Improving the Five-Photon Absorption from Core-Shell Perovskite Nanocrystals.

It is necessary to improve the action cross section (η × σn) of high-order multiphoton absorption (MPA) for fundamental research and practical applications. Herein, the core-shell FAPbBr3/CsPbBr3 nanocrystals (NCs) were constructed, and fluorescence induced by up to five-photon absorption was observed. The value of η × σ5 reaches 8.64 × 10-139 cm10 s4 photon-4 nm-3 at 2300 nm, which is nearly an order of magnitude bigger than that of the core-only NCs. It is found that the increased dielectric constant promotes modulation of MPA effects, addressing the electronic distortion in high-order nonlinear behaviors through the local field effect. Meanwhile, the quasi-type-II band alignment suppresses the biexciton Auger recombination, ensuring the stronger MPA induced fluorescence. In addition, the core-shell structure can not only reduce the defect density but also promote the nonradiative energy transfer though the antenna-like effect. This work provides a new avenue for the exploitation of high-performance multiphoton excited nanomaterials for future photonic integration.

A bioinspired hollow g-C3N4-CuPc heterostructure with remarkable SERS enhancement and photosynthesis-mimicking properties for theranostic applications.

Surface-enhanced Raman scattering (SERS) based on chemical mechanism (CM) has great potential for superior stability and selectivity. Moreover, a bioinspired CM-Raman substrate-Raman reporter system with charge separation and electron transport nature provides thylakoid-mimicking potential for multifunctional applications. Herein, hollow carbon nitride nanospheres hierarchically assembled with a well-oriented copper(ii) phthalocyanine layer and hyaluronic acid (HCNs@CuPc@HA) were designed as a light-harvesting nanocomposite and photosynthesis-mimicking nanoscaffold that enhance both CM-SERS and photoredox catalysis. Remarkable SERS enhancement was achieved due to the strengthened short-range substrate-molecule interaction, enriched CuPc molecule loading and enhanced light-mater interactions. Meanwhile, the uniform CuPc molecule film mimics a photo-pigment to accelerate the near infrared (NIR)-oxygen generation and photodynamic catalysis of photosynthetic membrane-like HCNs. The experimental findings were further validated by numerical theory analysis. The greatly enhanced SERS signal and photosynthetic-mimicking properties of the heterostructure (denoted as HCNCHs) were successfully employed for circulating tumor cell (CTC) diagnosis and SERS imaging-guided cancer catalytic therapy in tumor xenograft models.

Quasi-Type II Core-Shell Perovskite Nanocrystals for Improved Structural Stability and Optical Gain.

In recent years, core-shell lead halide perovskite nanocrystals (PeNCs) and their devices have attracted intensive attention owing to nearly perfect optoelectronic properties. However, the complex photophysical mechanism among them is still unclear. Herein, monodispersed core-shell PeNCs coated with an all-inorganic cesium lead bromide (CsPbBr3) shell epitaxially grown on the surface of formamidinium lead bromide (FAPbBr3) PeNCs were synthesized. Through power- and temperature-dependent photoluminescence (PL) measurements, it is found that the electronic structure of the core-shell FAPbBr3/CsPbBr3 PeNCs has a quasi-type II band alignment. The presence of Cs+ in the shell limits ion migration and helps to stabilize structural and optical properties. On this basis, after being exposed to pulsed nanosecond laser for a period, an amplified spontaneous emission (ASE) can be observed, which is attributed to the effective passivation induced by laser irradiation on defects at the interface. The ASE threshold of the core-shell PeNCs showing high structural and optical stability is 447 nJ/cm2 under pulsed nanosecond optical pumping. The results that are demonstrated here provide a new idea and perspective for improving the stability of perovskite and can be of practical interest for the utilization of the core-shell PeNCs in optoelectronic devices.

Highly Biocompatible Plasmonically Encoded Raman Scattering Nanoparticles Aid Ultrabright and Accurate Bioimaging.

Plasmonically engineered nanomaterials based on Au-Ag for surface-enhanced Raman scattering (SERS)-based biomedicine is of great importance but is still far behind clinical needs because of the poor compatibility between sensitivity and safety. Here, robust plasmonically encoded Raman scattering nanoparticles, named Au core-Raman-active molecule-Ag shell-Au shell nanoparticles (CMSS NPs), were synthesized. The as-developed CMSS NPs possess a unique exterior ultrathin Au shell (∼2.2 nm thickness) that plays double key roles as an effective wrapping layer as well as a plasmonic enhancing layer, thereby showing not only extraordinary stability against oxidative damages and bioerosion but also outstanding SERS sensitivity because of the stronger in-built electromagnetic field, achieving a significant SERS enhancement factor of 3.3 × 108. The results confirm that the individual CMSS NPs show ultrahigh brightness, reproducibility, selectivity, and biocompatibility in single-cell Raman imaging. Moreover, ultrabright in vivo tumor imaging with 1 × 1 mm2 area can be quickly achieved within 35 s under open-air condition. Furthermore, by secondary plasmonic encoding, the CMSS NPs flexibly serve as nanobeacon to monitor single-cell autophagy with improved accuracy. The CMSS NPs are expected as versatile SERS probes that enable ultrabright, fast, and precise Raman-based bioimaging and clinical bioapplications.