Biomimetic mineralization of collagen fibrils is an essential process because the mineralized collagen fibers constitute the basic building block of natural bone. To overcome the limited availability and high cost of the noncollagenous proteins (NCPs) that regulate the mineralization process of collagen, commercially available analogues were developed to replicate sequestration and templating functions of NCPs. The use of branched polymers in intrafibrillar mineralization applications has never been explored. In this work, two novel carboxyl-rich brushlike polymers, a carboxylated polyethylene glycol terpolymer (PEG-COOH) and a polyethylene glycol/poly(acrylic acid) copolymer (PEG-PAA), were synthesized and modified to mimic the sequestration function of NCPs to induce intrafibrillar mineralization of collagen fibrils. It was found that these synthetic brushlike polymers are able to induce intrafibrillar mineralization by stabilizing the amorphous calcium phosphate (ACP) nanoprecursors and subsequently facilitating the infiltration of ACP into the gap zone of collagen microfibrils. Moreover, the weight ratios of mineral to collagen in the mineralized collagen fibrils in the presence of these brushlike polymers were 2.17 ± 0.07 for PEG-COOH and 2.23 ± 0.03 for PEG-PAA, while it is only 1.81 ± 0.21 for linear PAA. Plausible mineralization mechanisms using brushlike polymers are proposed that offer significant insight into the understanding of collagen mineralization induced by synthetic NCP analogues.
Keywords: biomimetic mineralization; brush polymer; collagen; intrafibrillar and extrafibrillar; mineralization mechanism; poly(acrylic acid); polyethylene glycol.