Synthesis of Sugar-Substituted Poly(phenylenevinylene)s

Abstract

Sugar-containing PPVs, poly{2-[O-(2-acetamido-2-deoxy-beta-D-glucopyranosyl)]-5-methoxy-p-phenylenevinylene-alt-p-phenylenevinylene} (PPV-GlcNAc) and poly{2,5-bis-[O-(beta-d-glucopyranosyl)]-p-phenylenevinylene-alt-p-phenylenevinylene} (PPV-Glc(2)), were synthesized via Heck reaction of p-divinylbenzene (DVB) with O-glycosylated hydroquinones, 2,5-dibromo-4-methoxyphenyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-beta-D-glucopyranoside (3) and 1,4-bis(O-2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl)-2,5-dibromobenzene (6), respectively. Acetyl protecting groups of the PPVs are completely removable under mild conditions (yield 69-87%). The structures were confirmed using (1)H NMR and IR spectra. Size exclusion chromatography (SEC) (eluent: DMF, polystyrene standards) measurements indicated that respective M(n) and M(w)/M(n) values of the obtained polymers are 4.49 x 10(3) and 2.3(5) (PPV-GlcNAc) and 3.86 x 10(3) and 1.3(9) (PPV-Glc(2)). These sugar-containing PPVs are soluble in water/DMF (8/2, v/v) and are recognized by Concanavalin A (Con A), D-glucose-binding protein. Blue shift of lambda(max) of the conjugated polymer backbone was confirmed when the glucose-substituted PPV interacts with Con A. Based on those binding properties, these results revealed that the obtained PPVs with pendant sugars have capabilities for detection of biological stimuli.

Triphenylamine-based fluorescent conjugated glycopolymers: Synthesis, characterization and interactions with lectins

“…However, they show solubility in DMF, DMSO and HEPES buffer/DMF (8/2, v/v) as well. Similar results were reported by Takasu and coworkers [18] for sugar-carrying poly (phenylene-vinylene).…”

“…In particular, fluorescent conjugated glycopolymers that possess both fluorescent scaffolding and reporting carbohydrate ligands are attractively used in carbohydrate-protein interaction studies and biosensor applications because of their intrinsic optical properties, high sensitivities to minor stimuli, and good biocompatibilities [9][10][11][12][13]. A few conjugated polymers, such as polythiophene [10,11], polyfluorene [12], poly(p-phenylene-ethynylene) [13][14][15][16][17], poly(phenylene-vinylene) [18], and poly(p-phenylene) [19], have been chosen to design this type of multivalent glycoconjugates. One approach to such a system is represented by the polymerization or copolymerization of well-defined carbohydrate-carrying monomers through classical C-C coupling reactions [10,13,[15][16][17][18].…”

“…A few conjugated polymers, such as polythiophene [10,11], polyfluorene [12], poly(p-phenylene-ethynylene) [13][14][15][16][17], poly(phenylene-vinylene) [18], and poly(p-phenylene) [19], have been chosen to design this type of multivalent glycoconjugates. One approach to such a system is represented by the polymerization or copolymerization of well-defined carbohydrate-carrying monomers through classical C-C coupling reactions [10,13,[15][16][17][18]. Another synthetic approach is the so-called postpolymerization functionalization, in which sugar moieties are grafted to the backbones after the formation of conjugated polymers [11,12,14,19].…”

Conjugated Polymers as Optical Probes for Protein Interactions and Protein Conformations

“…[12] More recently solutionbased colorimetric detection principles using glycosubstituted polythiophenes interacting with E. coli, lectins, and influenza virus, [13] and sugar-substitued poly(phenylene vinylene) to detect lectin has been demonstrated (see Figure 2). [14] Apart from glycosubstituents, a favorable covalent modification of a CP for sensor applications is the attachment of biotin as a side chain. The binding between biotin and avidin or streptavidin is one of the strongest biological non-covalent interactions known.…”

Supramolecular Recognition of Escherichia coli Bacteria by Fluorescent Oligo(Phenyleneethynylene)s with Mannopyranoside Termini Groups

“…With respect to fluorescence detection of Escherichia coli , conjugated polymers such as poly(phenylene)s [5], poly(fluorene)s [6], poly(phenyleneethynylene)s (PE) [7,8,9,10,11], poly(thiophene)s [12], poly(phenylenevinylidene)s [13] functionalized with mannose or other carbohydrates were reported. All of these works demonstrate the specificity of the molecules to uropathogenic Escherichia coli compared to other bacteria or even other E. coli strains that do not express type 1 fimbriae.…”