Wattjes, J. et al. Patterns matter part 1: Chitosan polymers with non-random patterns of acetylation. React. Funct. Polym. 151, 1–9 (2020).Article
Google Scholar
Raafat, D. & Sahl, H. G. Chitosan and its antimicrobial potential—a critical literature survey. Microb. Biotechnol. 2, 186–201 (2009).Article
CAS
PubMed
PubMed Central
Google Scholar
Goy, R. C., De, Britto, D. & Assis, O. B. G. A review of the antimicrobial activity of chitosan. Polimeros 19, 241–247 (2009).Article
CAS
Google Scholar
Fuchs, K. et al. The fungal ligand chitin directly binds TLR2 and triggers inflammation dependent on oligomer size. EMBO Rep. 19, 1–14 (2018).Article
Google Scholar
Gubaeva, E. et al. ‘Slipped sandwich’ model for chitin and chitosan perception in Arabidopsis. Mol. Plant Microbe Interact. 31, 1145–1153 (2018).Article
CAS
PubMed
Google Scholar
Malerba, M. & Cerana, R. Recent advances of chitosan applications in plants. Polymers 10, 1–10 (2018).Article
Google Scholar
Sharif, R. et al. The multifunctional role of chitosan in horticultural crops; a review. Molecules 23, 1–20 (2018).Article
Google Scholar
Yang, R., Li, H., Huang, M., Yang, H. & Li, A. A review on chitosan-based flocculants and their applications in water treatment. Water Res. 95, 59–89 (2016).Article
CAS
PubMed
Google Scholar
Rinaudo, M. Chitin and chitosan: Properties and applications. Prog. Polym. Sci. 31, 603–632 (2006).Article
CAS
Google Scholar
Miguel, S. P., Moreira, A. F. & Correia, I. J. Chitosan based-asymmetric membranes for wound healing: A review. Int. J. Biol. Macromol. 127, 460–475 (2019).Article
CAS
PubMed
Google Scholar
Ali, A. & Ahmed, S. A review on chitosan and its nanocomposites in drug delivery. Int. J. Biol. Macromol. 109, 273–286 (2018).Article
CAS
PubMed
Google Scholar
Peniche, C., Argüelles-Monal, W. & Goycoolea, F. M. Chitin and chitosan: Major sources, properties and applications. in Monomers, Polymers and Composites from Renewable Resources (eds. Belgacem, M. N. & Gandini, A.) 517–542 (Elsevier, 2008).Heterogeneous Reaction. Encyclopædia Britannica https://www.britannica.com/science/heterogeneous-reaction (1998).Vårum, K. M., Anthonsen, M. W., Grasdalen, H. & Smidsrød, 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. 211, 17–23 (1991).Article
PubMed
Google Scholar
Lamarque, G., Viton, C. & Domard, A. Comparative study of the first heterogeneous deacetylation of α- and β-chitins in a multistep process. Biomacromolecules 5, 992–1001 (2004).Article
CAS
PubMed
Google Scholar
Lamarque, G., Viton, C. & Domard, A. Comparative study of the second and third heterogeneous deacetylations of α- and β-chitins in a multistep process. Biomacromolecules 5, 1899–1907 (2004).Article
CAS
PubMed
Google Scholar
Homogeneous Reaction. Encyclopædia Britannica https://www.britannica.com/science/heterogeneous-reaction (2016).Sannan, T., Kurita, K. & Iwakura, Y. Studies on chitin, 1: Solubility change by alkaline treatment and film casting. Die Makromol. Chem. 176, 1191–1195 (1975).Article
CAS
Google Scholar
Kurita, K., Sannan, T. & Iwakura, Y. Studies on chitin, 4: Evidence for formation of block and random copolymers of N-Acetyl-D-glucosamine and D-glucosamine by hetero- and homogeneous hydrolyses. Die Makromol. Chem. 178, 3197–3202 (1977).Article
CAS
Google Scholar
Schatz, C., Viton, C., Delair, T., Pichot, C. & Domard, A. Typical physicochemical behaviors of chitosan in aqueous solution. Biomacromolecules 4, 641–648 (2003).Article
CAS
PubMed
Google Scholar
Lamarque, G., Lucas, J.-M., Viton, C. & Domard, A. Physicochemical behavior of homogeneous series of acetylated chitosans in aqueous solution: Role of various structural parameters. Biomacromolecules 6, 131–142 (2005).Article
CAS
PubMed
Google Scholar
Jang, M.-K., Kong, B.-G., Jeong, Y.-I., Lee, C. H. & Nah, J.-W. Physicochemical characterization of α-chitin, β-chitin, and γ-chitin separated from natural resources. J. Polym. Sci. Part A Polym. Chem. 42, 3423–3432 (2004).Article
ADS
CAS
Google Scholar
Kaya, M. et al. On chemistry of γ-chitin. Carbohydr. Polym. 176, 177–186 (2017).Article
CAS
PubMed
Google Scholar
Hirai, A., Odani, H. & Nakajima, A. Determination of degree of deacetylation of chitosan by 1H NMR spectroscopy. Polym. Bull. 26, 87–94 (1991).Article
CAS
Google Scholar
Wattjes, J., Niehues, A. & Moerschbacher, B. M. Robust enzymatic-mass spectrometric fingerprinting analysis of the fraction of acetylation of chitosans. Carbohydr. Polym. 231, 115684 (2020).Article
CAS
PubMed
Google Scholar
Vårum, K. M., Anthonsen, M. W., Grasdalen, H. & Smidsrød, O. 13C-N.m.r. studies of the acetylation sequences in partially N-deacetylated chitins (chitosans). Carbohydr. Res. 217, 19–27 (1991).Article
PubMed
Google Scholar
Weinhold, M. X., Sauvageau, J. C. M., Kumirska, J. & Thöming, J. Studies on acetylation patterns of different chitosan preparations. Carbohydr. Polym. 78, 678–684 (2009).Article
CAS
Google Scholar
Kumirska, J. et al. Determination of the pattern of acetylation of chitosan samples: Comparison of evaluation methods and some validation parameters. Int. J. Biol. Macromol. 45, 56–60 (2009).Article
CAS
Google Scholar
Bovey, F. A. & Mirau, P. A. NMR of Polymers 1st edn, 459 (Academic Press, 1996).Sashiwa, H., Saimoto, H., Shigemasa, Y., Ogawa, R. & Tokura, S. Distribution of the acetamide group in partially deacetylated chitins. Carbohydr. Polym. 16, 291–296 (1991).Article
CAS
Google Scholar
Sashiwa, H., Saimoto, H., Shigemasa, Y. & Tokura, S. N-Acetyl group distribution in partially deacetylated chitins prepared under homogeneous conditions. Carbohydr. Res. 242, 167–172 (1993).Article
CAS
PubMed
Google Scholar
Aiba, S. Studies on chitosan: 3. Evidence for the presence of random and block copolymer structures in partially N-acetylated chitosans. Int. J. Biol. Macromol. 13, 40–44 (1991).Article
CAS
PubMed
Google Scholar
Aiba, S. Studies on chitosan: 4. Lysozymic hydrolysis of partially N-acetylated chitosans. Int. J. Biol. Macromol. 14, 225–228 (1992).Article
CAS
PubMed
Google Scholar
Pacheco, N. et al. Structural characterization of chitin and chitosan obtained by biological and chemical methods. Biomacromolecules 12, 3285–3290 (2011).Article
CAS
PubMed
Google Scholar
Ottøy, M. H., Vårum, K. M. & Smidsrød, O. Compositional heterogeneity of heterogeneously deacetylated chitosans. Carbohydr. Polym. 29, 17–24 (1996).Article
Google Scholar
Lamarque, G., Cretenet, M., Viton, C. & Domard, A. New route of deacetylation of α- and β-chitins by means of freeze−pump out−thaw cycles. Biomacromolecules 6, 1380–1388 (2005).Article
CAS
PubMed
Google Scholar
Wattjes, J. et al. Enzymatic production and enzymatic-mass spectrometric fingerprinting analysis of chitosan polymers with different nonrandom patterns of acetylation. J. Am. Chem. Soc. 141, 3137–3145 (2019).Article
CAS
PubMed
Google Scholar
Kohlhoff, M. et al. Chitinosanase: A fungal chitosan hydrolyzing enzyme with a new and unusually specific cleavage pattern. Carbohydr. Polym. 174, 1121–1128 (2017).Article
CAS
PubMed
Google Scholar
Sørbotten, A., Horn, S. J., Eijsink, V. G. H. & Vårum, K. M. Degradation of chitosans with chitinase B from Serratia marcescens. FEBS J. 272, 538–549 (2005).Article
PubMed
Google Scholar
Sasaki, C., Vårum, K. M., Itoh, Y., Tamoi, M. & Fukamizo, T. Rice chitinases: sugar recognition specificities of the individual subsites. Glycobiology 16, 1242–1250 (2006).Article
CAS
PubMed
Google Scholar
Heggset, E. B., Hoell, I. A., Kristoffersen, M., Eijsink, V. G. H. & Vårum, K. M. Degradation of chitosans with chitinase G from Streptomyces coelicolor A3(2): Production of chito-oligosaccharides and insight into subsite specificities. Biomacromolecules 10, 892–899 (2009).Article
CAS
PubMed
Google Scholar
Davies, G. J., Wilson, K. S. & Henrissat, B. Nomenclature for sugar-binding subsites in glycosyl hydrolases. Biochem. J. 321, 557–559 (1997).Article
CAS
PubMed
PubMed Central
Google Scholar
Hellmann, M. J., Moerschbacher, B. M. & Cord-Landwehr, S. Fast insights into chitosan-cleaving enzymes by simultaneous analysis of polymers and oligomers through size exclusion chromatography. Sci. Rep. 14, 1–11 (2024).Article
Google Scholar
Synowiecki, J. & Al-Khateeb, N. A. A. Q. Mycelia of Mucor rouxii as a source of chitin and chitosan. Food Chem. 60, 605–610 (1997).Article
CAS
Google Scholar
Hu, K.-J., Hu, J.-L., Ho, K.-P. & Yeung, K.-W. Screening of fungi for chitosan producers, and copper adsorption capacity of fungal chitosan and chitosanaceous materials. Carbohydr. Polym. 58, 45–52 (2004).Article
CAS
Google Scholar
Lecointe, K., Cornu, M., Leroy, J., Coulon, P. & Sendid, B. Polysaccharides cell wall architecture of Mucorales. Front. Microbiol. 10, 1–8 (2019).Article
Google Scholar
Weikert, T., Niehues, A., Cord-Landwehr, S., Hellmann, M. J. & Moerschbacher, B. M. Reassessment of chitosanase substrate specificities and classification. Nat. Commun. 8, 1698 (2017).Article
ADS
PubMed
PubMed Central
Google Scholar
Regel, E. K., Weikert, T., Niehues, A., Moerschbacher, B. M. & Singh, R. Protein‐engineering of chitosanase from Bacillus sp. MN to alter its substrate specificity. Biotechnol. Bioeng. 115, 863–873 (2018).Article
CAS
PubMed
Google Scholar
Gercke, D., Regel, E. K., Singh, R. & Moerschbacher, B. M. Rational protein design of Bacillus sp. MN chitosanase for altered substrate binding and production of specific chitosan oligomers. J. Biol. Eng. 13, 23 (2019).Article
PubMed
PubMed Central
Google Scholar
Bußwinkel, F., Goñi, O., Cord-Landwehr, S., O’Connell, S. & Moerschbacher, B. M. Endochitinase 1 (Tv-ECH1) from Trichoderma virens has high subsite specificities for acetylated units when acting on chitosans. Int. J. Biol. Macromol. 114, 453–461 (2018).Article
PubMed
Google Scholar
Eide, K. B. et al. Human chitotriosidase-catalyzed hydrolysis of chitosan. Biochemistry 51, 487–495 (2012).Article
CAS
PubMed
Google Scholar
Eide, K. B., Lindbom, A. R., Eijsink, V. G. H., Norberg, A. L. & Sørlie, M. Analysis of productive binding modes in the human chitotriosidase. FEBS Lett. 587, 3508–3513 (2013).Article
CAS
PubMed
Google Scholar
Gorzelanny, C., Pöppelmann, B., Pappelbaum, K., Moerschbacher, B. M. & Schneider, S. W. Human macrophage activation triggered by chitotriosidase-mediated chitin and chitosan degradation. Biomaterials 31, 8556–8563 (2010).Article
CAS
PubMed
Google Scholar
Vårum, K. M. & Ottøy, M. H. & Smidsrød, O. Acid hydrolysis of chitosans. Carbohydr. Polym. 46, 89–98 (2001).Einbu, A., Grasdalen, H. & Vårum, K. M. Kinetics of hydrolysis of chitin/chitosan oligomers in concentrated hydrochloric acid. Carbohydr. Res. 342, 1055–1062 (2007).Article
CAS
PubMed
Google Scholar
Hussain, I., Singh, T. & Chittenden, C. Preparation of chitosan oligomers and characterization: their antifungal activities and decay resistance. Holzforschung 66, 119–125 (2012).Article
CAS
Google Scholar
Gorbet, M. B. & Sefton, M. V. Endotoxin: The uninvited guest. Biomaterials 26, 6811–6817 (2005).Article
CAS
PubMed
Google Scholar
Richter, C., Cord-Landwehr, S., Singh, R. & Moerschbacher, B. M. Dissecting and finetuning bioactivities of chitosans by enzymatic modification. Carbohydr. Polym. (submitted in parallel to this manuscript).Bahrke, S. et al. Sequence analysis of chitooligosaccharides by matrix-assisted laser desorption ionization postsource decay mass spectrometry. Biomacromolecules 3, 696–704 (2002).Article
CAS
PubMed
Google Scholar
Tabata, E. et al. Residues of acidic chitinase cause chitinolytic activity degrading chitosan in porcine pepsin preparations. Sci. Rep. 9, 15609 (2019).Article
ADS
PubMed
PubMed Central
Google Scholar
Wakita, S. et al. Mouse acidic chitinase effectively degrades random-type chitosan to chitooligosaccharides of variable lengths under stomach and lung tissue pH conditions. Molecules 26, 6706 (2021).Article
CAS
PubMed
PubMed Central
Google Scholar
Sannan, T., Kurita, K. & Iwakura, Y. Studies on chitin, 2: Effect of deacetylation on solubility. Die Makromol. Chem. 177, 3589–3600 (1976).Article
CAS
Google Scholar
Jiang, C. J. & Xu, M. Q. Kinetics of heterogeneous deacetylation of β-chitin. Chem. Eng. Technol. 29, 511–516 (2006).Article
CAS
Google Scholar
de Souza, J. R. & Giudici, R. Effect of diffusional limitations on the kinetics of deacetylation of chitin/chitosan. Carbohydr. Polym. 254, 117278 (2021).Article
PubMed
Google Scholar
Roberts, G. A. F. in Advances in Chitin Science Vol. II (eds. Domard, A., Roberts, G. A. F. & Vårum, K. M.) 22–31 (Jaques André, 1997).Novikov, V. Y., Derkach, S. R., Konovalova, I. N., Dolgopyatova, N. V. & Kuchina, Y. A. Mechanism of heterogeneous alkaline deacetylation of chitin: A review. Polymers 15, 1–23 (2023).Article
Google Scholar
Lamarque, G., Chaussard, G. & Domard, A. Thermodynamic aspects of the heterogeneous deacetylation of β-chitin: Reaction mechanisms. Biomacromolecules 8, 1942–1950 (2007).Article
CAS
PubMed
Google Scholar
Sreekumar, S. et al. Biotechnologically produced chitosans with nonrandom acetylation patterns differ from conventional chitosans in properties and activities. Nat. Commun. 13, 7125 (2022).Article
ADS
CAS
PubMed
PubMed Central
Google Scholar
Basa, S. et al. The pattern of acetylation defines the priming activity of chitosan tetramers. J. Am. Chem. Soc. 142, 1975–1986 (2020).Article
CAS
PubMed
Google Scholar
Urs, M. J., Moerschbacher, B. M. & Cord-Landwehr, S. Quantitative enzymatic-mass spectrometric analysis of the chitinous polymers in fungal cell walls. Carbohydr. Polym. 301, 120304 (2023).Article
CAS
PubMed
Google Scholar
van Leeuwe, T. M. et al. A seven-membered cell wall related transglycosylase gene family in Aspergillus niger is relevant for cell wall integrity in cell wall mutants with reduced α-glucan or galactomannan. Cell Surf. 6, 100039 (2020).Article
PubMed
PubMed Central
Google Scholar
Moussa, A., Crépet, A., Ladavière, C. & Trombotto, S. Reducing-end “clickable” functionalizations of chitosan oligomers for the synthesis of chitosan-based diblock copolymers. Carbohydr. Polym. 219, 387–394 (2019).Article
CAS
PubMed
Google Scholar
Kösters, M. et al. pymzML v2.0: introducing a highly compressed and seekable gzip format. Bioinformatics 34, 2513–2514 (2018).Article
PubMed
Google Scholar
Lemke, P., Moerschbacher, B. M. & Singh, R. Transcriptome analysis of Solanum tuberosum genotype RH89-039-16 in response to chitosan. Front. Plant Sci. 11, 1–18 (2020).Article
Google Scholar
Hellmann, M. J., Moerschbacher, B. M. & Cord‐Landwehr, S. LCP simulator: An easy-to-use web tool to simulate binary linear copolymers and their behavior during analysis and enzymatic cleavage. SSRN Prepr. https://doi.org/10.2139/ssrn.4709938 (2024).