title: Crosslinking of Chitosan with Dialdehyde Derivatives of Nucleosides and Nucleotides. Mechanism and Comparison with Glutaraldehyde.
abstract: In medical and pharmaceutical applications, chitosan is used as a component of hydrogels-macromolecular networks swollen in water. Chemical hydrogels are formed by covalent links between the crosslinking reagents and amino functionalities of chitosan. To date, the most commonly used chitosan crosslinkers are dialdehydes, such as glutaraldehyde (GA). We have developed novel GA like crosslinkers with additional functional groups-dialdehyde derivatives of uridine (oUrd) and nucleotides (oUMP and oAMP)-leading to chitosan-based biomaterials with new properties. The process of chitosan crosslinking was investigated in details and compared to crosslinking with GA. The rates of crosslinking with oUMP, oAMP, and GA were essentially the same, though much higher than in the case of oUrd. The remarkable difference in the crosslinking properties of nucleoside and nucleotide dialdehydes can be clearly attributed to the presence of the phosphate group in nucleotides that participates in the gelation process through ionic interactions with the amino groups of chitosan. Using NMR spectroscopy, we have not observed the formation of aldimine bonds. It can be concluded that the real number of crosslinks needed to cause gelation of chitosan chains may be less than 1%.
authors: a Engelhardt Institute of Molecular Biology, Russian Academy of Sciences , Vavilov St 32, Moscow 119991 , Russia.
authors: Sergey N
authors: SN
authors: Mikhailov
authors: a Engelhardt Institute of Molecular Biology, Russian Academy of Sciences , Vavilov St 32, Moscow 119991 , Russia.
authors: Alexandra N
authors: AN
authors: Zakharova
authors: a Engelhardt Institute of Molecular Biology, Russian Academy of Sciences , Vavilov St 32, Moscow 119991 , Russia.
authors: Mikhail S
authors: MS
authors: Drenichev
authors: a Engelhardt Institute of Molecular Biology, Russian Academy of Sciences , Vavilov St 32, Moscow 119991 , Russia.
authors: Andrey V
authors: AV
authors: Ershov
authors: b Department of Chemical Technology and Industrial Ecology , Moscow State University of Design and Technology , Sadovnicheskaya St 33/1, Moscow 117997 , Russia.
authors: Mariya A
authors: MA
authors: Kasatkina
authors: c Semenov Institute of Chemical Physics, Russian Academy of Sciences , Kosygin St 4, Moscow 119991 , Russia.
authors: Leonid V
authors: LV
authors: Vladimirov
authors: d Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , Vavilov St 28, Moscow 119991 , Russia.
authors: Valentin V
authors: VV
authors: Novikov
authors: b Department of Chemical Technology and Industrial Ecology , Moscow State University of Design and Technology , Sadovnicheskaya St 33/1, Moscow 117997 , Russia.
authors: Natalia R
authors: NR
authors: Kildeeva
mesh_terms: D000249:Adenosine Monophosphate / Q000031:analogs & derivatives; D001672:Biocompatible Materials / Q000737:chemistry*; D048271:Chitosan / Q000737:chemistry*; D003432:Cross-Linking Reagents / Q000737:chemistry*; D005782:Gels / Q000737:chemistry; D005976:Glutaral / Q000031:analogs & derivatives* / Q000737:chemistry; D009705:Nucleosides / Q000737:chemistry*; D009711:Nucleotides / Q000737:chemistry*; D014529:Uridine / Q000031:analogs & derivatives; D014542:Uridine Monophosphate / Q000031:analogs & derivatives
chemical_list: D001672:Biocompatible Materials; D003432:Cross-Linking Reagents; D005782:Gels; D009705:Nucleosides; D009711:Nucleotides; D000249:Adenosine Monophosphate; D048271:Chitosan; D014542:Uridine Monophosphate; D005976:Glutaral; D014529:Uridine
keywords: Chitosan; crosslinking; dialdehyde derivatives; gelation; nucleoside; nucleotide