Biotechnologically Produced Chitosans with Nonrandom Acetylation Patterns Differ from Conventional Chitosans in Properties and Activities

Overview

Journal Nat Commun

Specialty Biology

Date 2022 Nov 23

PMID 36418307

Authors

Sruthi Sreekumar

Jasper Wattjes

Anna Niehues

Tamara Mengoni

Ana C Mendes

Edwin R Morris

Francisco M Goycoolea

Bruno M Moerschbacher

Affiliations

Soon will be listed here.

Abstract

Chitosans are versatile biopolymers with multiple biological activities and potential applications. They are linear copolymers of glucosamine and N-acetylglucosamine defined by their degree of polymerisation (DP), fraction of acetylation (F), and pattern of acetylation (PA). Technical chitosans produced chemically from chitin possess defined DP and F but random PA, while enzymatically produced natural chitosans probably have non-random PA. This natural process has not been replicated using biotechnology because chitin de-N-acetylases do not efficiently deacetylate crystalline chitin. Here, we show that such enzymes can partially N-acetylate fully deacetylated chitosan in the presence of excess acetate, yielding chitosans with F up to 0.7 and an enzyme-dependent non-random PA. The biotech chitosans differ from technical chitosans both in terms of physicochemical and nanoscale solution properties and biological activities. As with synthetic block co-polymers, controlling the distribution of building blocks within the biopolymer chain will open a new dimension of chitosan research and exploitation.

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References

Vaaje-Kolstad G, Horn S, Sorlie M, Eijsink V . The chitinolytic machinery of Serratia marcescens--a model system for enzymatic degradation of recalcitrant polysaccharides. FEBS J. 2013; 280(13):3028-49. DOI: 10.1111/febs.12181. View

Linhardt R, Turnbull J, Wang H, Loganathan D, Gallagher J . Examination of the substrate specificity of heparin and heparan sulfate lyases. Biochemistry. 1990; 29(10):2611-7. DOI: 10.1021/bi00462a026. View

Varum K, Anthonsen M, Grasdalen H, Smidsrod O . Determination of the degree of N-acetylation and the distribution of N-acetyl groups in partially N-deacetylated chitins (chitosans) by high-field n.m.r. spectroscopy. Carbohydr Res. 1991; 211(1):17-23. DOI: 10.1016/0008-6215(91)84142-2. View

Gorzelanny C, Poppelmann B, Strozyk E, Moerschbacher B, Schneider S . Specific interaction between chitosan and matrix metalloprotease 2 decreases the invasive activity of human melanoma cells. Biomacromolecules. 2007; 8(10):3035-40. DOI: 10.1021/bm0703214. View

Fuente M, Ravina M, Paolicelli P, Sanchez A, Seijo B, Alonso M . Chitosan-based nanostructures: a delivery platform for ocular therapeutics. Adv Drug Deliv Rev. 2009; 62(1):100-17. DOI: 10.1016/j.addr.2009.11.026. View

Kong M, Chen X, Xing K, Park H . Antimicrobial properties of chitosan and mode of action: a state of the art review. Int J Food Microbiol. 2010; 144(1):51-63. DOI: 10.1016/j.ijfoodmicro.2010.09.012. View

Sorbotten A, Horn S, Eijsink V, Varum K . Degradation of chitosans with chitinase B from Serratia marcescens. Production of chito-oligosaccharides and insight into enzyme processivity. FEBS J. 2005; 272(2):538-49. DOI: 10.1111/j.1742-4658.2004.04495.x. View

Kolonko A, Efing J, Gonzalez-Espinosa Y, Bangel-Ruland N, Van Driessche W, Goycoolea F . Capsaicin-Loaded Chitosan Nanocapsules for wtCFTR-mRNA Delivery to a Cystic Fibrosis Cell Line. Biomedicines. 2020; 8(9). PMC: 7554911. DOI: 10.3390/biomedicines8090364. View

Younes I, Sellimi S, Rinaudo M, Jellouli K, Nasri M . Influence of acetylation degree and molecular weight of homogeneous chitosans on antibacterial and antifungal activities. Int J Food Microbiol. 2014; 185:57-63. DOI: 10.1016/j.ijfoodmicro.2014.04.029. View

10.

Espinosa-Garcia B, Arguelles-Monal W, Hernandez J, Felix-Valenzuela L, Acosta N, Goycoolea F . Molecularly imprinted chitosan-genipin hydrogels with recognition capacity toward o-xylene. Biomacromolecules. 2007; 8(11):3355-64. DOI: 10.1021/bm700458a. View

11.

Naqvi S, Cord-Landwehr S, Singh R, Bernard F, Kolkenbrock S, El Gueddari N . A Recombinant Fungal Chitin Deacetylase Produces Fully Defined Chitosan Oligomers with Novel Patterns of Acetylation. Appl Environ Microbiol. 2016; 82(22):6645-6655. PMC: 5086558. DOI: 10.1128/AEM.01961-16. View

12.

Raafat D, Sahl H . Chitosan and its antimicrobial potential--a critical literature survey. Microb Biotechnol. 2011; 2(2):186-201. PMC: 3815839. DOI: 10.1111/j.1751-7915.2008.00080.x. View

13.

Weikert T, Niehues A, Cord-Landwehr S, Hellmann M, Moerschbacher B . Reassessment of chitosanase substrate specificities and classification. Nat Commun. 2017; 8(1):1698. PMC: 5700058. DOI: 10.1038/s41467-017-01667-1. View

14.

Petutschnig E, Jones A, Serazetdinova L, Lipka U, Lipka V . The lysin motif receptor-like kinase (LysM-RLK) CERK1 is a major chitin-binding protein in Arabidopsis thaliana and subject to chitin-induced phosphorylation. J Biol Chem. 2010; 285(37):28902-11. PMC: 2937917. DOI: 10.1074/jbc.M110.116657. View

15.

Hembach L, Cord-Landwehr S, Moerschbacher B . Enzymatic production of all fourteen partially acetylated chitosan tetramers using different chitin deacetylases acting in forward or reverse mode. Sci Rep. 2017; 7(1):17692. PMC: 5735187. DOI: 10.1038/s41598-017-17950-6. View

16.

Kalagara T, Moutsis T, Yang Y, Pappelbaum K, Farken A, Cladder-Micus L . The endothelial glycocalyx anchors von Willebrand factor fibers to the vascular endothelium. Blood Adv. 2018; 2(18):2347-2357. PMC: 6156889. DOI: 10.1182/bloodadvances.2017013995. View

17.

Osorio S, Castillejo C, Quesada M, Medina-Escobar N, Brownsey G, Suau R . Partial demethylation of oligogalacturonides by pectin methyl esterase 1 is required for eliciting defence responses in wild strawberry (Fragaria vesca). Plant J. 2007; 54(1):43-55. DOI: 10.1111/j.1365-313X.2007.03398.x. View

18.

Verlee A, Mincke S, Stevens C . Recent developments in antibacterial and antifungal chitosan and its derivatives. Carbohydr Polym. 2017; 164:268-283. DOI: 10.1016/j.carbpol.2017.02.001. View

19.

Merzendorfer H . The cellular basis of chitin synthesis in fungi and insects: common principles and differences. Eur J Cell Biol. 2011; 90(9):759-69. DOI: 10.1016/j.ejcb.2011.04.014. View

20.

Vander , V rum KM , Domard , Eddine El Gueddari N , Moerschbacher . Comparison of the ability of partially N-acetylated chitosans and chitooligosaccharides to elicit resistance reactions in wheat leaves . Plant Physiol. 1998; 118(4):1353-9. PMC: 34751. DOI: 10.1104/pp.118.4.1353. View