Synthesis and characterization of hydroxy‐bisphosphonate micrometer‐sized particles by dispersion polymerization of a new styrylbisphosphonate monomer

Abstract

Bisphosphonates (BPs) are nonhydrolyzable pyrophosphate (P‐O‐P) analogs possessing two phosphonate groups linked to a single carbon (P‐C‐P). The hydroxy‐bisphosphonates (hydroxyBPs) are obtained when the hydroxy group is also linked to this bridging carbon. Their ability to form bidentate or tridentate chelates with calcium ions results in a high affinity to hydroxyapatite (HAP) in dentin, enamel and bones. In this study, we designed and prepared crosslinked poly(styrylbisphosphonate) (PStBP) micrometer‐sized particles by dispersion polymerization of the styrylbisphosphonate (StBP) and ethylene glycol dimethacrylate (EDMA) monomers. The new StBP monomer was synthesized in an efficient one‐pot synthesis using tris(trimethylsilyl)phosphite as the phosphorus source followed by methanolysis. The StBP monomer was successfully isolated and characterized as tri‐sodium salt. Polymerization of the StBP monomer was carried out in two steps: in situ conversion of the tri‐sodium StBP monomer back to its acid form, followed by radical dispersion polymerization in the presence of the crosslinker EDMA monomer. The resulting crosslinked PStBP micrometer‐sized particles retained the unique high affinity of the hydroxy‐bisphosphonate side groups to calcium ions and exhibited good adhesive properties to HAP. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

New biodegradable bisphosphonate vinylic monomers and near infrared fluorescent nanoparticles for biomedical applications

“…In our laboratory, a number of new BP vinylic monomers were synthesized, some via direct C–P bonds, in the absence of an amide bond, each monomer has different properties and can be used in numerous fields (Fig. ) . This synthesis of various vinylic monomers was the outcome of an ongoing research in the field of biodegradable polymers and molecules …”

Engineering of new crosslinked near-infrared fluorescent polyethylene glycol bisphosphonate nanoparticles for bone targeting

“…In our previous studies, we reported on the synthesis of new bisphosphonate vinylic monomers: styryl BP and PEG methacrylate BP (MA‐PEG‐BP) and formation of micrometer‐sized particles prepared from these monomer . This manuscript describes the synthesis and characterization of NIR fluorescent crosslinked BP nanoparticles for bone imaging and targeting.…”

One‐Pot Synthesis of Selected P‐Vinylbenzyls under Solvent‐Free Conditions

“…[5][6][7] Despite its remarkable value, only a few syntheses strategies have been developed for the preparation of phosphorylated or phosphonylated vinylbenzyls, and related molecules. [5][6][7][8]13,[15][16][17][18][19][20] The aforementioned compounds' syntheses were realized by the formation of the bond between phosphorus with benzyl carbon atoms via nucleophilic substitution adapting Michaelis-Arbuzov or Michaelis-Becker reaction (Scheme 1).…”

“…[2][3][4] Phosphonated polymers have been demonstrated strong adsorption to tooth enamel which could be used as a new type of restorative material or act as an effective adhesive between conventional polymeric restorative materials and the tooth. [5][6][7][8] Phosphoruscontaining polymers also improve the flame retardant properties of materials. [9][10][11] The phosphonated polymers have been used for metal separation or metal sorption from solutions.…”