Enzymatic polymerization
{{Short description|Possible alternative polymerization process}}
Enzymatic polymerization is a potential area in polymer research, providing a sustainable and adaptable alternative to conventional polymerization processes. Its capacity to manufacture polymers with exact structures in mild circumstances opens up new possibilities for material design and application, helping to progress both research and industry. It is a novel and sustainable method of synthesizing polymers that utilizes the catalytic properties of enzymes to both initiate and regulate the polymerization process. It works under mild circumstances, usually at room temperature and pressure as well as in aqueous environments, in contrast to conventional chemical polymerization techniques that frequently need for harsh conditions and harmful reagents. This approach allows fine control over the structure and functionality of polymers while simultaneously consuming less energy and having a less environmental impact.{{Cite journal |last1=Kobayashi |first1=Shiro |last2=Uyama |first2=Hiroshi |last3=Kimura |first3=Shunsaku |date=2001-12-01 |title=Enzymatic Polymerization |url=https://pubs.acs.org/doi/10.1021/cr990121l |journal=Chemical Reviews |language=en |volume=101 |issue=12 |pages=3793–3818 |doi=10.1021/cr990121l |pmid=11740921 |issn=0009-2665|url-access=subscription }}{{Citation |last1=Kobayashi |first1=Shiro |title=Enzymatic polymerization and oligomerization |date=1995 |work=Polymer Synthesis/Polymer Engineering |volume=121 |pages=1–30 |url=http://link.springer.com/10.1007/BFb0018577 |access-date=2024-06-06 |place=Berlin/Heidelberg |publisher=Springer-Verlag |language=en |doi=10.1007/bfb0018577 |isbn=978-3-540-58733-0 |last2=Shoda |first2=Shin-ichiro |last3=Uyama |first3=Hiroshi|url-access=subscription }}
This polymerization technique has the considerable advantage of being compatible with renewable resources. Many of the monomers utilized in these procedures come from natural sources, which aligns with the ideas of green chemistry and sustainability.{{Citation |last1=Bruns |first1=Nico |title=Enzymatic Polymerizations |date=2019 |pages=xv–xix |url=http://dx.doi.org/10.1016/s0076-6879(19)30400-8 |access-date=2024-06-07 |publisher=Elsevier |last2=Loos |first2=Katja|chapter=Preface |series=Methods in Enzymology |volume=627 |doi=10.1016/s0076-6879(19)30400-8 |pmid=31630750 |isbn=978-0-12-817095-3 }} This alignment is especially crucial given growing environmental concerns and the quest for more sustainable industrial operations. The potential applications of polymers produced via enzymatic polymerization are vast, spanning the fields of biomedicine, materials science, and environmental engineering. For example, biodegradable polymers produced using this method are very useful for medical applications such as drug delivery systems, biosensors and tissue engineering scaffolds. Furthermore, enzymatic polymerization opens up fascinating possibilities for the production of innovative biomaterials with tailored characteristics for specific industrial applications.{{Cite journal |last1=Orio |first1=Saya |last2=Yamamoto |first2=Kazuya |last3=Kadokawa |first3=Jun-ichi |date=2017 |title=Preparation and Material Application of Amylose-Polymer Inclusion Complexes by Enzymatic Polymerization Approach |journal=Polymers |language=en |volume=9 |issue=12 |pages=729 |doi=10.3390/polym9120729 |doi-access=free |issn=2073-4360 |pmc=6418592 |pmid=30966029}}{{Cite journal |last1=Miletić |first1=Nemanja |last2=Nastasović |first2=Aleksandra |last3=Loos |first3=Katja |date=2012 |title=Immobilization of biocatalysts for enzymatic polymerizations: Possibilities, advantages, applications |url=https://doi.org/10.1016/j.biortech.2011.11.054 |journal=Bioresource Technology |volume=115 |pages=126–135 |doi=10.1016/j.biortech.2011.11.054 |pmid=22142507 |bibcode=2012BiTec.115..126M |issn=0960-8524}}{{Cite journal |last1=Figueiredo |first1=Pedro |last2=Almeida |first2=Beatriz C. |last3=Carvalho |first3=Alexandra T. P. |date=2019-10-17 |title=Enzymatic Polymerization of PCL-PEG Co-polymers for Biomedical Applications |journal=Frontiers in Molecular Biosciences |language=English |volume=6 |page=109 |doi=10.3389/fmolb.2019.00109 |doi-access=free |issn=2296-889X |pmc=6811512 |pmid=31681797}}{{Cite journal |last1=Behabtu |first1=Natnael |last2=Kralj |first2=Slavko |date=2020-07-13 |title=Enzymatic Polymerization Routes to Synthetic–Natural Materials: A Review |url=https://pubs.acs.org/doi/10.1021/acssuschemeng.0c01664 |journal=ACS Sustainable Chemistry & Engineering |language=en |volume=8 |issue=27 |pages=9947–9954 |doi=10.1021/acssuschemeng.0c01664 |issn=2168-0485|url-access=subscription }}
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Mechanism of enzymatic polymerization
File:Enzyme mechanism 2.svgEnzymatic polymerization can happen in a variety of ways, including:
Condensation Polymerization: Enzymes such as lipases and proteases catalyze the step-growth polymerization of monomers by establishing ester, amide, or peptide bonds, releasing tiny molecules such as water or alcohol as waste.{{Citation |last=Kobayashi |first=S. |title=Enzymatic Polymerization |date=2012 |work=Polymer Science: A Comprehensive Reference |pages=217–237 |url=https://doi.org/10.1016/B978-0-444-53349-4.00137-0 |access-date=2024-06-06 |publisher=Elsevier |doi=10.1016/b978-0-444-53349-4.00137-0 |isbn=978-0-08-087862-1|url-access=subscription }}{{Cite journal |last1=Douka |first1=Aliki |last2=Vouyiouka |first2=Stamatina |last3=Papaspyridi |first3=Lefki-Maria |last4=Papaspyrides |first4=Constantine D. |date=2018 |title=A review on enzymatic polymerization to produce polycondensation polymers: The case of aliphatic polyesters, polyamides and polyesteramides |url=https://doi.org/10.1016/j.progpolymsci.2017.10.001 |journal=Progress in Polymer Science |volume=79 |pages=1–25 |doi=10.1016/j.progpolymsci.2017.10.001 |issn=0079-6700|url-access=subscription }}
Addition Polymerization: This method includes radical-mediated processes, in which enzymes such as peroxidases initiate polymerization by producing radical species that propagate the polymer chain.{{Citation |last1=Romero-García |first1=Jorge |title=Enzymatic Polymerizations |date=2019 |pages=321–337 |url=https://doi.org/10.1016/bs.mie.2019.08.009 |access-date=2024-06-06 |publisher=Elsevier |doi=10.1016/bs.mie.2019.08.009 |last2=Ledezma-Pérez |first2=Antonio |last3=Martínez-Cartagena |first3=Manuel |last4=Alvarado-Canché |first4=Carmen |last5=Jiménez-Cárdenas |first5=Paola |last6=De-León |first6=Arxel |last7=Gallardo-Vega |first7=Carlos|chapter=Radical addition polymerization: Enzymatic template-free synthesis of conjugated polymers and their nanostructure fabrication |series=Methods in Enzymology |volume=627 |pmid=31630746 |isbn=978-0-12-817095-3 |url-access=subscription }}
Ring-Opening Polymerization: Enzymes help to open cyclic monomers to produce linear polymers, which is a typical process for synthesizing polyesters and polyamides.{{Cite journal |last1=Kobayashi |first1=Shiro |last2=Uyama |first2=Hiroshi |last3=Ohmae |first3=Masashi |date=2001-04-01 |title=Enzymatic Polymerization for Precision Polymer Synthesis |url=https://doi.org/10.1246/bcsj.74.613 |journal=Bulletin of the Chemical Society of Japan |volume=74 |issue=4 |pages=613–635 |doi=10.1246/bcsj.74.613 |issn=0009-2673|url-access=subscription }}
Types of enzymes used in polymerization
Polymerases, or polymerase enzymes, can catalyze the synthesis of different kinds of polymers. Key enzymes involved include: Lipases are used in the synthesis of polyesters and polyamides, lipases accelerate esterification and transesterification processes, which are required for polymer chain formation.{{Cite journal |last=Kobayashi |first=Shiro |date=1999-08-15 |title=Enzymatic polymerization: A new method of polymer synthesis |url=https://onlinelibrary.wiley.com/doi/10.1002/(SICI)1099-0518(19990815)37:163.0.CO;2-V |journal=Journal of Polymer Science Part A: Polymer Chemistry |language=en |volume=37 |issue=16 |pages=3041–3056 |doi=10.1002/(SICI)1099-0518(19990815)37:16<3041::AID-POLA1>3.0.CO;2-V |bibcode=1999JPoSA..37.3041K |issn=0887-624X|url-access=subscription }}{{Cite journal |last1=Maniar |first1=Dina |last2=Hohmann |first2=Katharina F. |last3=Jiang |first3=Yi |last4=Woortman |first4=Albert J. J. |last5=van Dijken |first5=Jur |last6=Loos |first6=Katja |date=2018-06-28 |title=Enzymatic Polymerization of Dimethyl 2,5-Furandicarboxylate and Heteroatom Diamines |url=http://dx.doi.org/10.1021/acsomega.8b01106 |journal=ACS Omega |volume=3 |issue=6 |pages=7077–7085 |doi=10.1021/acsomega.8b01106 |pmid=30259005 |pmc=6150640 |issn=2470-1343}} In oxidative polymerization, peroxidases aid in the polymerization of phenolic and aniline derivatives, resulting in the production of conductive polymers.{{Citation |last1=Reihmann |first1=Matthias |title=Synthesis of Phenol Polymers Using Peroxidases |work=Enzyme-Catalyzed Synthesis of Polymers |pages=1–49 |url=http://dx.doi.org/10.1007/12_034 |access-date=2024-06-07 |place=Berlin/Heidelberg |publisher=Springer-Verlag |isbn=3-540-29212-8 |last2=Ritter |first2=Helmut|series=Advances in Polymer Science |date=2006 |volume=194 |doi=10.1007/12_034 |url-access=subscription }} Glycosyltransferases are necessary for polysaccharide formation because they catalyze the transfer of sugar moieties to create glycosidic linkages.{{Cite journal |last1=Montilla |first1=Antonia |last2=Ruiz-Matute |first2=Ana I. |last3=Corzo |first3=Nieves |last4=Giacomini |first4=Cecilia |last5=Irazoqui |first5=Gabriela |date=2013-10-16 |title=Enzymatic Generation of Chitooligosaccharides from Chitosan Using Soluble and Immobilized Glycosyltransferase (Branchzyme) |url=http://dx.doi.org/10.1021/jf403321r |journal=Journal of Agricultural and Food Chemistry |volume=61 |issue=43 |pages=10360–10367 |doi=10.1021/jf403321r |pmid=24090050 |hdl=10261/99979 |issn=0021-8561|hdl-access=free }} Proteases are enzymes that help create peptide bonds, allowing amino acid monomers to be polymerized into polyamides or proteins.{{Cite journal |last1=Fukuoka |first1=Tokuma |last2=Tachibana |first2=Yoichi |last3=Tonami |first3=Hiroyuki |last4=Uyama |first4=Hiroshi |last5=Kobayashi |first5=Shiro |date=2002-05-01 |title=Enzymatic Polymerization of Tyrosine Derivatives. Peroxidase- and Protease-Catalyzed Synthesis of Poly(tyrosine)s with Different Structures |url=http://dx.doi.org/10.1021/bm020016c |journal=Biomacromolecules |volume=3 |issue=4 |pages=768–774 |doi=10.1021/bm020016c |pmid=12099821 |issn=1525-7797|url-access=subscription }}