title: Facile and Efficient Preparation of Tri-component Fluorescent Glycopolymers via RAFT-controlled Polymerization.
abstract: Synthetic glycopolymers are instrumental and versatile tools used in various biochemical and biomedical research fields. An example of a facile and efficient synthesis of well-controlled fluorescent statistical glycopolymers using reversible addition-fragmentation chain-transfer (RAFT)-based polymerization is demonstrated. The synthesis starts with the preparation of β-galactose-containing glycomonomer 2-lactobionamidoethyl methacrylamide obtained by reaction of lactobionolactone and N-(2-aminoethyl) methacrylamide (AEMA). 2-Gluconamidoethyl methacrylamide (GAEMA) is used as a structural analog lacking a terminal β-galactoside. The following RAFT-mediated copolymerization reaction involves three different monomers: N-(2-hydroxyethyl) acrylamide as spacer, AEMA as target for further fluorescence labeling, and the glycomonomers. Tolerant of aqueous systems, the RAFT agent used in the reaction is (4-cyanopentanoic acid)-4-dithiobenzoate. Low dispersities (≤1.32), predictable copolymer compositions, and high reproducibility of the polymerizations were observed among the products. Fluorescent polymers are obtained by modifying the glycopolymers with carboxyfluorescein succinimidyl ester targeting the primary amine functional groups on AEMA. Lectin-binding specificities of the resulting glycopolymers are verified by testing with corresponding agarose beads coated with specific glycoepitope recognizing lectins. Because of the ease of the synthesis, the tight control of the product compositions and the good reproducibility of the reaction, this protocol can be translated towards preparation of other RAFT-based glycopolymers with specific structures and compositions, as desired.
authors.affiliation: Department of Biochemistry, University of Missouri.
authors.forename: Wei
authors.initials: W
authors.lastname: Wang
authors.affiliation: Department of Biochemistry, University of Missouri.
authors.forename: John M
authors.initials: JM
authors.lastname: Lester
authors.affiliation: Department of Biological Sciences, University of Missouri.
authors.forename: Anthony E
authors.initials: AE
authors.lastname: Amorosa
authors.affiliation: Department of Molecular Microbiology & Immunology, University of Missouri.
authors.forename: Deborah L
authors.initials: DL
authors.lastname: Chance
authors.affiliation: Department of Biochemistry, University of Missouri.
authors.forename: Valeri V
authors.initials: VV
authors.lastname: Mossine
authors.affiliation: Department of Biochemistry, University of Missouri; Department of Child Health, University of Missouri; MawhinneyT@missouri.edu.
authors.forename: Thomas P
authors.initials: TP
authors.lastname: Mawhinney
mesh_terms: D000178:Acrylamides / Q000737:chemistry; D005456:Fluorescent Dyes / Q000138:chemical synthesis*; D005690:Galactose / Q000031:analogs & derivatives* / Q000737:chemistry; D008689:Methacrylates / Q000138:chemical synthesis* / Q000737:chemistry; D058105:Polymerization; D011108:Polymers / Q000138:chemical synthesis*
chemical_list: D000178:Acrylamides; D005456:Fluorescent Dyes; D008689:Methacrylates; D011108:Polymers; D005690:Galactose