Visualization of Collagen–Mineral Arrangement Using Atom Probe Tomography

Bone is a functional material comprised of mainly two phases: an organic collagenous phase and an inorganic mineral phase. Collagen-mineral arrangement has implications for bone function, aging, and disease. However, theories on collagen-mineral arrangement have been confined to studies with low spatial and/or compositional resolution resulting in an extensive debate over the location of mineral with respect to collagen. Herein, a strategy is developed to extract a single mineralized collagen fibril from bone and analyze its composition and structure atom-by-atom with 3D sub-nanometer accuracy and compositional clarity using atom probe tomography (APT). It is shown for the first time a method to probe fibril-level mineralization and collagen-mineral arrangement from an in vivo system with both the spatial and compositional precision required to comment on nanoscale collagen-mineral arrangement. APT of leporine bone shows distinct and helical collagen fibrils with mineralized deposits both encapsulating and incorporated into the collagenous structures. This study demonstrates a novel fibril-level detection method that can be used to probe the composition of bone and contribute new insights to the structure and organization of mineralized materials such as bones and teeth.