Excessive Iodine Enabled Ultrathin Inorganic Perovskite Growth at the Liquid-Air Interface.

The liquid-air interface offers a platform for the in-plane growth of free-standing materials. However, it is rarely used for inorganic perovskites and ultrathin non-layered perovskites. Herein the liquid-air interfacial synthesis of inorganic perovskite nanosheets (Cs3 Bi2 I9 , Cs3 Sb2 I9 ) is achieved simply by drop-casting the precursor solution with only the addition of iodine. The products are inaccessible without iodine addition. The thickness and lateral size of these nanosheets can be adjusted through the iodine concentration. The high volatility of the iodine spontaneously drives precursors that normally stay in the liquid to the liquid-air interface. The iodine also repairs in situ iodine vacancies during perovskite growth, giving enhanced optical and optoelectronic properties. The liquid-air interfacial growth of ultrathin perovskites provides multi-degree-of-freedom for constructing perovskite-based heterostructures and devices at atomic scale.

Multifunctional Rbx WO3 nanorods for simultaneous combined chemo-photothermal therapy and photoacoustic/CT imaging.

Light-triggered drug delivery based on near-infrared (NIR)-mediated photothermal nanocarriers has received tremendous attention for the construction of cooperative therapeutic systems in nanomedicine. Herein, a new paradigm of light-responsive drug carrier that doubles as a photothermal agent is reported based on the NIR light-absorber, Rb(x) WO3 (rubidium tungsten bronze, Rb-TB) nanorods. With doxorubicin (DOX) payload, the DOX-loaded Rb-TB composite (Rb-TB-DOX) simultaneously provides a burst-like drug release and intense heating effect upon 808-nm NIR light exposure. MTT assays show the photothermally enhanced antitumor activity of Rb-TB-DOX to the MCF-7 cancer cells. Most remarkably, Rb-TB-DOX combined with NIR irradiation also shows dramatically enhanced chemotherapeutic effect to DOX-resistant MCF-7 cells compared with free DOX, demonstrating the enhanced efficacy of combinational chemo-photothermal therapy for potentially overcoming drug resistance in cancer chemotherapy. Furthermore, in vivo study of combined chemo-photothermal therapy is also conducted and realized on pancreatic (Pance-1) tumor-bearing nude mice. Apart from its promise for cancer therapy, the as-prepared Rb-TB can also be employed as a new dual-modal contrast agent for photoacoustic tomography and (PAT) X-ray computed tomography (CT) imaging because of its high NIR optical absorption capability and strong X-ray attenuation ability, respectively. The results presented in the current study suggest promise of the multifunctional Rb(x)WO3 nanorods for applications in cancer theranostics.

Upconversion Perovskite Nanocrystal Heterostructures with Enhanced Luminescence and Stability by Lattice Matching.

Lead halide perovskite quantum dots (PQDs) exhibit excellent photoelectric and optical properties, but their poor stability and low multiphoton absorption efficiency greatly limit their biological applications. Efforts have been made to combine upconversion nanoparticles (UCNPs) with PQDs to produce a composite material that is NIR-excitable, upconverting, and emission-tunable due to the unique optical properties of UCNPs, which converts tissue-penetrating near-infrared light into visible light based on an upconversion multiphoton excitation process. However, it is challenging to make such a nanocrystal heterostructure and maintain good optical properties and stability of both UCNPs and PQDs because they have different crystal structures. Here, we report the synthesis of heterostructured UCNP-PQD nanocrystals to bring hexagonal-phase NaYF4 UCNPs and cubic-phase CsPbBr1X2 PQDs in close proximity in a single nanocrystal, leading to efficient Förster resonance energy transfer (FRET) from the UCNP to the PQD under NIR excitation, as compared to their counterparts in solution. Moreover, by further improving the lattice matching between the UCNP and PQD using Gd to replace Y, heterostructured CsPbBr3-NaGdF4:Yb,Tm nanocrystals are successfully synthesized, with much enhanced luminescence and stability at high temperatures or in polar solvents or under continuous ultraviolet light excitation as compared to those of the CsPbBr3-NaYF4:Yb,Tm nanocrystals and pure PQDs.

NIR-excitable heterostructured upconversion perovskite nanodots with improved stability.

There is a great need to develop heterostructured nanocrystals which combine two or more different materials into single nanoparticles with combined advantages. Lead halide perovskite quantum dots (QDs) have attracted much attention due to their excellent optical properties but their biological applications have not been much explored due to their poor stability and short penetration depth of the UV excitation light in tissues. Combining perovskite QDs with upconversion nanoparticles (UCNP) to form hybrid nanocrystals that are stable, NIR excitable and emission tunable is important, however, this is challenging because hexagonal phase UCNP can not be epitaxially grown on cubic phase perovskite QDs directly or vice versa. In this work, one-pot synthesis of perovskite-UCNP hybrid nanocrystals consisting of cubic phase perovskite QDs and hexagonal phase UCNP is reported, to form a watermelon-like heterostructure using cubic phase UCNP as an intermediate transition phase. The nanocrystals are NIR-excitable with much improved stability.

Reversible light-mediated compositional and structural transitions between CsPbBr3 and CsPb2Br5 nanosheets.

This communication describes a new method to achieve reversible light-induced chemical composition and phase structural transitions from polyvinylpyrrolidone-capped orthorhombic CsPbBr3 to tetragonal CsPb2Br5 nanosheets or vice versa. This work will deepen our understanding of the controlled synthesis, post-processing, and decomposition pathway of cesium lead halide perovskite nanocrystals.

Ligand-mediated synthesis of compositionally related cesium lead halide CsPb2X5 nanowires with improved stability.

Compositionally related cesium lead halide materials, such as CsPb2X5, have attracted great interest due to their considerable optoelectronic/optical properties as well as improved stability. Currently, CsPb2Br5 nanocrystals can be well-designed by tuning the ligands or precursor ratio, whereas, CsPb2X5 (with Cl- or I-) nanocrystals can only be obtained by the anion exchange method. Herein, we report a method to directly synthesize CsPb2X5 facilitated by thiol ligands. The morphology of CsPb2X5 can be designed as a nanowire. Importantly, the stability of directly synthesized CsPb2X5 nanowires is much improved when compared with the stabilities of the materials obtained by the anion-exchange method. We believe that this method will promote the application of 1D tetragonal CsPb2X5 in optoelectronics, optics and other fields.

Stable and conductive lead halide perovskites facilitated by X-type ligands.

Lead halide perovskites exhibit outstanding optoelectronic and optical properties. However, some applications of perovskites are hindered by their instability in polar environments; thus, how to balance stability with conductivity is a great challenge. Here, we report a new approach of using X-type ligands to address this issue. Surface treatments containing multi-step ligand exchanges and ion filling were necessary to obtain X-type ligand-protected perovskites. Performances of this material show that: (1) the crystal structure of perovskites is stable in ethanol; (2) surface defects can be fixed by a photoactivation process and photoluminescence intensity can be enhanced to 136%; and (3) electronic devices fabricated from such materials show stabilility even after washing with ethanol. X-type ligand-protected perovskites with high stability and good conductivity are promising new materials for wide applications in electronic and optoelectronics devices.

Alkyl-Thiol Ligand-Induced Shape- and Crystalline Phase-Controlled Synthesis of Stable Perovskite-Related CsPb2Br5 Nanocrystals at Room Temperature.

Controlled synthesis of colloidal all-inorganic lead halide perovskite semiconductor nanocrystals, such as CsPbBr3, with tunable size, shape, composition, and crystalline phase have recently attracted wide interest for photonic and optoelectronic applications. Herein, we report a new strategy for using alkyl-thiols to induce the transformation of CsPbBr3 to perovskite-related cesium lead halide (CsPb2Br5) with controlled morphology and a crystalline phase at room temperature. By rational tuning the ratios of the alkyl-thiol ligands to alkyl-amines or to alkyl-acids, the as-synthesized colloidal nanocrystals can be rationally controlled from orthorhombic crystalline-phase CsPbBr3 to tetragonal-phase CsPb2Br5 nanosheets and nanowires with high yield. Significantly, the tetragonal CsPb2Br5 nanowires and nanosheets have high stability in high-temperature and high-humidity environments. These findings may open new directions for large-scale synthesis of shape- and crystalline phase-controlled perovskite nanocrystals for high-performance, low-cost optical electronic and optoelectronic devices.

Mesoporous NaYbF4@NaGdF4 core-shell up-conversion nanoparticles for targeted drug delivery and multimodal imaging.

We developed a facile strategy to obtain a new kind of mesoporous core-shell structured up-conversion nanoparticles (mUCNPs), composed of a NaYbF4:2%Er core and a mesoporous NaGdF4 shell. This mesoporous shell not only enhanced the up-conversion luminescence but also endowed many other functionalities of the nanoparticles such as drug delivery and bio-imaging capabilities. Moreover, after being conjugated with polyethylenimine (PEI) and folic acid (FA), core-shell mUCNPs exhibited good water dispersibility, enhanced drug delivery efficiency, and remarkable targeting ability to cancer cells. To certify the folate receptors (FR)-mediated targeted drug delivery, cell viability assay, cell up-conversion luminescence imaging and flow cytometry analysis were carried out. Furthermore, apart from the application for targeted drug delivery, the as-prepared core-shell mUCNPs could also be employed as the contrast agents for X-ray computed tomography (CT) and magnetic resonance (MR) imaging, because of the strong X-ray attenuation ability of Yb and high longitudinal molar relaxivity (r1) of Gd in the nanoparticles, providing the potential for simultaneously bio-imaging and cancer-targeting therapy.