Atomic scale investigation and cytocompatibility of copper and zinc-loaded phosphate-based glasses prepared by coacervation

Abstract

Phosphate-based glasses (PBGs) are bioresorbable materials that find application in the field of controlled drug delivery and tissue engineering. The structural arrangements of the phosphate units in PBGs, along with the knowledge of how therapeutic metallic ions are embedded in the phosphate network are important in understanding the degradation and targeted release properties of these materials. Using a combination of Raman spectroscopy, high-energy X-ray diffraction and ³¹P and ²³Na solid-state magic angle spinning nuclear magnetic resonance, the atomic structure of coacervate PBGs in the system P₂O₅-CaO-Na₂O-MO_x (M = Cu or Zn) with loadings of 2, 10 and 15 mol % of M²⁺ have been studied as functions of composition and calcination temperature. After drying at room temperature, the structures of the phosphate network in PBG-Cu and PBG-Zn are quite similar, with that of PBG-Zn exhibiting slightly higher connectivity. Heating at 300 °C causes degradation of the polyphosphate chains, even though Q² species remain predominant. X-ray photoelectron spectroscopy demonstrates that Cu in calcined PBGs is present in both oxidation states +1 and +2, with a predominance of the +2 state. Cu and Zn ion release data after 24 h exposure of PBGs in deionized water and cell medium DMEM show that release is proportional to their loadings. Cytotoxicity MTT assays of dissolution products of PBG-Cu/ZnX calcined at 300 °C on human osteosarcoma cells (MG-63) and on human skin cells (HaCaTs) showed good cellular response for all compositions, indicating that PBGs have great potential for both hard and soft tissue regeneration.