Abstract
Limited enzymatic surface hydrolysis of polyamides, polyethyleneterphthalates (PET) and polyacrylonitriles has been demonstrated to be a powerful and yet mild strategy for directly improving polymer surface properties (e.g., hydrophilicity) or activating materials for further processing. Recently, mechanistic details on enzymatic surface hydrolysis have become available, especially for the functionalisation of PET, which has been investigated in most detail. Generally, enzymes show a strong preference for amorphous regions of polymers. Consequently, during hydrolysis, the degree of crystallinity increases according to FTIR and DSC analysis. MALDI-TOF analysis has shown that PET hydrolases (i.e. cutinases and lipases) cleave the polymer endo-wise, in contrast to alkaline hydrolysis. As a result, an increase in the amount of carboxyl and hydroxyl groups has been found upon enzymatic hydrolysis, according to X-ray photoelectron spectroscopy and various derivatisation and titration methods recently adapted for this purpose. These mechanistic data, combined with advances in structural and molecular biology, help to explain the considerably different activities of closely related enzymes (e.g. cutinases) on polymers.
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References
Brueckner T, Eberl A, Heumann S et al (2008) Enzymatic and chemical hydrolysis of poly(ethylene terephthalate) fabrics. J Polym Sci 46:6435–6443
Eberl A, Heumann S, Brueckner T et al (2009) Enzymatic surface hydrolysis of poly(ethylene terephthalate) and bis(benzoyloxyethyl) terephthalate by lipase and cutinase in the presence of surface active molecules. J Biotechnol 143:207–212
Zeronian SH, Collins MJ (1989) Surface modification of polyester by alkaline treatments. Textil Progr 20:1–34
Hsieh YL, Miller A, Thompson J (1996) Wetting, pore structure and liquid retention of hydrolyzed polyester fabrics. Textil Res J 66:1–10
Fischer-Colbrie G, Matama T, Heumann S et al (2007) Surface hydrolysis of polyacrylonitrile with a nitrilase of a new strain of Micrococcus luteus. J Biotechnol 128:849–857
Asatekin A, Kang S, Elimelech M et al (2007) Anti-fouling ultrafiltration membranes containing polyacrylonitrile-graft-poly(ethylene oxide) comb copolymer additives. J Membr Sci 298:136–146
Kim HA, Choi JH, Takizawa S (2007) Comparison of initial filtration resistance by pretreatment processes in the nanofiltration for drinking water treatment. Separ Purif Technol 56:354–362
Qiao X, Zhang Z, Ping Z (2007) Hydrophilic modification of ultrafiltration membranes and their application in Salvia miltiorrhiza decoction. Separ Purif Technol 56:265–269
Li JX, Wang J, Shen LR et al (2007) The influence of polyethylene terephthalate surfaces modified by silver ion implantation on bacterial adhesion behavior. Surf Coat Technol 201:8155–8159
Guebitz GM, Cavaco-Paulo A (2008) Enzymes go big: surface hydrolysis and functionalisation of synthetic polymers. Trends Biotechnol 26:32–38
Almansa E, Heumann S, Eberl A et al (2008) Enzymatic surface hydrolysis of PET enhances bonding in PVC coating. Biocatal Biotrans 26:365–370
Laskarakis A, Logothetidis S, Kassavetis S et al (2007) Surface modification of poly(ethylene terephthalate) polymeric films for flexible electronics applications. Thin solid films 516: 1443–1448
Vertommen MAME, Nierstrasz VA, Veer Mvd et al (2005) Enzymatic surface modification of poly(ethylene terephthalate). J Biotechnol 120:376–386
Donelli M, Taddei P, Smet P F et al (2009) Enzymatic surface modification and functionalization of PET. A water contact angle, FTIR, and fluorescence spectroscopy study. Biotechnol Bioeng 103:845–856
Eberl A, Heumann S, Kotek R. et al (2008) Enzymatic hydrolysis of PTT polymers and oligomers. J Biotechnol 135:45–51
Fischer-Colbrie G, Herrmann M, Heumann S et al (2006) Surface modification of polyacrylonitrile with nitrile hydratase and amidase from Agrobacterium tumefaciens. Biocatal Biotrans 24:419–425
Wang N, Xu Y, Lu D (2004) Enzymatic surface modification of acrylic fiber. AATCC Rev 4:28–30
Ronkvist AM, Xie WC, Lu WH et al (2009) Cutinase-catalyzed hydrolysis of poly(ethylene terephthalate). Macromolecules 42:5128–5138
Parvinzadeh M, Assefipour R, Kiumarsi A (2009) Biohydrolysis of nylon 6,6 fiber with different proteolytic enzymes. Polym Degrad Stab 94:1197–1205
Heumann S, Eberl A, Fischer-Colbrie G et al (2009) A novel aryl acylamidase from Nocardia farcinica hydrolyses polyamide. Biotechnol Bioeng 102:1003–1011
Miettinen-Oinonen A, Puolakka A, Buchert J (2007) Method for modifying polyamide. Patent EP1761670 Finland
Silva C, Araujo R, Casal M et al (2007) Influence of mechanical agitation on cutinases and protease activity towards polyamide substrates. Enzyme Microb Technol 40:1678–1685
Silva C, Carneiro F, O’Neill A et al (2005) Cutinase – a new tool for biomodification of synthetic fibers. J Polym Sci 43:2448–2450
Araujo R, Silva C, O’Neill A et al (2007) Tailoring cutinase activity towards polyethylene terephthalate and polyamide 6,6 fibers. J Biotechnol 128:849–857
Silva C, Matama T, Guebitz G M et al (2005) Influence of organic solvents on cutinase stability and accessibility to polyamide fibers. J Polym Sci A Polym Chem 43:2749–2753
Crouzet J, Faucher D, Favre-Bovine G, Jourdat C, Petre D, Pierrard J, Thibault J, Guitton C Enzymes and micro organisms with amidase activity which hydrolyze polyamides. US Patent 6180388
Negoro S, Ohki T, Shibata N et al (2007) Nylon-oligomer degrading enzyme/substrate complex: catalytic mechanism of 6-aminohexanoate-dimer hydrolase. J Mol Biol 370:142–156
De Geyter N, Morent R, Leys C et al (2007) Treatment of polymer films with a dielectric barrier discharge in air, helium and argon at medium pressure. Surf Coat Technol 201:7066–7075
McCord MG, Hwang YJ, Hauser PJ et al (2002) Modifying nylon and polypropylene fabrics with atmospheric pressure plasmas. Textil Res J 72:491–498
Tusek L, Nitschke M, Werber C et al (2001) Surface characterization of NH3 plasma treated polyamide foils. Colloid Surf. A: Physicochem. Eng. Aspect 195:81–95
Parvinzadeh M (2009) A new approach to improve dyeability of nylon 6 fibre using a subtilisin enzyme. Coloration Technol 125:228–233
Parvinzadeh M, Kiumarsi A (2010) Lipase enzyme to improve dyeability of polyamide substrate. J Biotechnol 136:299
Almansa E, Heumann S, Eberl A et al (2008) Surface hydrolysis of polyamide with a new polyamidase from Beauveria brongniartii. Biocatal Biotrans 26:371–377
Yoshioka H, Nagasawa T, Yamada H (1991) Purification and characterization of aryl acylamidase from Nocardia globerula. Eur J Biochem 199:17–24
Labahn J, Neumann S, Buldt G et al (2002) An alternative mechanism for amidase signature enzymes. J Mol Biol 322:1053–1064
Valina ALB, Mazumder-Shivakumar D, Bruice T C (2004) Probing the Ser-Ser-Lys catalytic triad mechanism of peptide amidase: computational studies of the ground state, transition state, and intermediate. Biochemistry 43:15657–15672
Kakudo S, Negoro S, Urabe I et al (2000) Nylon oligomer degradation gene, nylC, on plasmid pOAD2 from a Flavobacterium strain encodes endo-type 6-aminohexanoate oligomer. Appl Environ Microbiol 59:3978–3980
Negoro S (2000) Biodegradation of nylon oligomers. Appl Microbiol Biotechnol 54:461–466
Fett WF, Wijey C, Moreau RA et al (1998) Production of cutinase by Thermomonospora fusca ATCC 27730. J Appl Microbiol 86:561–568
Carvalho CML, Aires-Barros MR, Cabral JMS (1998) Cutinase structure, function and biocatalytic applications. Electron J Biotechnol 1:160–173
Kolattukudy PE (1981) Structure, biosynthesis, and biodegradation of cutin and suberin. Annu Rev Plant Physiol Plant Mol Biol 32:539–567
Kolattukudy PE, Rogers LM, Li DX et al (1995) Surface signaling in pathogenesis. Proc Natl Acad Sci USA 92:4080–4087
Lin TS, Kolattukudy PE (1978) Induction of a biopolyester hydrolase (cutinase) by low levels of cutin monomers in Fusarium solani f. sp. pisi. J Bacteriol 133:942–951
Mueller RJ (2006) Biological degradation of synthetic polyesters – enzymes as potential catalysts for polyester recycling. Process Biochem 41:2124–2128
Liebminger S, Eberl A, Sousa F et al (2007) Hydrolysis of PET and bis-(benzoyloxyethyl) terephthalate with a new polyesterase from Penicillium citrinum. Biocatal Biotrans 25: 171–177
Alisch-Mark M, Herrmann A, Zimmermann W (2006) Increase of the hydrophilicity of polyethylene terephthalate fibres by hydrolases from Thermomonospora fusca and Fusarium solani f. sp. pisi. Biotechnol Lett 28:681–685
Nimchua T, Punnapayak H, Zimmermann W (2007) Comparison of the hydrolysis of polyethylene terephthalate fibers by a hydrolase from Fusarium oxysporum LCH I and Fusarium solani f. sp. pisi. Biotechnol J 2:361–364
Gouveia I, Queiroz J, Antunes L (2009) Improving surface energy and hydrophilization of poly(ethylene terephthalate) by enzymatic treatments. In: Freire Bastos T, Gamboa H (eds) Biodevices 2009. INSTICC Press, Setúbal
Wang X, Lu D, Jonsson LJ et al (2008) Preparation of a PET-hydrolyzing lipase from Aspergillus oryzae by the addition of bis(2-hydroxyethyl) terephthalate to the culture medium and enzymatic modification of PET fabrics. Eng Life Sci 8:268–276
Uchida H, Kurakata Y, Sawamura H et al (2003) Purification and properties of an esterase from Aspergillus nomius HS-1 degrading ethylene glycol dibenzoate. FEMS Microbiol Lett 223:123–127
Liu YB, Wu GF, Gu LH (2008) Enzymatic treatment of PET fabrics for improved hydrophilicity. AATCC Rev 8:44–48
Korpecka J (2009) Cutinase activity of PET-hydrolases. In: Proceedings of INTB 2009, Ghent, Belgium, September 2009
Liu ZQ, Gosser Y, Baker PJ et al (2009) Structural and functional studies of Aspergillus oryzae cutinase: enhanced thermostability and hydrolytic activity of synthetic ester and polyester degradation. J Am Chem Soc 131:15711–15716
Alisch M, Feuerhack A, Mueller H et al (2004) Biocatalytic modification of polyethylene terephthalate fibres by esterases from actinomycete isolates. Biocatal Biotrans 22:347–351
Andersen BK, Borch K, Abo M et al (1999) Method of treating polyester fabrics. US Patent 5,997,584, pp 1–20
Heumann S, Eberl A, Pobeheim H et al (2006) New model substrates for enzymes hydrolysing polyethyleneterephthalate and polyamide fibres. J Biochem Biophys Methods 69:89–99
Lee CW, Do Chung J (2009) Synthesis and biodegradation behavior of poly(ethylene terephthalate) oligomers. Polymer (Korea) 33:198–202
Yoon MY, Kellis J, Poulouse AJ (2002) Enzymatic modification of polyester. AATCC Rev 2:33–36
Michels A, Pütz A, Maurer KH, Eggert T, Jäger K-E Use of esterases for separating plastics. WO/2007/017181 Germany
Kellis J, Poulose AJ, Yoon MY Enzymatic modification of the surface of a polyester fiber or article. US Patent 6,254,645 B1, US 6,254,645 B1
Grochulski P, Li Y, Schrag JD et al (1993) Insights into interacial activation from an open structure of Candida rugosa Lipase. J Biol Chem 286:12843–12847
Fojan P, Jonson PH, Petersen MTN et al (2000) What distinguishes an esterase from a lipase: a novel structural approach. Biochimie 82:1033–1041
Pleiss J, Fischer M, Schmid RD (1998) Anatomy of lipase binding sites: the scissile fatty acid binding site. Chem Phys Lipids 93:67–80
Kim HR, Song WS (2006) Lipase treatment of polyester fabrics. Fibers Polym 7:339–343
Fischer-Colbrie G, Heumann S, Liebminger S et al (2004) New enzymes with potential for PET surface modification. Biocatal Biotrans 22:341–346
Herzog K, Müller RJ, Deckwer WD (2006) Mechanism and kinetics of the enzymatic hydrolysis of polyester nanoparticles by lipases. Polym Degrad Stab 91:2486–2498
Müller RJ, Schrader H, Profe J et al (2005) Enzymatic degradation of poly(ethylene terephthalate): Rapid hydrolyse using a hydrolase from T. fusca. Macromol Rapid Commun 26:1400–1405
Feng YS, Chen PC, Wen FS et al (2008) Nitrile hydratase from Mesorhizobium sp F28 and its potential for nitrile biotransformation. Process Biochem 43:1391–1397
Wang CC, Lee CM, Wu AS (2009) Acrylic acid removal from synthetic wastewater and industrial wastewater using Ralstonia solanacearum and Acidovorax avenae isolated from a wastewater treatment system manufactured with polyacrylonitrile fiber. Water Sci Technol 60:3011–3016
Tauber MM, Cavaco-Paulo A, Gübitz GM (2001) Enzymatic treatment of acrylic fibers and granulates. AATCC Rev 1:17–19
Tauber MM, Cavaco-Paulo A, Robra K-H et al (2000) Nitrile hydratase and amidase from Rhodococcus rhodochrous hydrolyse acrylic fibers and granulates. Appl Environ Microbiol 66:1634–1638
Matama T, Carneiro F, Caparrós C et al (2007) Using a nitrilase for the surface modification of acrylic fibres. Biotechnol J 2:353–360
Battistel E, Morra M, Marinetti M (2001) Enzymatic surface modification of acrylonitrile fibers. Appl Surface Sci 177:32–41
Matama T, Vaz F, Gubitz GM et al (2006) The effect of additives and mechanical agitation in surface modification of acrylic fibres by cutinase and esterase. Biotechnol J 1:842–849
Acknowledgement
The work was financed by the SFG, the FFG, the city of Graz and the province of Styria within the MacroFun project and supported by the European COST868 program.
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Guebitz, G.M. (2010). Hydrolases in Polymer Chemistry: Part III: Synthesis and Limited Surface Hydrolysis of Polyesters and Other Polymers. In: Palmans, A., Heise, A. (eds) Enzymatic Polymerisation. Advances in Polymer Science, vol 237. Springer, Berlin, Heidelberg. https://doi.org/10.1007/12_2010_89
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DOI: https://doi.org/10.1007/12_2010_89
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