym Sci 98(5):1916–1921

    CAS  Google Scholar 

  • Timbart L (2005) Elaboration of biopolymers based copolymers aimed at the drug release. Thesis, Université Paris 12-Val de Marne

    Google Scholar 

  • Timbart L, Renard E, Langlois V, Guérin P (2004) Novel biodegradable copolyesters containing block of poly(3-hydroxyoctanoate) and poly(εcaprolactone): synthesis and characterization. Macromol Biosci 4:1014–1020

    CAS  PubMed  Google Scholar 

  • Timbart L, Renard E, Tessier M, Langlosis V (2007) Monohydroxylated poly(3-hydroxyoctaucate) oligomers and its functionalized derivatives used as macroinitiator. In the synthesis of degradable diblock copolyesters. Biomacromoleculs 8(4):1255–1265

    Google Scholar 

  • Tokiwa Y, Calabia BP (2004) Degradation of microbial polyesters. Biotechnol Lett 26:1183–1189

    Google Scholar 

  • Tomasi G, Scandola M, Holger B, Briese BH, Jendrossek D (1996) Enzymatic degradation of bacterial poly(3-hydroxybutyrate) by a depolymerase from Pseudomonas lemoignei. Macromolecules 29:507–513

    CAS  Google Scholar 

  • Tseng CL, Chen HJ, Shaw GC (2006) Identification and characterization of the Bacillus thuringiensis phaZ gene, encoding new intracellular poly-3-hydroxybutyrate depolymerase. J Bacteriol 188:7592–7599

    CAS  PubMed  Google Scholar 

  • Tsuji H, Suzuyoshshi K (2002) Environmental degradation of biodegradable polyesters 2 poly(epsilon-caprolactone), poly[(R)-3-hydroxybutyrate], and poly(L-lactide) films in natural dynamic sea water. Polym Degrad Stab 75:357–367

    CAS  Google Scholar 

  • Uchino K, Saito T, Jendrossek D (2008) Poly(3-hydroxybutyrate) (PHB) depolymerase PhaZa1 is involved in mobilization of accumumated PHB in Ralstonia eutropha H 16. Appl Environ Microbiol 74:1058–1063

    CAS  PubMed  Google Scholar 

  • Uefuji M, Kasuya K, Doi Y (1997) Enzymatic degradation of poly[(R)-3-hydroxybutyrate]: secretion and properties of PHB depolymerase from Pseudomonas stutzeri. Polym Degrad Stab 58:275–281

    CAS  Google Scholar 

  • VanderHart DL, Orts WJ, Marchessault RH (1995) 13C NMR determination of the degree of cocrystallization in random copolymers of poly(β-hydroxybutyrate-co-β-hydroxyvalerate). Macromolecules 28:6394–6400

    CAS  Google Scholar 

  • Wang YA, Mo W, Yao H, Wu Q, Chen J, Chen GG (2004) Biodegradation studies of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate. Polym Degrad Stab 85:815–821

    CAS  Google Scholar 

  • Yamashita K, Yamada M, Numata K, Taguchi S (2006) Nonspecific hydrophobic interactions of a repressor protein, PhaR, with poly[(R)-3-hydroxybutyrate] film studied with a quartz crystal microbalance. Macromolecules 7:2449–2454

    CAS  Google Scholar 

  • Yokouchi M, Chatani Y, Tadokoro H, Teranishi T, Tani H (1973) Structural studies of polyesters. 5. Molecular and crystal structures of optically active and racemic poly(β-hydroxybutyrate). Polymer 14:267–272

    CAS  Google Scholar 

  • Yoon SC, Choi MH (1999) Local sequence dependence of polyhydroxyalkanoic acid degradation in Hydrogenophaga pseudoflava. J Biol Chem 274(53):37800–37808 December 31

    CAS  PubMed  Google Scholar 

  • York GM, Lupberger J, Tian J, Lawrence AG, Stubbe J, Sinskey AJ (2003) Ralstonia eutropha H16 encodes two and possibly three intracellular poly[D-(–)-3-hydroxybutyrate] depolymerase genes. J Bacteriol 185:3788–3794

    CAS  PubMed  Google Scholar 

  • Yoshie N, Oike Y, Kasuya K, Doi Y, Yinoue (2002) Change of surface structure of poly(3-hydroxybutyrate) film upon enzymatic hydrolysis by PHB depolymerase. Biomacromolecules 3:1320–1326

    CAS  PubMed  Google Scholar 

  • Yu DG, Lin WC, Lin CH, Yang MC (2006) Cytocompatibility and antibacterial activity of a PHBV membrane with surface-immobilized water-soluble chitosan and chondroitin-6-sulfate. Macromol Biosci 6:348–357

    CAS  PubMed  Google Scholar 

  • Zhang L, Xiong C, Deng X (1995) J Appl Polym Sci 56:103

    CAS  Google Scholar 

  • Zhang L, Xiong C, Deng X (1997) Biodegradable polyster blends for biomedical application 56:103–112

    Google Scholar 

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  1. Institut de Chimie et des Matériaux Paris-Est, Université Paris-Est, 2–8, rue Henri Dunant, 94320, Thiais, France

    Philippe Guérin, Estelle Renard & Valérie Langlois

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  1. Philippe Guérin
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  2. Estelle Renard
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  3. Valérie Langlois
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Correspondence to Philippe Guérin .

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  1. Dept. Biological Sciences, Tsinghua University, Beijing, 100084, China, People's Republic

    George Guo-Qiang Chen

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Guérin, P., Renard, E., Langlois, V. (2010). Degradation of Natural and Artificial Poly[(R)-3-hydroxyalkanoate]s: From Biodegradation to Hydrolysis. In: Chen, GQ. (eds) Plastics from Bacteria. Microbiology Monographs, vol 14. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-03287-5_12

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