Excited-state charge polarization and electronic structure of mixed-cation halide perovskites: the role of mixed inorganic-organic cations in CsFAPbI3.

Mixed-cation perovskite materials have shown great potential for sunlight harvesting and have surpassed unmixed perovskite materials in solar cell efficiency and stability. The role of mixed monovalent cations in the enhanced optoelectronic properties and excited state response, however, are still elusive from a theoretical perspective. Herein, through time dependent density functional theory calculations of mixed cation perovskites, we report the electronic structure of Cs formamidinium (FA) mixed cationic lead iodide (Cs0.17FA0.87PbI3) in comparison to the corresponding single monovalent cation hybrid perovskite. The results show that the Cs0.17FA0.87PbI3 and FAPbI3 had negligible differences in the optical band gap, and partial and total density of states in comparison to a single cation perovskite, while the effective mass of carriers, the local atomic density of states, the directional transport, and the structural distortions were significantly different. A lattice-distortion-induced asymmetry in the ground-state charge density is found, and originates from the co-location of caesium atoms in the lattice and signifies the effect on the charge density upon cation mixing and corresponding symmetry breaking. The excited-state charge response and induced polarizabilities are quantified, and discussed in terms of their importance for effective light absorption, charge separation, and final solar cell performance. We also quantify the impact of such polarizabilities on the dynamics of the structure of the perovskites and the implications this has for hot carrier cooling. The results shed light on the mechanism and origin of the enhanced performance in mixed-cation perovskite-based devices and their merits in comparison to single cation perovskites.

Tin-based halide perovskite materials: properties and applications.

Organic-inorganic hybrid halide perovskite materials have attracted considerable research interest, especially for photovoltaics. In addition, their scope has been extended towards light-emitting devices, photodetectors, or detectors. However, the toxicity of lead (Pb) element in perovskite compositions limits their applications. Therefore, a tremendous research effort on replacing is underway. More specifically, tin-based perovskites have shown the highest potential for this purpose. However, many challenges remain before these materials reach the goals of stability, safety, and eventually commercial application. This perspective considers many aspects and the critical development possibilities of tin-based perovskites, including drawbacks and challenges based on their physical properties. Additionally, it provides insights for future device applications that go beyond solar cells. Finally, the existing challenges and opportunities in tin-based perovskites are discussed.

Dedoping of Lead Halide Perovskites Incorporating Monovalent Cations.

We report significant improvements in the optoelectronic properties of lead halide perovskites with the addition of monovalent ions with ionic radii close to Pb2+. We investigate the chemical distribution and electronic structure of solution processed CH3NH3PbI3 perovskite structures containing Na+, Cu+, and Ag+, which are lower valence metal ions than Pb2+ but have similar ionic radii. Synchrotron X-ray diffraction reveals a pronounced shift in the main perovskite peaks for the monovalent cation-based films, suggesting incorporation of these cations into the perovskite lattice as well as a preferential crystal growth in Ag+ containing perovskite structures. Furthermore, the synchrotron X-ray photoelectron measurements show a significant change in the valence band position for Cu- and Ag-doped films, although the perovskite bandgap remains the same, indicating a shift in the Fermi level position toward the middle of the bandgap. Such a shift infers that incorporation of these monovalent cations dedope the n-type perovskite films when formed without added cations. This dedoping effect leads to cleaner bandgaps as reflected by the lower energetic disorder in the monovalent cation-doped perovskite thin films as compared to pristine films. We also find that in contrast to Ag+ and Cu+, Na+ locates mainly at the grain boundaries and surfaces. Our theoretical calculations confirm the observed shifts in X-ray diffraction peaks and Fermi level as well as absence of intrabandgap states upon energetically favorable doping of perovskite lattice by the monovalent cations. We also model a significant change in the local structure, chemical bonding of metal-halide, and the electronic structure in the doped perovskites. In summary, our work highlights the local chemistry and influence of monovalent cation dopants on crystallization and the electronic structure in the doped perovskite thin films.

Multifunctional Gadolinium-Doped Mesoporous TiO2 Nanobeads: Photoluminescence, Enhanced Spin Relaxation, and Reactive Oxygen Species Photogeneration, Beneficial for Cancer Diagnosis and Treatment.

Materials with controllable multifunctional abilities for optical imaging (OI) and magnetic resonant imaging (MRI) that also can be used in photodynamic therapy are very interesting for future applications. Mesoporous TiO2 sub-micrometer particles are doped with gadolinium to improve photoluminescence functionality and spin relaxation for MRI, with the added benefit of enhanced generation of reactive oxygen species (ROS). The Gd-doped TiO2 exhibits red emission at 637 nm that is beneficial for OI and significantly improves MRI relaxation times, with a beneficial decrease in spin-lattice and spin-spin relaxation times. Density functional theory calculations show that Gd3+ ions introduce impurity energy levels inside the bandgap of anatase TiO2 , and also create dipoles that are beneficial for charge separation and decreased electron-hole recombination in the doped lattice. The Gd-doped TiO2 nanobeads (NBs) show enhanced ability for ROS monitored via • OH radical photogeneration, in comparison with undoped TiO2 nanobeads and TiO2 P25, for Gd-doping up to 10%. Cellular internalization and biocompatibility of TiO2 @xGd NBs are tested in vitro on MG-63 human osteosarcoma cells, showing full biocompatibility. After photoactivation of the particles, anticancer trace by means of ROS photogeneration is observed just after 3 min irradiation.

Biocompatibility of different nanostructured TiO2 scaffolds and their potential for urologic applications.

Despite great efforts in tissue engineering of the ureter, urinary bladder, and urethra, further research is needed in order to improve the patient's quality of life and minimize the economic burden of different lower urinary tract disorders. The nanostructured titanium dioxide (TiO2) scaffolds have a wide range of clinical applications and are already widely used in orthopedic or dental medicine. The current study was conducted to synthesize TiO2 nanotubes by the anodization method and TiO2 nanowires and nanospheres by the chemical vapor deposition method. These scaffolds were characterized with scanning electron microscopy (SEM) and X-ray diffraction (XRD) methods. In order to test the urologic applicability of generated TiO2 scaffolds, we seeded the normal porcine urothelial (NPU) cells on TiO2 nanotubes, TiO2 nanowires, TiO2 nanospheres, and on the standard porous membrane. The viability and growth of the cells were monitored everyday, and after 3 weeks of culturing, the analysis with scanning electron microscope (SEM) was performed. Our results showed that the NPU cells were attached on all scaffolds; they were viable and formed a multilayered epithelium, i.e., urothelium. The apical plasma membrane of the majority of superficial NPU cells, grown on all three different TiO2 scaffolds and on the porous membrane, exhibited microvilli; thus, indicating that they were at a similar differentiation stage. The maximal caliper diameter measurements of superficial NPU cells revealed significant alterations, with the largest cells being observed on nanowires and the smallest ones on the porous membrane. Our findings indicate that different nanostructured TiO2 scaffolds, especially nanowires, have a great potential for tissue engineering and should be further investigated for various urologic applications.

Growth of a Novel Nanostructured ZnO Urchin: Control of Cytotoxicity and Dissolution of the ZnO Urchin.

The applications of zinc oxide (ZnO) nanowires (NWs) in implantable wireless devices, such as diagnostic nanobiosensors and nanobiogenerators, have recently attracted enormous attention due to their unique properties. However, for these implantable nanodevices, the biocompatibility and the ability to control the behaviour of cells in contact with ZnO NWs are demanded for the success of these implantable devices, but to date, only a few contrasting results from their biocompatibility can be found. There is a need for more research about the biocompatibility of ZnO nanostructures and the adhesion and viability of cells on the surface of ZnO nanostructures. Here, we introduce synthesis of a new nature-inspired nanostructured ZnO urchin, with the dimensions of the ZnO urchin's acicula being controllable. To examine the biocompatibility and behaviour of cells in contact with the ZnO urchin, the Madin-Darby canine kidney (MDCK) epithelial cell line was chosen as an in vitro experimental model. The results of the viability assay indicated that, compared to control, the number of viable cells attached to the surface of the ZnO urchin and its surrounding area were reduced. The measurements of the Zn contents of cell media confirmed ZnO dissolution, which suggests that the ZnO dissolution in cell culture medium could lead to cytotoxicity. A purposeful reduction of ZnO cytotoxicity was achieved by surface coating of the ZnO urchin with poly(vinylidene fluorid-co-hexafluoropropylene) (PVDF-HFP), which changed the material matrix to slow the Zn ion release and consequently reduce the cytotoxicity of the ZnO urchin without reducing its functionality.

On/off-switchable anti-neoplastic nanoarchitecture.

Throughout the world, there are increasing demands for alternate approaches to advanced cancer therapeutics. Numerous potentially chemotherapeutic compounds are developed every year for clinical trial and some of them are considered as potential drug candidates. Nanotechnology-based approaches have accelerated the discovery process, but the key challenge still remains to develop therapeutically viable and physiologically safe materials suitable for cancer therapy. Here, we report a high turnover, on/off-switchable functionally popping reactive oxygen species (ROS) generator using a smart mesoporous titanium dioxide popcorn (TiO2 Pops) nanoarchitecture. The resulting TiO2 Pops, unlike TiO2 nanoparticles (TiO2 NPs), are exceptionally biocompatible with normal cells. Under identical conditions, TiO2 Pops show very high photocatalytic activity compared to TiO2 NPs. Upon on/off-switchable photo activation, the TiO2 Pops can trigger the generation of high-turnover flash ROS and can deliver their potential anticancer effect by enhancing the intracellular ROS level until it crosses the threshold to open the 'death gate', thus reducing the survival of cancer cells by at least six times in comparison with TiO2 NPs without affecting the normal cells.

Band edge engineering of TiO2@DNA nanohybrids and implications for capacitive energy storage devices.

Novel mesoporous TiO2@DNA nanohybrid electrodes, combining covalently encoded DNA with mesoporous TiO2 microbeads using dopamine as a linker, were prepared and characterised for application in supercapacitors. Detailed information about donor density, charge transfer resistance and chemical capacitance, which have an important role in the performance of an electrochemical device, were studied by electrochemical methods. The results indicated the improvement of electrochemical performance of the TiO2 nanohybrid electrode by DNA surface functionalisation. A supercapacitor was constructed from TiO2@DNA nanohybrids with PBS as the electrolyte. From the supercapacitor experiment, it was found that the addition of DNA played an important role in improving the specific capacitance (Cs) of the TiO2 supercapacitor. The highest Cs value of 8 F g(-1) was observed for TiO2@DNA nanohybrids. The nanohybrid electrodes were shown to be stable over long-term cycling, retaining 95% of their initial specific capacitance after 1500 cycles.

Combined cytotoxic effect of UV-irradiation and TiO2 microbeads in normal urothelial cells, low-grade and high-grade urothelial cancer cells.

The differentiation of urothelial cells results in normal terminally differentiated cells or by alternative pathways in low-grade or high-grade urothelial carcinomas. Treatments with traditional surgical and chemotherapeutical approaches are still inadequate and expensive, as bladder tumours are generally highly recurrent. In such situations, alternative approaches, using irradiation of the cells and nanoparticles, are promising. The ways in which urothelial cells, at different differentiation levels, respond to UV-irradiation (photolytic treatment) or to the combination of UV-irradiation and nanoparticles (photocatalytic treatment), are unknown. Here we tested cytotoxicity of UV-irradiation on (i) normal porcine urothelial cells (NPU), (ii) human low-grade urothelial cancer cells (RT4), and (iii) human high-grade urothelial cancer cells (T24). The results have shown that 1 minute of UV-irradiation is enough to kill 90% of the cells in NPU and RT4 cultures, as determined by the live/dead viability assay. On the other hand, the majority of T24 cells survived 1 minute of UV-irradiation. Moreover, even a prolonged UV-irradiation for 30 minutes killed <50% of T24 cells. When T24 cells were pre-supplemented with mesoporous TiO2 microbeads and then UV-irradiated, the viability of these high-grade urothelial cancer cells was reduced to <10%, which points to the highly efficient cytotoxic effects of TiO2 photocatalysis. Using electron microscopy, we confirmed that the mesoporous TiO2 microbeads were internalized into T24 cells, and that the cell's ultrastructure was heavily compromised after UV-irradiation. In conclusion, our results show major differences in the sensitivity to UV-irradiation among the urothelial cells with respect to cell differentiation. To achieve an increased cytotoxicity of urothelial cancer cells, the photocatalytic approach is recommended.

Morphological alterations of T24 cells on flat and nanotubular TiO2 surfaces.

AIM: To investigate morphological alterations of malignant cancer cells (T24) of urothelial origin seeded on flat titanium (Ti) and nanotubular TiO(2) (titanium dioxide) nanostructures. METHODS: Using anodization method, TiO(2) surfaces composed of vertically aligned nanotubes of 50-100 nm diameters were produced. The flat Ti surface was used as a reference. The alteration in the morphology of cancer cells was evaluated using scanning electron microscopy (SEM). A computational model, based on the theory of membrane elasticity, was constructed to shed light on the biophysical mechanisms responsible for the observed changes in the contact area of adhesion. RESULTS: Large diameter TiO(2) nanotubes exhibited a significantly smaller contact area of adhesion (P<0.0001) and had more membrane protrusions (eg, microvilli and intercellular membrane nanotubes) than on flat Ti surface. Numerical membrane dynamics simulations revealed that the low adhesion energy per unit area would hinder the cell spreading on the large diameter TiO(2) nanotubular surface, thus explaining the small contact area. CONCLUSION: The reduction in the cell contact area in the case of large diameter TiO(2) nanotube surface, which does not enable formation of the large enough number of the focal adhesion points, prevents spreading of urothelial cells.