Abstract
A wide range of diverse polyhydroxyalkanoates, PHAs, is currently available due to the low substrate specificity of PHA synthases and subsequent modifications by chemical reactions. These polymers are promising materials for a number of different applications due to their biocompatibility and biodegradability. This review summarizes the large variability of PHAs regarding chemical structure and material properties that can be currently produced. In the first part, in vivo and in vitro biosynthesis processes for production of a large variety of different PHAs will be summarized with regard to obtaining saturated and unsaturated copolyesters and side chain functionalized polyesters, including brominated, hydroxylated, methyl-branched polyesters, and phenyl derivatives of polyesters. In the second part, established chemical modifications of PHAs will be summarized as that by means of grafting reactions and graft/block copolymerizations, as well as by chlorination, cross-linking, epoxidation, hydroxylation, and carboxylation, reactions yield further functionalized PHAs.
Similar content being viewed by others
References
Andrade AP, Witholt B, Hany R, Egli T, Li Z (2002) Preparation and characterization of enantiomerically pure telechelic diols from mcl-poly[(R)-3-hydroxyalkanoates]. Macromolecules 35:684–689
Arestogui SM, Aponte MA, Diaz E, Schröder E (1999) Bacterial polyesters produced by Pseudomonas oleovorans containing nitrophenyl groups. Macromolecules 32:2889–2895
Arkin AH, Hazer B (2002) Chemical modification of chlorinated microbial polyesters. Biomacromolecules 3:1327–1335
Arkin AH, Hazer B, Borcakli M (2000) Chlorination of poly-3-hydroxy alkanoates containing unsaturated side chains. Macromolecules 33:3219–3223
Arslan H, Hazer B, Yoon SC (2006) Grafting of poly(3-hydroxyalkanoate) and linoleic acid onto chitosan. J Appl Polym Sci (in press)
Ashby RD, Foglia TA (1998) Poly(hydroxyalkanoate) biosynthesis from trigliceride substrates. Appl Microbiol Biotechnol 49:431–437
Ashby RD, Foglia TA, Solaiman DKY, Liu CK, Nunez A, Eggink G (2000) Viscoelastic properties of linseed oil-based medium chain length poly(hydroxyalkanoate) films: effects of epoxidation and curing. Int J Biol Macromol 27:355–361
Ballistreri A, Montauda G, Impallomeni G, Lenz RW, Ulmer HW, Fuller RC (1995) Synthesis and characterization of polyesters produced by Rhodospirillum rubrum from pentenoic acid. Macromolecules 28:3664–3671
Ballistreri A, Giuffrida M, Guglielmino SPP, Carnazza S, Ferreri A, Impallomeni G (2001) Biosynthesis and structural characterization of medium-chain-length poly(3-hydroxyalkanoates) produced by Pseudomonas aeruginosa from fatty acids. Int J Biol Macromol 29:107–114
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
Cakmakli B, Hazer B, Borcakli M (2001) Polystyreneperoxide and poly(methyl methacrylate) peroxide for grafting on unsaturated bacterial polyesters. Macromol Biosci 1:348–354
Choi MH, Yoon SC, Lenz RW (1999) Production of poly(3-hydroxybutyric acid-co-4-hydroxybutyric acid) and poly(4-hydroxybutyric acid) without subsequent degradation by Hydrogenophage pseudoflava. Appl Environ Microbiol 65:1570–1577
Chung CW, Kim HW, Kim YB, Rhee YH (2003) Poly(ethylene glycol)-grafted poly(3-hydroxyundecenoate) networks for enhanced blood compatibility. Int J Biol Macromol 32:17–22
Constantin M, Simionescu CI, Carpov A, Samain E, Driguez H (1999) Chemical modification of poly(hydroxyalkanoates) copolymers bearing pendant sugars. Macromol Rapid Commun 20:91–94
Curley JM, Hazer B, Lenz RW, Fuller RC (1996) Production of poly(3-hydroxyalkanoates) containing aromatic substituents by Pseudomonas oleovorans. Macromolecules 29:1762–1766
Deng XM, Hao JY (2001) Synthesis and characterization of poly(3-hydroxybutyrate) macromer of bacterial origin. Eur Polym J 37:211–214
D’Haene P, Remsen EE, Asrar J (1999) Preparation and characterization of a branched bacterial polyester. Macromolecules 32:5229–5235
Doi Y (1990) Microbial polyesters. VCH, New York
Doi Y, Segawa A, Kunioka M (1990) Biosynthesis and characterization of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) in Alcaligenes eutrophus. Int J Biol Macromol 12:106–111
Doi Y, Kitamura S, Abe H (1995) Microbial synthesis and characterization of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate). Macromolecules 28:4822–4828
Dufresne A, Reche L, Marchessault RH, Lacroix M (2001) Gamma-ray crosslinking of poly(hydroxyoctanoate-co-undecenoate). Int J Biol Macromol 29:73–82
Eggink G, van der Wal H, Huijberts GNM, de Waard P (1993) Oleic acid as substrate for poly-3-hydroxyalkanoate formation in Alcaligenes eutrophus and Pseudomonas putida. Ind Crops Prod 1:157–163
Eroğlu MS, Çaykara T, Hazer B (1998) Gamma rays induced grafting of methyl methacrylate onto poly(β-hydroxynonanoate). Polym Bull 41:53–60
Eroğlu MS, Hazer B, Ozturk T, Caykara T (2005) Hydroxylation of pendant vinyl groups of poly(3-hydroxy undec-10-enoate) in high yield. J Appl Polym Sci 97:2132–2139
Feng L, Yoshie N, Asakawa N, Inoue Y (2004) Comonomer-unit compositions, physical properties and biodegradability of bacterial copolyhydroxyalkanoates. Macromol Biosci 4:186–198
Förster S, Antonietti M (1998) Amphiphilic block copolymers in structure-controlled nanomaterial hybrids. Adv Mater 10:195–217
Fritzsche K, Lenz RW, Fuller RC (1990a) An unusual bacterial polyester with a phenyl pendant group. Makromol Chem 191:1957–1965
Fritzsche K, Lenz RW, Fuller RC (1990b) Bacterial polyesters containing branched poly(β-hydroxyalkanoate) units. Int J Biol Macromol 12:92–101
Fukui T, Abe H, Doi Y (2002) Engineering of Ralstonia eutropha for production of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) from fructose and solid-state propserties of the copolymer. Biomacromolecules 3:618–624
Gagnon KD, Lenz RW, Farris RJ, Fuller RC (1994a) Chemical modification of bacterial elastomers: 1. Peroxide crosslinking. Polymer 35:4358–4367
Gagnon KD, Lenz RW, Farris RJ, Fuller RC (1994b) Chemical modification of bacterial elastomers: 2. Sulfur vulcanization. Polymer 35:4368–4375
Gerngross TU, Martin DP (1995) Enzyme-catalyzed synthesis of poly[(R)-(−)-3-hydroxybutyrate]: formation of macroscopic granules in vitro. Proc Natl Acad Sci USA 92:6279–6283
Grassie N, Murray EJ, Holmes PA (1984) The thermal degradation of poly(-(d)-β-hydroxybutyric acid): part 3—the reaction mechanism. Polym Degrad Stab 6:127–134
Grondahl L, Chandler-Temple A, Trau M (2005) Polymeric grafting of acrylic acid onto poly(3-hydroxybutyrate-co-valerate): surface functionalization for tissue engineering applications. Biomacromolecules 6:2197–2203
Gross RA, DeMello C, Lenz RW, Brandle H, Fuller RC (1989) Biosynthesis and characterization of poly(β-hydroxyalkanoates) produced by Pseudomonas oleovorans. Macromolecules 22:1106–1115
Hany R, Böhlen C, Geiger T, Hartmann R, Kawada J, Schimid M, Zinn M, Marchessault RH (2004) Chemical synthesis of crystalline comb polymers from olefinic medium-chain-length poly(3-hydroxyalkanoates). Macromolecules 37:385–389
Hao J, Deng X (2001) Semi-interpenetrating networks of bacterial poly(3-hydroxybutyrate) with net-poly(ethylene glycol). Polymer 42:4091–4097
Hartmann R, Hany R, Geiger T, Egli T, Witholt B, Zinn M (2004) Tailored biosynthesis of olefinic medium-chain-length poly[(R)-3-hydroxyalkanoates] in Pseudomonas putida Gpo1 with improved thermal properties. Macromolecules 37:6780–6785
Hartmann R, Hany R, Pletscher E, Ritter A, Witholt B, Zinn M (2006) Tailor-made olefinic medium-chain-length poly[(R)-3-hydroxyalkanoates] by Pseudomonas putida Gpo1: batch versus chemostat production. Biotechnol Bioeng 93:737–746
Hazer B (1985) Multiblock copolymers by polymeric initiators via free radical mechanism. Angew Makromol Chem 129:31–41
Hazer B (1987) Polymerization of vinyl monomers by a new oligoperoxide. Oligo (adipoyl 5-peroxy 2,5-dimethyl n hexyl) peroxide). J Polym Sci Polym Chem Ed 25:3349–3354
Hazer B (1989) Synthesis and characterization of block copolymers. In: Cheremisinoff NP (ed) Handbook of polymer science and engineering, vol 1. Marcel Dekker, New York, pp 133–176
Hazer B (1991) Synthesis of PS-PEG and PMMA-PEG branched block copolymers by macroinimers. J Macromol Sci Pure Appl Chem A28:47–52
Hazer B (1994) Preparation of polystyrene-poly(β-hydroxynonanoate) graft copolymers. Polym Bull 33:431–438
Hazer B (1995) Grafting reactions onto polymer backbone with polymeric initiator. J Macromol Sci Pure Appl Chem A32(5, 6):679–685
Hazer B (1996a) Macromonomeric initiators. In: Salamone JC (ed) Polymeric materials encyclopedia, vol 6. CRC Press, Boca Raton, pp 3911–3918
Hazer B (1996b) Poly(β-hydroxynonanoate) and polystyrene or poly(methylmethacrylate) graft copolymers : microstructure characteristics and mechanical and thermal behavior. Macromol Chem Phys 197:431–441
Hazer B (1997) Macrointermediates for block and graft copolymers. In: Cheremisinoff NP (ed) Handbook of engineering polymeric materials. Marcel Dekker, New York, pp 725–734
Hazer B (2002) Chemical modification of bacterial polyester. Curr Trends Polym Sci 7:131–138
Hazer B (2003) Chemical modification of synthetic and biosynthetic polyesters. In: Steinbüchel A (ed) Biopolymers, vol 10. Wiley–VCH, Weinheim, pp 181–208
Hazer B, Baysal BM (1986) Preparation of block copolymers using a new polymeric peroxycarbamate. Polymer 27:961–986
Hazer B, Kurt A (1995) Polymerization kinetics of styrene by oligododecandioylperoxide, ODDP, and synthesis of poly(styrene-g-butadiene) graft copolymers. Eur Polym J 31:449–503
Hazer B, Lenz RW, Fuller RC (1994a) Biosynthesis of methyl branched poly(β-hydroxy alkanoate)s with Pseudomonas oleovorans. Macromolecules 27:45–49
Hazer B, Erdem B, Lenz RW (1994b) Styrene polymerization with some new macro or macromer initiators having PEG units. J Polym Sci A Polym Chem 32:1739–1746
Hazer B, Lenz RW, Fuller RC (1996) Production of some new biopolyesters containing aromatic substituents by either Pseudomonas oleovorans or Pseudomonas putida. Polymer 37:5951–5957
Hazer B, Torul O, Borcakli M, Lenz RW, Fuller RC, Goodwin SD (1998) Bacterial production of polyesters from free fatty acids obtained from natural oils by Pseudomonas oleovorans. J Environ Polym Degrad 6:109–113
Hazer B, Lenz RW, Çakmaklı B, Borcaklı M, Koçer H (1999) Preparation of poly(ethylene glycol) grafted poly(3-hydroxyalkanoate)s. Macromol Chem Phys 200:1903–1907
Hazer B, Demirel SI, Borcakli M, Eroğlu MS, Cakmak M, Erman B (2001) Free radical crosslinking of unsaturated bacterial polyester obtained from soybean oily acids. Polym Bull 46:389–394
Hirt TD, Neuenschwander P, Suter UW (1996) Telechelic diols from poly[(R)-3-hydroxy-butyric acid] and poly[(R)-3-hydroxybutyric acid-co-[(R)-3-hydroxyvaleric acid]. Macromol Chem Phys 197:1609–1614
Hrabak O (1992) Industrial production of poly-β-hydroxybutyrate. FEMS Microbiol Rev 103:251–256
İbaoğlu K, Hazer B, Arkin AH, Lenz RW (2000) Production of poly-3-hydroxyalkanoates from methyl branched alkanoic acids by Pseudomonas oleovorans. Bulletin of the Chemists and Technologists of Macedonia 19:41–48
Ilter S, Hazer B, Borcakli M, Atici M (2001) Graft copolymerization of methyl methacrylate onto bacterial polyester containing unsaturated side chains. Macromol Chem Phys 202:2281–2286
Imamura T, Kenmoku T, Honma T, Kobayashi S, Yano T (2001) Direct biosynthesis of poly(3-hydroxyalkanoates) bearing epoxide groups. Int J Biol Macromol 29:95–301
Jiang T, Hu P (2001) Radiation-induced graft polymerization of isoprene onto polyhydroxybutyrate. Polym J 33:647–653
Jossek R, Reichelt R, Steinbüchel A (1998) In vitro biosynthesis of poly(3-hydroxybutyric acid) by using purified poly(hydroxyalkanoic acid) synthase of Chromatium vinosum. Appl Microbiol Biotechnol 49:258–266
Kamachi M, Zhang S, Goodwin S, Lenz RW (2001) Enzymatic polymerization and characterization of new poly(3-hydroxyalkanoate)s by a bacterial polymerase. Macromolecules 34:6889–6894
Kawada J, Lütke-Eversloh T, Steinbüchel A, Marchessault RH (2003) Physical properties of microbial polythioesters: characterization of poly(3-mercaptoalkanoates) synthesized by engineered Escherichia coli. Biomacromolecules 4:1698–1702
Kim YB, Lenz RW, Fuller RC (1992) Poly(β-hydroxyalkanoate) copolymers containing brominated repeating units produced by Pseudomonas oleovorans. Macromolecules 25:1852–1857
Kim YB, Lenz RW, Fuller RC (1995) Poly-3-hydroxyalkanoates containing unsaturated repeating units produced by Pseudomonas oleovorans. J Polym Sci A Polym Chem 33:1367–1374
Kim YB, Rhee YH, Han SH, Heo GS, Kim JS (1996) Poly-3-hydroxyalkanoates produced from Pseudomonas oleovorans grown with ω-phenoxyalkanoates. Macromolecules 29:3432–3435
Kim YB, Kim DY, Rhee YH (1999) PHAs produced by Pseudomonas putida and Pseudomonas oleovorans grown with n-alkanoic acids containing aromatic groups. Macromolecules 32:6058–6064
Kim DY, Kim YB, Rhee YH (2000) Evaluation of various carbon substrates for the biosynthesis of polyhydroxyalkanoates bearing functional groups by Pseudomonas putida. Int J Biol Macromol 28:23–29
Kim HW, Chung CW, Kim SS, Kim YB, Rhee YH (2002) Preparation and cell compatibility of acrylamid-grafted poly(3-hydroxyoctanoate). Int J Biol Macromol 30:129–135
Kim HW, Chung CW, Rhee YH (2005) UV-induced graft copolymerization of monoacrylate-poly(ethylene glycol) onto poly(3-hydroxyoctanoate) to reduce protein adsorption and platelet adhesion. Int J Biol Macromol 35:47–53
Koçer H, Borcaklı M, Demirel S, Hazer B (2003) Production of bacterial polyesters from some various new substrates by Alcaligenes eutrophus and Pseudomonas oleovorans. Turk J Chem 27:365–373
Konig GJM, van Bilsen HMM, Lemstra PJ, Hazenberg W, Witholt B, Preusting H, van der Galien JG, Schirmer A, Jendrossek D (1994) A biodegradable rubber by crosslinking poly(hydroxyalkanoate) from Pseudomonas oleovorans. Polymer 35:2090–2097
Kukula H, Schlaad H, Antonietti M, Förster S (2002) The formation of polymer vesicles or “peptosomes” by polybutadiene-block-poly(l-glutamate)s in dilute aqueous solution. J Am Chem Soc 124:1658–1663
Kurth N, Renard E, Brachet F, Robic D, Guerin Ph, Bourbouze R (2002) Poly(3-hydroxyoctanoate) containing pendant carboxylic groups for the preparation of nanoparticles aimed at drug transport and release. Polymer 43:1095–1101
Lageveen RG, Huisman 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)-hydroxyalkanoates and poly-(R)-3-hydroxyalkenoates. Appl Environ Microbiol 54:2924–2932
Laverty LJ, Gardlund ZG (1977) Poly(vinyl chloride)-poly(ethylene oxide) block copolymers: synthesis and characterization. J Polym Sci A Polym Chem 15:2001–2011
Lee MY, Park WH (2000) Preparation of bacterial copolyesters. Macromol Chem Phys 201:2771–2774
Lee SH, Oh DH, Ahn WS, Lee Y, Choi J, Lee SY (2000a) Production of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) by high-cell-density cultivation of Aeromonas hydrophila. Biotechnol Bioeng 67:240–244
Lee MY, Park WH, Lenz RW (2000b) Hydrophilic bacterial polyesters modified with pendant hydroxyl groups. Polymer 41:1703–1709
Lenz RW (1993) Biodegradable polymers. Adv Polym Sci 107:1–40
Lenz RW, Marchessault RH (2005) Bacterial polyesters: biosynthesis, biodegradable plastics and biotechnology. Biomacromolecules 6:1–8
Li J, Li X, Ni X, Leong KW (2003) Synthesis and characterization of new biodegradable amphiphilic poly(ethylene oxide)-b-poly[(R)-3-hydroxy butyrate]-b-poly(ethylene oxide) triblock copolymers. Macromolecules 36:2661–2667
Li J, Ni X, Li X, Tan NK, Lim CT, Ramakrishna S, Leong KW (2005a) Micellization phenomena of biodegradable amphiphilic triblock copolymers consisting of poly(β-hydroxyalkanoic acid) and poly(ethylene oxide). Langmuir 21:8681–8685
Li X, Loh XJ, Wang K, He C, Li J (2005b) Poly(ester urethane)s consisting of poly[(R)-3-hydroxy butyrate] and poly(ethylene glycol) as candidate biomaterials: characterization and mechanical property study. Biomacromolecules 6:2740–2747
Lütke-Eversloh T, Bergander K, Luftmann H, Steinbüchel A (2001a) Biosynthesis of a new class of biopolymer: bacterial synthesis of a sulfur containing polymer with thioester linkages. Microbiology 147:11–19
Lütke-Eversloh T, Bergander K, Luftman H, Steinbüchel A (2001b) Biosynthesis of poly(3-hydroxybutyrate-co-3-mercaptobutyrate) as a sulfur analog to poly(3-hydroxybutyrate). Biomacromolecules 2:1061–1065
Lütke-Eversloh T, Fischer A, Remminghorst U, Kawada J, Marchessault RH, Bögershausen A, Kalwei M, Eckert H, Reichelt R, Liu SJ, Steinbüchel A (2002) Biosynthesis of novel thermoplastic polythioesters by engineered Escherichia coli. Nature Mater 1:236–240
Nguyen S, Marchessault RH (2004) Synthesis and properties of graft copolymers based on poly(3-hydroxybutyrate) macromonomers. Macromol Biosci 4:262–268
Nuyken O, Weidner R (1986) Graft and block copolymers via polymeric azo initiators. Adv Polym Sci 145:73–74
Park WH, Lenz RW, Goodwin S (1998a) Epoxidation of bacterial polyesters with unsaturated side chains. I. Production and epoxidation of polyesters from 10-undecenoic acid. Macromolecules 31:1480–1486
Pederson EN, McChalicher CWJ, Srienc F (2006) Bacterial synthesis of PHA block copolymers. Biomacromolecules 7:1904–1911
Park WH, Lenz RW, Goodwin S (1998b) Epoxidation of bacterial polyesters with unsaturated side chains. III. Crosslinking of epoxidized polymers. J Polym Sci A Polym Chem 36:2389–2396
Qiu YZ, Ouyang SP, Shen Z, Wu Q, Chen GQ (2004) Metabolic engineering for the production of copolyesters consisting of 3-hydroxybutyrate and 3-hydroxyhexanoate by Aeromonas hydrophila. Macromol Biosci 4:255–261
Qiu YZ, Han J, Guo JJ, Chen GQ (2005) Production of poly(3-hydroxybutyrate and 3-hydroxyhexanoate) by Aeromonas hydrophila and Pseudomonas putida. Biotechnol Lett 27:1381–1386
Ramsay BA, Lomaliza K, Chavarie C, Dube B, Bataille B, Ramsay JA (1990) Production of poly-(β-hydroxybutyric-co-β-hydroxyvaleric) acids. Appl Environ Microbiol 56:2093–2098
Ravenelle F, Marchessault R (2003) Self assembly of poly[(R)-3-hydroxybutyric acid)-block-Poly(ethylene glycol) diblock copolymers. Biomacromolecules 4:856–858
Ritter H, von Spee AG (1994) Bacterial production of polyesters bearing phenoxy groups in the side chains, 1 poly(3-hydroxy-5-phenoxypentanoate-co-3-hydroxy-9-phenoxy-nonanoate) from Pseudomonas oleovorans. Macromol Chem Phys 195:1665–1672
Saad GR (2001) Calorimetric and dielectric study of the segmented biodegradable poly(ester-urethane)s based on bacterial poly[(R)-3-hydroxy butyrate]. Macromol Biosci 1:387–396
Schmack G, Gorenflo V, Steinbüchel A (1998) Biotechnological production and characterization of polyesters containing 4-hydroxyvaleric acid and medium-chain-length hydroxyalkanoic acids. Macromolecules 31:644–649
Shah DT, Tran M, Berger PA, Aggarwal P, Asrar J, Madden LA, Anderson AJ (2000) Synthesis and properties of hydroxy-terminated poly(hydroxyalkanoate)s. Macromolecules 33:2875–2880
Steinbüchel A (1991) Polyhydroxyalkanoic acids. In: Byrom D (ed) Biomaterials. Macmillan, New York, pp 123–213
Steinbüchel A (2001) Perspectives for biotechnological production and utilization of biopolymers: metabolic engineering of polyhydroxyalkanoate biosynthesis pathways as a successful example. Macromol Biosci 1:1–24
Steinbüchel A, Füchtenbusch B (1998) Bacterial and other biological systems for polyester production. TIBTECH 16:419–427
Steinbüchel A, Valentin HE (1995) Diversity of bacterial polyhydroxyalkanoic acids. FEMS Microbiol Lett 128:219–228
Stigers DJ, Tew GN (2003) Poly(3-hydroxyalkanoate)s functionalized with carboxylic acid groups in the side chain. Biomacromolecules 4:193–195
Sudesh K, Doi Y (2005) Polyhydroxyalkanoates. In: Bastioli C (ed) Handbook of biodegradable polymers. Rapra Technology, UK, pp 219–256
Sudesh K, Abe H, Doi Y (2000) Synthesis, structure and properties of polyhydroxyalkanoates: biological polyesters. Progr Polym Sci 25:1503–1555
Tanaka T, Fujita M, Takeuchi A, Suzuki Y, Uesugi K, Ito K, Fujisawa T, Doi Y, Iwata T (2006) Formation of highly ordered structure in poly[(R)-3-hydroxybutyrate-co-3-hydroxyvalerate] high-strength fibers. Macromolecules 39:2940–2946
Timbart L, Renard E, Langlois V, Guerin P (2004) Novel biodegradable copolyesters containing blocks of poly(3-hydroxyoctanoate) and poly(ɛ-caprolactone): synthesis and characterization. Macromol Biosci 4:1014–1020
Timm A, Steinbüchel A (1990) Formation of polyesters consisting of medium-chain-length 3-hydroxyalkanoic acids from gluconate by Pseudomonas aeruginosa and other fluorescent pseudomonads. Appl Environ Microbiol 56:3360–3367
Tsuge T, Saito Y, Kikkawa Y, Hiraishi T, Doi Y (2004) Biosynthesis and compositional regulation of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) in recombinant Ralstonia eutropha expressing mutated polyhydroxyalkanoate synthase genes. Macromol Biosci 4:238–242
Ulmer HW, Gross RA, Posada M, Weisbach P, Fuller RC, Lenz RW (1994) Bacterial production of poly(β-hydroxyalkanoates) containing repeating units by Rhodospirillum rubrum. Macromolecules 27:1675–1679
van der Walle GAM, Buisman GJH, Weusthuis RA, Eggink G (1999) Development of environmentally friendly coatings and paints using medium-chain-length poly(3-hydroxy-alkanoates) as the polymer binder. Int J Biol Macromol 25:123–128
Valentin HE, Lee EY, Choi CY, Steinbüchel A (1994) Identification of 4-hydroxyhexanoic acid as a new constituent of biosynthetic polyhydroxyalkanoic acids from bacteria. Appl Microbiol Biotechnol 40:710–716
Valentin HE, Berger PA, Gruys KJ, Rodrigues MFA, Steinbüchel A, Tran M, Asrar J (1999) Biosynthesis and characterization of poly(3-hydroxy-4-pentenoic acid). Macromolecules 32:7389–7395
Yalpani M, Marchessault RH, Morin FG, Monasterios CJ (1991) Synthesis of poly(3-hydroxyalkanoate) (PHA) conjugates: PHA-carbohydrate and PHA-synthetic polymer conjugates. Macromolecules 24:6046–6049
Walz R, Bömer B, Heitz W (1977) Preparation and characterization of a branched bacterial polyester. Makromol Chem 178:2527–2534
Zagar E, Krzan A, Adamus G, Kowalczuk M (2006) Sequence distribution in microbial poly(3-hydroxybutyrate and 3-hydroxyvalerate) co-polyesters determined by NMR and MS. Biomacromolecules 7:2210–2216
Zhang S, Kolvek S, Goodwin S, Lenz RW (2004) Poly(hydroxyalkanoic acid) biosynthesis in Ectothiorhodospira shaposhnikovii: characterization and reactivity of a type III PHA synthase. Biomacromolecules 5:40–48
Zhu KJ, Bihai S, Shilin Y (1989) Super microcapsules (SMC). I. Preparation and characterization of star polymethylene oxide (PEO)-polylactide (PLA) copolymers. J Polym Sci A Polym Chem 27:2151–2159
Acknowledgment
This work was financially supported by TUBITAK (Turkey) grant no. 104M128. Studies of A.S. were supported by the grant provided by the Deutsche Forschungsgemeinschaft in the past.
Author information
Authors and Affiliations
Corresponding author
Glossary of PHAs
- mclPHA
-
medium chain length poly(3-hydroxyalkanoic acid)
- PHA
-
polyhydroxyalkanoates
- PHB
-
poly(3-hydroxybutyrate)
- PHBV
-
poly(3-hydroxybutyrate-co-3-hydroxyvalerate)
- PHBHp
-
poly(3-hydroxybutyrate-co-3-hydroxyheptanoate
- PHBHx
-
poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)
- PHD
-
poly(3-hydroxydecanoate)
- PHN
-
poly(3-hydroxynonanoate)
- PHO
-
poly(3-hydroxyoctanoate)
- PHOU
-
poly(3-hydroxy octanoate-co-3-hydroxy undecenoate)
- PHPE
-
poly(3-hydroxy-4-pentenoic acid)
- PHU
-
poly(3-hydroxy-10-undecenoate)
- PHV
-
poly(3-hydroxyvalerate)
- PH5PoxV
-
poly(3-hydroxy-5-phenoxy valerate)
- PH6PHx
-
poly(3-hydroxy-6-phenyl hexanoate)
- PH8-pMPoxO
-
poly(3-hydroxy-p-methylphenoxy octanoate)
- PH-p-nitroPV
-
poly(3-hydroxy-p-nitrophenyl valerate)
- PH-p5TV
-
poly(3-hydroxy-p-tolyl valerate)
- P(H6MN)
-
poly(3-hydroxy-6-methylnonanoate)
- sclPHA
-
short chain length poly(3-hydroxyalkanoic acid)
- 3MB
-
3-mercaptobutyrate
- 3MP
-
3-mercaptopropionate
- 3MV
-
3-mercaptovalerate
Rights and permissions
About this article
Cite this article
Hazer, B., Steinbüchel, A. Increased diversification of polyhydroxyalkanoates by modification reactions for industrial and medical applications. Appl Microbiol Biotechnol 74, 1–12 (2007). https://doi.org/10.1007/s00253-006-0732-8
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00253-006-0732-8