Microspheres are one type of promising cell‐supporting matrices. However, the synthesis of nanofibrous and hollow microspheres as drug‐laden cell carriers is still a great challenge. Here, the nanofibrous and hollow titania nanowire (NH‐TiNW) microspheres were synthesized by in situ alkali hydrothermal treatment of hollow titania (H‐Ti) microspheres, and their microstructure, biocompatibility, and drug delivery property were evaluated. By controlling hydrothermal temperature from 80 to 120°C and hydrothermal time from 1 to 4 h, the surface of H‐Ti microspheres was controllably tailored with nanoparticles and NWs. The results showed that NH‐TiNW microspheres were spherical in morphology with a diameter of 100–200 µm, hierarchically assembled by numerous TiNWs with the diameter of 10–20 nm, and possessed a nanofibrous and hollow structure. In vitro biocompatibility evaluation showed that NH‐TiNW microspheres presented an enhanced cell attachment and proliferation compared with H‐Ti microspheres due to the presence of the nanofibrous surface. Drug delivery evaluation showed that NH‐TiNW microspheres strongly adsorbed tetracycline hydrochloride (one type of antibiotic, model drug) with a loading efficiency of 81.5% ± 1% due to the presence of the nanofibrous and hollow structure and also effectively maintained the biological efficiency of the loaded drugs to inhibit the growth of bacteria.
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