The proposed PhD thesis aims at optimizing ⁴³Ca DNP NMR for the analysis of Ca environments in synthetic biomaterials, and then extending this new technique to the in-depth study of bones of normal and genetically engineered mice, in view of expanding our understanding of human bone pathologies. Moreover, the investigation of other poorly-sensitive cations of biological relevance (Mg²⁺, K⁺ ) using these new DNP methods will be looked into, to gain additional information on the structure of biomaterials.