Solution-processed hybrid perovskite of CH3NH3PbI3 (MAPbI3) exhibits an abnormal luminescence behavior at around the tetragonal-orthorhombic phase transition temperature. The combination of time resolved photoluminescence (PL), variable excitation power PL, and variable-temperature X-ray diffraction (XRD) allows us to clearly interpret the abnormal luminescence features in the phase transition region of MAPbI3. Both PL and XRD results unambiguously prove the coexistence of the tetragonal and orthorhombic phases of MAPbI3 in the temperature range of 150 to 130 K. The two luminescence features observed in the orthorhombic phase at T < 130 K originate from free excitons and donor-acceptor-pair (DAP) transitions, respectively. The comprehensive understanding of optical properties upon phase transition in MAPbI3 will benefit the development of new optoelectronic devices.

Effective bone tissue engineering can restore bone and skeletal functions that are impaired by traumas and/or certain medical conditions. Bone is a complex tissue and functions through orchestrated interactions between cells, biomechanical forces, and biofactors. To identify ideal scaffold materials for effective mesenchymal stem cell (MSC)-based bone tissue regeneration, here we develop and characterize a composite nanoparticle hydrogel by combining carboxymethyl chitosan (CMCh) and amorphous calcium phosphate (ACP) (designated as CMCh-ACP hydrogel). We demonstrate that the CMCh-ACP hydrogel is readily prepared by incorporating glucono δ-lactone (GDL) into an aqueous dispersion or rehydrating the acidic freeze-dried nanoparticles in a pH-triggered controlled-assembly fashion. The CMCh-ACP hydrogel exhibits excellent biocompatibility and effectively supports MSC proliferation and cell adhesion. Moreover, while augmenting BMP9-induced osteogenic differentiation, the CMCh-ACP hydrogel itself is osteoinductive and induces the expression of osteoblastic regulators and bone markers in MSCs in vitro. The CMCh-ACP scaffold markedly enhances the efficiency and maturity of BMP9-induced bone formation in vivo, while suppressing bone resorption occurred in long-term ectopic osteogenesis. Thus, these results suggest that the pH-responsive self-assembled CMCh-ACP injectable and bioprintable hydrogel may be further exploited as a novel scaffold for osteoprogenitor-cell-based bone tissue regeneration.