It is increasingly popular for titanium and its alloys to be utilized as the medical implants. However, their bio-inert nature and lack of antibacterial ability limit their applications. In this work, by utilizing plasma immersion ion implantation and deposition (PIII&D) technology, the titanium surface was modified by C/Cu co-implantation. The mechanical property, corrosion resistance, antibacterial ability and cytocompatibility of modified samples were studied. Results indicate that after C/Cu co-implantation, copper nanoparticles were observed on the surface of titanium, and titanium carbide existed on the near surface region of titanium. The modified surface displayed good mechanical property and corrosion resistance. The Cu/C galvanic corrosion existed on the titanium surface implanted by C/Cu dual ions, and release of copper ions can be effectively controlled by the galvanic corrosion effect. Moreover, improved antibacterial performance of titanium surface can be achieved without cytotoxicity.

Ds-block elements have been gaining increasing attention in the field of biomaterials modification, owing to their excellent biological properties, such as antibiosis, osteogenesis, etc. However, their function mechanisms are not well understood and conflicting conclusions were drawn by previous studies on this issue, which are mainly resulted from the inconsistent experimental conditions. In this work, three most widely used ds-block elements, copper, zinc, and silver were introduced on titanium substrate by plasma immersion ion implantation method to investigate the rule of ds-block elements in the immune responses. Results showed that the implanted samples could decrease the inflammatory responses compared with Ti sample. The trend of anti-inflammatory effects of macrophages on samples was in correlation with cellular ROS levels, which was induced by the implanted biomaterials and positively correlated with the number of valence electrons of ds-block elements. The co-culture experiments of macrophages and bone marrow mesenchymal stem cells showed that these two kinds of cells could enhance the anti-inflammation and osteogenesis of samples by the paracrine manner of PGE2. In general, in their steady states on titanium substrate (Cu2+, Zn2+, Ag), the ds-block elements with more valence electrons exhibit better anti-inflammatory and osteogenic effects. Moreover, molecular biology experiments indicate that the PGE2-related signaling pathway may contribute to the desired immunoregulation and osteoinduction capability of ds-block elements. These findings suggest a correlation between the number of valence electrons of ds-block elements and the relevant biological responses, which provides new insight into the selection of implanted ions and surface design of biomaterials.