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Synthesis of Vinyl Polymers via Enzymatic Oxidative Polymerisation

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Enzymatic Polymerization towards Green Polymer Chemistry

Part of the book series: Green Chemistry and Sustainable Technology ((GCST))

Abstract

Enzymatic methods for the polymerisation of vinyl monomers are presented and critically discussed. Vinyl monomers can be polymerised initiated by enzyme-catalysed radical formation. The most widely used initiators for this purpose are β-diketo compounds, which can be transformed into the corresponding radicals via peroxidase- or laccase-catalysed oxidation. For this, peroxidases use hydrogen peroxide as oxidant, while laccases rely on molecular oxygen. Both enzyme classes comprise specific advantages and disadvantages that are discussed in this chapter. Also, parameters to control the polymer properties are introduced and discussed.

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References

  1. Torrelo G, Hanefeld U, Hollmann F (2015) Biocatalysis. Catal Lett 145(1):309–345

    Article  CAS  Google Scholar 

  2. Shoda S, Uyama H, Kadokawa J et al (2016) Enzymes as green catalysts for precision macromolecular synthesis. Chem Rev 116(4):2307–2413

    Article  CAS  PubMed  Google Scholar 

  3. Kobayashi S, Makino A (2009) Enzymatic polymer synthesis: an opportunity for green polymer chemistry. Chem Rev 109(11):5288–5353

    Article  CAS  PubMed  Google Scholar 

  4. Hollmann F, Arends IWCE (2012) Enzyme initiated radical polymerizations. Polymers 4(1):759–793

    Article  Google Scholar 

  5. Hofrichter M, Ullrich R (2014) Oxidations catalyzed by fungal peroxygenases. Curr Opin Chem Biol 19(0):116–125

    Article  CAS  PubMed  Google Scholar 

  6. Riva S (2006) Laccases: blue enzymes for green chemistry. Trends Biotechnol 24(5):219–226

    Article  CAS  PubMed  Google Scholar 

  7. Rodríguez-Delgado MM, Alemán-Nava GS, Rodríguez-Delgado JM et al (2015) Laccase-based biosensors for detection of phenolic compounds. Trends Anal Chem 74:21–45

    Article  Google Scholar 

  8. Gross RA, Kumar A, Kalra B (2001) Polymer synthesis by in vitro enzyme catalysis. Chem Rev 101(7):2097–2124

    Article  CAS  PubMed  Google Scholar 

  9. Durand A, Lalot T, Brigodiot M et al (2001) Enzyme-mediated radical initiation of acrylamide polymerization: main characteristics of molecular weight control. Polymer 42(13):5515–5521

    Article  CAS  Google Scholar 

  10. Hollmann F, Gumulya Y, Toelle C et al (2008) Evaluation of the laccase from Myceliophthora thermophila as industrial biocatalyst for polymerization reactions. Macromolecules 41(22):8520–8524

    Article  CAS  Google Scholar 

  11. Valderrama B, Ayala M, Vazquez-Duhalt R (2002) Suicide inactivation of peroxidases and the challenge of engineering more robust enzymes. Chem Biol 9(5):555–565

    Article  CAS  PubMed  Google Scholar 

  12. Zhang W, Fernández-Fueyo E, Ni Y et al (2018) Selective aerobic oxidation reactions using a combination of photocatalytic water oxidation and enzymatic oxyfunctionalizations. Nat Catal 1:55–62

    Article  PubMed  Google Scholar 

  13. Gomez de Santos P, Canellas M, Tieves F et al (2018) Selective synthesis of the human drug metabolite 5′-hydroxypropranolol by an evolved self-sufficient peroxygenase. ACS Catal 8(6):4789–4799

    Article  CAS  Google Scholar 

  14. Zhang W, Burek BO, Fernández-Fueyo E et al (2017) Selective activation of C-H bonds by cascading photochemistry with biocatalysis. Angew Chem Int Ed 56(48):15451–15455

    Article  CAS  Google Scholar 

  15. Ni Y, Fernández-Fueyo E, Baraibar AG et al (2016) Peroxygenase-catalyzed oxyfunctionalization reactions promoted by the complete oxidation of methanol. Angew Chem Int Ed 55:798–801

    Article  CAS  Google Scholar 

  16. Paul CE, Churakova E, Maurits E et al (2014) In situ formation of H2O2 for P450 peroxygenases. Bioorg Med Chem 22(20):5692–5696

    Article  CAS  PubMed  Google Scholar 

  17. Churakova E, Kluge M, Ullrich R et al (2011) Specific photobiocatalytic oxyfunctionalization reactions. Angew Chem Int Ed 50(45):10716–10719

    Article  CAS  Google Scholar 

  18. Perez DI, Mifsud Grau M, Arends IWCE et al (2009) Visible light-driven and chloroperoxidase-catalyzed oxygenation reactions. Chem Commun 44:6848–6850

    Article  Google Scholar 

  19. Zavada S, Battsengel T, Scott T (2016) Radical-mediated enzymatic polymerizations. Int J Mol Sci 17(2):195

    Article  PubMed Central  Google Scholar 

  20. Zavada SR, McHardy NR, Scott TF (2014) Oxygen-mediated enzymatic polymerization of thiol-ene hydrogels. J Mater Chem B 2(17):2598–2605

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  21. Chapman R, Gormley Adam J, Stenzel Martina H et al (2016) Combinatorial low-volume synthesis of well-defined polymers by enzyme degassing. Angew Chem Int Ed 55(14):4500–4503

    Article  CAS  Google Scholar 

  22. Chapman R, Gormley AJ, Herpoldt K-L et al (2014) Highly controlled open vessel RAFT polymerizations by enzyme degassing. Macromolecules 47(24):8541–8547

    Article  CAS  Google Scholar 

  23. Baader WJ, Bohne C, Cilento G et al (1985) Peroxidase-catalyzed formation of triplet acetone and chemiluminescence from isobutyraldehyde and molecular oxygen. J Biol Chem 260(18):10217–10225

    CAS  PubMed  Google Scholar 

  24. Chang A, Scheer M, Grote A et al (2009) BRENDA, AMENDA and FRENDA the enzyme information system: new content and tools in 2009. Nucleic Acids Res 37:D588–D592

    Article  CAS  PubMed  Google Scholar 

  25. Singh A, Ma D, Kaplan DL (2000) Enzyme-mediated free radical polymerization of styrene. Biomacromolecules 1(4):592–596

    Article  CAS  PubMed  Google Scholar 

  26. Teixeira D, Lalot T, Brigodiot M et al (1999) ß-Diketones as key compounds in free-radical polymerization by enzyme-mediated initiation. Macromolecules 32(1):70–72

    Article  CAS  Google Scholar 

  27. Parravano G (1951) Chain reactions induced by Enzymic systems. J Am Chem Soc 73(1):183–184

    Article  CAS  Google Scholar 

  28. Derango R, Chiang L-C, Dowbenko R et al (1992) Enzyme-mediated polymerization of acrylic monomers. Biotechnol Tech 6(6):523–526

    Article  CAS  Google Scholar 

  29. Emery O, Lalot T, Brigodiot M et al (1997) Free-radical polymerization of acrylamide by horseradish peroxidase-mediated initiation. J Polymer Sci A: Polymer Chem 35(15):3331–3333

    CAS  Google Scholar 

  30. Kalra B, Gross RA (2000) Horseradish peroxidase mediated free radical polymerization of methyl methacrylate. Biomacromolecules 1(3):501–505

    Article  CAS  PubMed  Google Scholar 

  31. Qi GG, Jones CW, Schork FJ (2006) Enzyme-initiated miniemulsion polymerization. Biomacromolecules 7(11):2927–2930

    Article  CAS  PubMed  Google Scholar 

  32. Shan J, Kitamura Y, Yoshizawa H (2005) Emulsion polymerization of styrene by horseradish peroxidase-mediated initiation. Coll Polym Sci 284(1):108–111

    Article  CAS  Google Scholar 

  33. Hanefeld U, Gardossi L, Magner E (2009) Understanding enzyme immobilisation. Chem Soc Rev 38(2):453–468

    Article  CAS  PubMed  Google Scholar 

  34. Iyer PV, Ananthanarayan L (2008) Enzyme stability and stabilization–Aqueous and non-aqueous environment. Process Biochem 43(10):1019–1032

    Article  CAS  Google Scholar 

  35. Zhao Q, Sun JZ, Ren H et al (2008) Horseradish peroxidase immobilized in macroporous hydrogel for acrylamide polymerization. J Polym Sci Pol Chem 46(6):2222–2232

    Article  CAS  Google Scholar 

  36. Fernández-Fueyo E, Ni Y, Gomez Baraibar A et al (2016) Towards preparative peroxygenase-catalyzed oxyfunctionalization reactions in organic media. J Mol Catal B Enzym 134:347–352

    Article  Google Scholar 

  37. Dordick JS, Marletta MA, Klibanov AM (1987) Polymerization of phenols catalyzed by peroxidase in nonaqueous media. Biotechnol Bioeng 30(1):31–36

    Article  CAS  PubMed  Google Scholar 

  38. Zaks A, Klibanov AM (1985) Enzyme-catalyzed processes in organic solvents. Proc Natl Acad Sci U S A 82(10):3192–3196

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  39. Zaks A, Klibanov AM (1984) Enzymatic catalysis in organic media at 100°C. Science 224(4654):1249–1251

    Article  CAS  PubMed  Google Scholar 

  40. Klibanov AM, Berman Z, Alberti BN (1981) Preparative hydroxylation of aromatic compounds catalyzed by peroxidase. J Am Chem Soc 103(20):6263–6264

    Article  CAS  Google Scholar 

  41. Kreuzer LP, Männel MJ, Schubert J et al (2017) Enzymatic catalysis at nanoscale: enzyme-coated nanoparticles as colloidal biocatalysts for polymerization reactions. ACS Omega 2(10):7305–7312

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  42. Angerer PS, Studer A, Witholt B et al (2005) Oxidative polymerization of a substituted phenol with ion-paired horseradish peroxidase in an organic solvent. Macromolecules 38(15):6248–6250

    Article  CAS  Google Scholar 

  43. Kohri M, Uzawa S, Kobayashi A et al (2013) Enzymatic emulsifier-free emulsion polymerization to prepare polystyrene particles using horseradish peroxidase as a catalyst. Polymer J 45(3):354–358

    Article  CAS  Google Scholar 

  44. Kohri M (2014) Development of HRP-mediated enzymatic polymerization under heterogeneous conditions for the preparation of functional particles. Polymer J 46(7):373–380

    Article  CAS  Google Scholar 

  45. Singh A, Roy S, Samuelson L et al (2001) Peroxidase, hematin, and Pegylated-Hematin catalyzed vinyl polymerizations in water. J Macromol Sci A 38(12):1219–1230

    Article  Google Scholar 

  46. Sanchez-Leija RJ, Torres-Lubian JR, Resendiz-Rubio A et al (2016) Enzyme-mediated free radical polymerization of acrylamide in deep eutectic solvents. RSC Adv 6(16):13072–13079

    Article  CAS  Google Scholar 

  47. Villarroya S, Thurecht KJ, Howdle SM (2008) HRP-mediated inverse emulsion polymerisation of acrylamide in supercritical carbon dioxide. Green Chem 10(8):863–867

    Article  CAS  Google Scholar 

  48. Durand A, Lalot T, Brigodiot M et al (2000) Enzyme-mediated initiation of acrylamide polymerization: reaction mechanism. Polymer 41(23):8183–8192

    Article  CAS  Google Scholar 

  49. Lalot T, Brigodiot M, Maréchal E (1999) A kinetic approach to acrylamide radical polymerization by horse radish peroxidase-mediated initiation. Polymer Int 48(4):288–292

    Article  CAS  Google Scholar 

  50. Kalra B, Gross RA (2002) HRP-mediated polymerizations of acrylamide and sodium acrylate. Green Chem 4:174–178

    Article  CAS  Google Scholar 

  51. Bao S, Wu D, Su T et al (2015) Microgels formed by enzyme-mediated polymerization in reverse micelles with tunable activity and high stability. RSC Adv 5(55):44342–44345

    Article  CAS  Google Scholar 

  52. Singh A, Kaplan DL (2004) Vitamin C functionalized poly(methyl methacrylate) for free radical scavenging. J Macromol Sci A 41(12):1377–1386

    Article  Google Scholar 

  53. Ikeda R, Tanaka H, Uyama H et al (1998) Laccase-catalyzed polymerization of acrylamide. Macromol Rapid Commun 19(8):423–425

    Article  CAS  Google Scholar 

  54. Fodor C, Gajewska B, Rifaie-Graham O et al (2016) Laccase-catalyzed controlled radical polymerization of N-vinylimidazole. Polym Chem 7(43):6617–6625

    Article  CAS  Google Scholar 

  55. Shogren RL, Willett JL, Biswas A (2009) HRP-mediated synthesis of starch-polyacrylamide graft copolymers. Carbohyd Polym 75(1):189–191

    Article  CAS  Google Scholar 

  56. Wang S, Wang Q, Fan X et al (2016) Synthesis and characterization of starch-poly(methyl acrylate) graft copolymers using horseradish peroxidase. Carbohydr Polym 136:1010–1016

    Article  CAS  PubMed  Google Scholar 

  57. Wang S, Xu J, Wang Q et al (2017) Preparation and rheological properties of starch-g-poly(butyl acrylate) catalyzed by horseradish peroxidase. Process Biochem 59:104–110

    Article  CAS  Google Scholar 

  58. Karaki N, Aljawish A, Humeau C et al (2016) Enzymatic modification of polysaccharides: Mechanisins, properties, and potential applications: a review. Enz Microb Technol 90:1–18

    Article  CAS  Google Scholar 

  59. Qiao L, Wang X, Gao Y et al (2016) Laccase-mediated formation of mesoporous silica nanoparticle based redox stimuli-responsive hybrid nanogels as a multifunctional nanotheranostic agent. Nanoscale 8(39):17241–17249

    Article  CAS  PubMed  Google Scholar 

  60. Fukushima H, Kohri M, Kojima T et al (2012) Surface-initiated enzymatic vinyl polymerization: synthesis of polymer-grafted silica particles using horseradish peroxidase as catalyst. Polym Chem 3(5):1123–1125

    Article  CAS  Google Scholar 

  61. Munk L, Punt AM, Kabel MA et al (2017) Laccase catalyzed grafting of -N-OH type mediators to lignin via radical-radical coupling. RSC Adv 7(6):3358–3368

    Article  Google Scholar 

  62. Mai C, Milstein O, Hüttermann A (2000) Chemoenzymatical grafting of acrylamide onto lignin. J Biotechnol 79(2):173–183

    Article  CAS  PubMed  Google Scholar 

  63. Mai C, Milstein O, Hüttermann A (1999) Fungal laccase grafts acrylamide onto lignin in presence of peroxides. Appl Microbiol Biotechnol 51(4):527–531

    Article  CAS  Google Scholar 

  64. Witayakran S, Ragauskas AJ (2009) Modification of high-lignin softwood kraft pulp with laccase and amino acids. Enz Microb Technol 44(3):176–181

    Article  CAS  Google Scholar 

  65. Gillgren T, Hedenström M, Jönsson LJ (2017) Comparison of laccase-catalyzed cross-linking of organosolv lignin and lignosulfonates. Int J Biol Macromol 105:438–446

    Article  CAS  PubMed  Google Scholar 

  66. Yu C, Wang F, Fu S et al (2017) Laccase-assisted grafting of acrylic acid onto lignin for its recovery from wastewater. J Polymers Environ 25(4):1072–1079

    Article  CAS  Google Scholar 

  67. Dong A, Yuan J, Wang Q et al (2014) Modification of jute fabric via laccase/t-BHP-mediated graft polymerization with acrylamide. J Appl Poly Sci 131(12)

    Google Scholar 

  68. Sun H, Huang W, Yang H et al (2016) Co-immobilization of laccase and mediator through a self-initiated one-pot process for enhanced conversion of malachite green. J Colloid Interface Sci 471:20–28

    Article  CAS  PubMed  Google Scholar 

  69. Renggli K, Sauter N, Rother M et al (2017) Biocatalytic atom transfer radical polymerization in a protein cage nanoreactor. Polym Chem 8(14):2133–2136

    Article  CAS  Google Scholar 

  70. Zhang B, Wang X, Zhu A et al (2015) Enzyme-initiated reversible addition–fragmentation chain transfer polymerization. Macromolecules 48(21):7792–7802

    Article  CAS  Google Scholar 

  71. Martínez AT, Ruiz-Dueñas FJ, Camarero S et al (2017) Oxidoreductases on their way to industrial biotransformations. Biotechnol Adv 35:815–831

    Article  PubMed  Google Scholar 

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Authors and Affiliations

  1. Department of Biotechnology, Delft University of Technology, Delft, The Netherlands

    W. Zhang & F. Hollmann

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  1. W. Zhang
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  2. F. Hollmann
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Correspondence to F. Hollmann .

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Editors and Affiliations

  1. Kyoto University, Yoshida-honmachi, Sakyo-ku, Kyoto, Japan

    Shiro Kobayashi

  2. Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Japan

    Hiroshi Uyama

  3. Department of Chemistry, Biotechnology, and Chemical Engineering, Graduate School of Science and Engineering, Kagoshima University, Kagoshima, Japan

    Jun-ichi Kadokawa

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Zhang, W., Hollmann, F. (2019). Synthesis of Vinyl Polymers via Enzymatic Oxidative Polymerisation. In: Kobayashi, S., Uyama, H., Kadokawa, Ji. (eds) Enzymatic Polymerization towards Green Polymer Chemistry. Green Chemistry and Sustainable Technology. Springer, Singapore. https://doi.org/10.1007/978-981-13-3813-7_11

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