Hybrid Organic-Inorganic Perovskite Superstructures for Ultrapure Green Emissions.

All inorganic CsPbBr3 superstructures (SSs) have attracted much research interest due to their unique photophysical properties, such as their large emission red-shifts and super-radiant burst emissions. These properties are of particular interest in displays, lasers and photodetectors. Currently, the best-performing perovskite optoelectronic devices incorporate organic cations (methylammonium (MA), formamidinium (FA)), however, hybrid organic-inorganic perovskite SSs have not yet been investigated. This work is the first to report on the synthesis and photophysical characterization of APbBr3 (A = MA, FA, Cs) perovskite SSs using a facile ligand-assisted reprecipitation method. At higher concentrations, the hybrid organic-inorganic MA/FAPbBr3 nanocrystals self-assemble into SSs and produce red-shifted ultrapure green emissions, meeting the requirement of Rec. 2020 displays. We hope that this work will be seminal in advancing the exploration of perovskite SSs using mixed cation groups to further improve their optoelectronic applications.

Tunable concentration-dependent upconversion and downconversion luminescence in NaYF4: Yb3+, Er3+@ NaYF4: Yb3+, Nd3+ core-shell nanocrystals for a dual-mode anti-counterfeiting imaging application.

Lanthanide-doped luminescent nanocrystals display both upconversion luminescence (UCL) and downconversion luminescence (DCL) properties, which offer potential applications in the second near-infrared window (NIR-II) images and biology sensors. Both UCL and DCL are sensitive to concentrations of activators. However, few works reveal the mechanism of concentration-dependent UCL and DCL. Herein, we synthesize core-shell upconversion nanocrystals (UCNCs) NaYF4: Yb3+(20%), Er3+ (2%)@NaYF4: Yb3+ (x%), Nd3+ (y%) with varying concentration of Nd and Yb ions. The UCL and DCL spectra are recorded under excitation of 980 nm and 808 nm lasers. The results indicate that the luminescence of core-shell UCNCs is influenced by the non-radiative rate between activators (Yb3+ and Nd3+) and the back energy transfer rate from Er3+ ions to activators. UCL tends to be obtained at a relatively low concentration of Yb3+ and Nd3+ ions (about 5%), whereas NIR emission tends to be obtained at a relatively high concentration of Yb3+ and Nd3+ ions (not higher than 20%). Dual-mode anti-counterfeiting imaging is successfully fabricated using core-shell UCNCs, which can be detected and distinguished by visible and infrared detectors. The visible versus infrared brightness of dual-mode anti-counterfeiting imaging can be tuned by varying the concentration of activators (Yb3+, Nd3+). Our work demonstrates concentration-dependent UCL and DCL in core-shell UCNCs, which provides reference to obtain NIR emission in the NIR-II region and adds encrypted dimensions for anti-counterfeiting patterns in the field of file encryption.

Scar prevention through topical delivery of gelatin-tyramine-siSPARC nanoplex loaded in dissolvable hyaluronic acid microneedle patch across skin barrier.

Currently, there is no effective method to prevent the formation of hypertrophic scars and keloids, which can cause severe physical and psychological burdens to patients. Secreted protein acidic and cysteine-rich (SPARC) is involved in wound fibrosis by modulating fibroblast functions, causing excessive collagen deposition during wound healing. Thus, the reduction in SPARC gene expression after wounding can contribute to the downstream reduction in collagen production at the wound site and prevent scar formation. In this study, a dissolvable and biocompatible hyaluronic acid (HA) microneedle patch loaded with nanoplexes containing tyramine-modified gelatin and siRNA for SPARC (siSPARC/Gtn-Tyr) was investigated for topical scar prevention. Tyramine-modified gelatin (Gtn-Tyr) provides electrostatic protection and enhances cell internalization for siSPARC. In vitro studies using human dermal fibroblasts showed that both siSPARC/Gtn-Tyr nanoplexes and siSPARC/Gtn-Tyr-loaded microneedle patches can significantly reduce SPARC gene expression (P < 0.05) and do not cause discernable cytotoxic effects. Further studies using a mouse wound model demonstrate that the siSPARC/Gtn-Tyr-loaded microneedle patch can reduce collagen production during wound healing without triggering an immune response. When Gtn-Tyr-siSPARC is administered transdermally at the wound site, effective collagen reduction is achieved through silencing of the matricellular SPARC protein, thus promising the reduction of scar formation. Overall, the siSPARC/Gtn-Tyr loaded microneedle patch can potentially provide an effective transdermal anti-fibrotic treatment.

Near-infrared-II activated inorganic photothermal nanomedicines.

The emergence of near-infrared-II (NIR-II) activated photomedicines has extended the penetration depth for noninvasive theranostics, especially for photothermal nanomedicines. The current early development stage for NIR-II activated photomedicines has focused on creating a greater variety of photothermal agents (PTAs) with superior photothermal conversion ability. However, there is no thorough review for NIR-II inorganic PTAs and most comparisons of the photothermal performances of NIR-II inorganic PTAs are made with NIR-I PTAs. This review will first discuss about the key mechanisms of NIR-II absorption and photothermal conversion. Subsequently, this review will summarize recently developed advanced NIR-II inorganic PTAs based on the dominant inorganic elements and provide a comparison of their NIR-II photothermal performances. The nanostructure design, enhancement strategies and potential biomedical applications will be listed and discussed. We hope this review will further inspire active development and study of NIR-II activated inorganic PTAs with good photothermal conversion ability, multifunctionality, biocompatibility or biodegradability, and disease targeting ability.

Balancing the thickness of sensitizing and inert layers in neodymium-sensitized tetralayer nanoconstructs for optimal ultraviolet upconversion and near-infrared cross-linked hydrogel tissue sealants.

Tuning the configuration of lanthanide-doped upconversion nanoparticles (UCNPs) has been proven to be an effective approach to enhance upconversion (UC) efficiency, especially for neodymium (Nd3+)-sensitized UCNPs. Rational configuration design can spatially separate activators and sensitizers, achieving the evolution from single core to multilayer structures. However, optimizing multiphoton UC emission via configuration modulation, especially in the ultraviolet range, is yet to be fully investigated. In this work, thickness tuning of the sensitizing layer containing Nd3+ ions and the inert layer containing gadolinium ions at a fixed combined thickness of 5 nm in tetralayer UCNPs to exclude the size effect is reported for the first time. The optimal thickness of sensitizing and inert layers was determined to be 3 and 2 nm respectively, showing a new strategy of balancing sensitization and surface passivation to enhance 4-photon (360 nm) emission. Although 3-photon emission (475 nm) is mainly influenced by the overall size, its emission intensity remains similar in all the tetralayer UCNPs. Additionally, an 808 nm cross-linked hydrogel has been demonstrated as a potential near-infrared activated tissue sealant. Our results have uncovered the structural parameters for optimal ultraviolet UC emissions and elucidated the strategic importance of nano-configuration design to minimize the energy loss in the high-photon UC process.

Neodymium-Sensitized Nanoconstructs for Near-Infrared Enabled Photomedicine.

Neodymium (Nd3+ )-sensitized nanoconstructs have gained increasing attention in recent decades due to their unique properties, especially optical properties. The design of various Nd3+ -sensitized nanosystems is expected to contribute to medical and health applications, due to their advantageous properties such as high penetration depth, excellent photostability, non-photobleaching, low cytotoxicity, etc. However, the low conversion efficiency and potential long-term toxicity of Nd3+ -sensitized nanoconstructs are huge obstacles to their clinical translations. This review article summarizes three energy transfer pathways of all kinds of Nd3+ -sensitized nanoconstructs focusing on the properties of Nd3+ ions and discusses their recent potential applications as near-infrared (NIR) enabled photomedicine. This review article will contribute to the design and fabrication of novel Nd3+ -sensitized nanoconstructs for NIR-enabled photomedicine, aiming for potentially safer and more efficient designs to get closer to clinical usage.