“…While organic biomaterials including gelatin, [44,45] chitosan, [46] hyaluronic acid, collagen, [47] and alginate as well as synthetic polymers such as poly(lactic acid) (PLA), poly(glycolic acid)(PGA), poly(propylene fumarate) (PPF), and poly(caprolactone) (PCL) have been extensively studied, successful incorporation of biomimetic levels of ceramic has remained elusive, with significant instances of phase separation, brittleness and mechanical failure, and poor in vivo integration and regeneration. [24,[48][49][50][51][52] Modification strategies to one or both phases, such as conjugation of ceramic binding groups to polymer chains or surface modification of ceramics with lactic acid oligomers, [53] isocyanates, [54] poly(amino acids), catechols, [52,55] or silanes have resulted in enhanced physical properties; however, such processes are inherently limited due to the low reactivity of ceramic surface groups and increase both cost and complexity, motivating the search for composite systems with inherent biomimetic structures. [52,56] Citrate has emerged as a critical structural component of native bone, comprising 5% by weight and covering 1/6 of the inorganic bone surface, strongly associating with both the fibrous collagen organic phase and amorphous calcium phosphate (ACP) inorganic phase during bone formation, decreasing surface binding energy between the two phases and facilitating intra-and interfibrillar mineralization.…”