Imaging through Nonlinear Metalens Using Second Harmonic Generation

The abrupt phase change of light at metasurfaces provides high flexibility in wave manipulation without the need for accumulation of propagating phase through dispersive materials. In the linear optical regime, one important application field of metasurfaces is imaging by planar metalenses, which enables device miniaturization and aberration correction compared to conventional optical microlens systems. With the incorporation of nonlinear responses into passive metasurfaces, optical functionalities of metalenses are anticipated to be further enriched, leading to completely new application areas. Here, imaging with nonlinear metalenses that combine the function of an ultrathin planar lens with simultaneous frequency conversion is demonstrated. With such nonlinear metalenses, imaging of objects with near infrared light while the image appears in the second harmonic signal of visible frequency range is experimentally demonstrated. Furthermore, the functionality of these nonlinear metalenses can be modified by switching the handedness of the circularly polarized fundamental wave, leading to either real or virtual nonlinear image formation. Nonlinear metalenses not only enable infrared light imaging through a visible detector but also have the ability to modulate nonlinear optical responses through an ultrathin metasurface device while the fundamental wave remains unaffected, which offers the capability of nonlinear information processing with novel optoelectronic devices.     

Resource‐Efficient Low‐Temperature Synthesis of Microcrystalline Pb2B5O9X (X = Cl,Br) for Surfaces Studies by Optical Second Harmonic Generation

Optically nonlinear Pb₂B₅O₉X (X = Cl, Br) borate halides are an important group of materials for second harmonic generation (SHG). Additionally, they also possess excellent photocatalytic activity and stability in the process of dechlorination of chlorophenols, which are typical persistent organic pollutants. It would be of great interest to conduct in situ (photo‐) catalysis investigations during the whole photocatalytic process by SHG when considering them as photocatalytic materials. In order to get superior photocatalytic efficiency and maximum surface information, small particles are highly desired. Here, a low‐cost and fast synthesis route that allows growing microcrystalline optically nonlinear Pb₂B₅O₉X borate halides at large quantities is introduced. When applying the ionothermal growth process at temperatures between 130 and 170 °C, microcrystallites with an average size of about 1 µm precipitate with an orthorhombic hilgardite‐like borate halide structure. Thorough examinations using powder X‐ray diffraction and scanning electron microscopy, the Pb₂B₅O₉X microcrystals are indicated to be chemically pure and single‐phased. Besides, the Pb₂B₅O₉X borate halides' SHG efficiencies are confirmed using confocal SHG microscopy. The low‐temperature synthesis route thus makes these borate halides a highly desirable material for surface studies such as monitoring chemical reactions with picosecond time resolution and in situ (photo‐) catalysis investigations.     

二次谐波在二维材料结构表征中的应用

二次谐波作为非线性光学的重要分支,逐渐成为表征晶体结构的重要手段之一。在众多表征方法中,二次谐波因其无损检测、高稳定性、可调谐性、超快响应、偏振敏感性、通用性、操作简单等特点被广泛应用于二维材料结构表征,为二维材料的物性研究和功能应用提供了重要信息,大大推动了二维材料基础研究的快速发展。本文综述了近几年二次谐波在二维材料结构表征中的研究,简述了二次谐波产生原理,介绍了飞秒激光器接入共聚焦拉曼光谱仪产生二次谐波测试装置,分别讨论了二次谐波在二维材料的层间堆垛层数、层间堆垛角度、单层二维材料晶界及晶体取向表征方面的应用。同时,本文还介绍了采用二次谐波强度直接、灵敏地检测晶体中应变幅度以及通过二次谐波信号变化跟踪材料中的缺陷变化,接着讨论了二次谐波与拉曼光谱、光致发光的多维度关联分析在材料全面深度表征方面的重要性。最后展望了二次谐波未来在材料结构表征中的潜在研究方向。     

Polarization-Independent Second Harmonic Generation in 2D Van Der Waals Kagome Nb3SeI7 Crystals

Second harmonic generation (SHG) of 2D crystals has been of great interest due to its advantages of phase-matching and easy integration into nanophotonic devices. However, the polarization-dependence character of the SHG signal makes it highly troublesome but necessary to match the laser polarization orientation relative to the crystal, thus achieving the maximum polarized SHG intensity. Here, it is demonstrated a polarization-independent SHG, for the first time, in the van der Waals Nb₃SeI₇ crystals with a breathing Kagome lattice. The Nb₃ triangular clusters and Janus-structure of each Nb₃SeI₇ layer are confirmed by the STEM. Nb₃SeI₇ flake shows a strong SHG response due to its noncentrosymmetric crystal structure. More interestingly, the SHG signals of Nb₃SeI₇ are independent of the polarization of the excitation light owing to the in-plane isotropic arrangement of nonlinear active units. This work provides the first layered nonlinear optical crystal with the polarization-independent SHG effect, providing new possibilities for nonlinear optics.     

Water-Assisted Growth of Twisted 3R-Stacked MoSe2 Spirals and Its Dramatically Enhanced Second Harmonic Generations

Enhanced second-harmonic generation (SHG) responses are reported in monolayer transition metal dichalcogenides (e.g., MX₂, M: Mo, W; X: S, Se) due to the broken symmetries. The 3R-like stacked MX₂ spiral structures possessing the similar broken inversion symmetry should present dramatically enhanced SHG responses, thus providing great flexibility in designing miniaturized on-chip nonlinear optical devices. To achieve this, the first direct synthesis of twisted 3R-stacked chiral molybdenum diselenide (MoSe₂) spiral structures with specific screw dislocations (SD) arms is reported, via designing a water-assisted chemical vapor transport (CVT) approach. The study also clarifies the formation mechanism of the MoSe₂ spiral structures, by precisely regulating the precursor supply accompanying with multiscale characterizations. Significantly, an up to three orders of magnitude enhancement of the SHG responses in twisted 3R stacked MoSe₂ spirals is demonstrated, which is proposed to arise from the synergistic effects of broken inversion symmetry, strong light–matter interaction, and band nesting effects. Briefly, the work provides an efficient synthetic route for achieving the 3R-stacked TMDCs spirals, which can serve as perfect platforms for promoting their applications in on-chip nonlinear optical devices.     

Biomimetic Nanobomb for Synergistic Therapy with Inhibition of Cancer Stem Cells

Cancer stem cells (CSCs), a type of cell with self-renewal, unlimited proliferation, and insensitivity to common physical and chemical factors, are the key to cancer metastasis, recurrence, and chemo-resistance. Available CSCs inhibition strategies are mainly based on small molecule drugs, yet are limited by their off-target toxicity. The link between CSCs and non-CSCs interconversion is difficult to sever. In this work, a nanotherapeutic strategy based on MnO_x-loaded polydopamine (MnO_x/PDA) nanobombs with chemodynamic, photodynamic, photothermal and biodegradation properties to inhibit CSCs and non-CSCs concurrently is reported. The MnO_x/PDA nanobombs can directly disrupt the microenvironment and tumorigenic capacity of CSCs by generating hyperthermia, oxidative stress and alleviating hypoxia. The markers of CSCs are subsequently downregulated, leading to the clearance of CSCs. Meanwhile, the synergistic therapy mediated by MnO_x/PDA nanobombs can directly ablate the bulk tumor cells, thus cutting off the supply of CSCs transformation. For tumor targeting, MnO_x/PDA is coated with macrophage membrane. The final tumor inhibition rate of the synergistic therapy is 70.8% in colorectal cancer (CRC) model. Taken together, the present work may open up the exploration of nanomaterial-based synergistic therapy for the simultaneous elimination of therapeutically resistant CSCs and non-CSCs.     

Effective Gene Delivery into Human Stem Cells with a Cell‐Targeting Peptide‐Modified Bioreducible Polymer

Stem cells are poorly permissive to non‐viral gene transfection reagents. In this study, we explored the possibility of improving gene delivery into human embryonic (hESC) and mesenchymal (hMSC) stem cells by synergizing the activity of a cell‐binding ligand with a polymer that releases nucleic acids in a cytoplasm‐responsive manner. A 29 amino acid long peptide, RVG, targeting the nicotinic acetylcholine receptor (nAchR) was identified to bind both hMSC and H9‐derived hESC. Conjugating RVG to a redox‐sensitive biodegradable dendrimer‐type arginine‐grafted polymer (PAM‐ABP) enabled nanoparticle formation with plasmid DNA without altering the environment‐sensitive DNA release property and favorable toxicity profile of the parent polymer. Importantly, RVG‐PAM‐ABP quantitatively enhanced transfection into both hMSC and hESC compared to commercial transfection reagents like Lipofectamine 2000 and Fugene. ～60% and 50% of hMSC and hESC were respectively transfected, and at increased levels on a per cell basis, without affecting pluripotency marker expression. RVG‐PAM‐ABP is thus a novel bioreducible, biocompatible, non‐toxic, synthetic gene delivery system for nAchR‐expressing stem cells. Our data also demonstrates that a cell‐binding ligand like RVG can cooperate with a gene delivery system like PAM‐ABP to enable transfection of poorly‐permissive cells.     

Universal Imaging of Full Strain Tensor in 2D Crystals with Third‐Harmonic Generation

Quantitatively mapping and monitoring the strain distribution in 2D materials is essential for their physical understanding and function engineering. Optical characterization methods are always appealing due to unique noninvasion and high‐throughput advantages. However, all currently available optical spectroscopic techniques have application limitation, e.g., photoluminescence spectroscopy is for direct‐bandgap semiconducting materials, Raman spectroscopy is for ones with Raman‐active and strain‐sensitive phonon modes, and second‐harmonic generation spectroscopy is only for noncentrosymmetric ones. Here, a universal methodology to measure the full strain tensor in any 2D crystalline material by polarization‐dependent third‐harmonic generation is reported. This technique utilizes the third‐order nonlinear optical response being a universal property in 2D crystals and the nonlinear susceptibility has a one‐to‐one correspondence to strain tensor via a photoelastic tensor. The photoelastic tensor of both a noncentrosymmetric D_3h WS₂ monolayer and a centrosymmetric D_3d WS₂ bilayer is successfully determined, and the strain tensor distribution in homogenously strained and randomly strained monolayer WS₂ is further mapped. In addition, an atlas of photoelastic tensors to monitor the strain distribution in 2D materials belonging to all 32 crystallographic point groups is provided. This universal characterization on strain tensor should facilitate new functionality designs and accelerate device applications in 2D‐materials‐based electronic, optoelectronic, and photovoltaic devices.     

Revealing the Fate of Transplanted Stem Cells In Vivo with a Novel Optical Imaging Strategy

Stem‐cell‐based regenerative medicine holds great promise in clinical practices. However, the fate of stem cells after transplantation, including the distribution, viability, and the cell clearance, is not fully understood, which is critical to understand the process and the underlying mechanism of regeneration for better therapeutic effects. Herein, we develop a dual‐labeling strategy to in situ visualize the fate of transplanted stem cells in vivo by combining the exogenous near‐infrared fluorescence imaging in the second window (NIR‐II) and endogenous red bioluminescence imaging (BLI). The NIR‐II fluorescence of Ag₂S quantum dots is employed to dynamically monitor the trafficking and distribution of all transplanted stem cells in vivo due to its deep tissue penetration and high spatiotemporal resolution, while BLI of red‐emitting firefly luciferase (RfLuc) identifies the living stem cells after transplantation in vivo because only the living stem cells express RfLuc. This facile strategy allows for in situ visualization of the dynamic trafficking of stem cells in vivo and the quantitative evaluation of cell translocation and viability with high temporal and spatial resolution, and thus reports the fate of transplanted stem cells and how the living stem cells help, regeneration, for an instance, of a mouse with acute liver failure.     

TiO2 Nanorod Array Constructed Nanotopography for Regulation of Mesenchymal Stem Cells Fate and the Realization of Location‐Committed Stem Cell Differentiation

As a physical cue for controlling the fate of stem cells, surface nanotopography has attracted much attention to improve the integration between implants and local host tissues and cells. A biocompatible surface TiO₂ nanorod array is proposed to regulate the fate of bone marrow derived mesenchymal stem cells (MSCs). TiO₂ substrates with different surface nanotopographies: a TiO₂ nanorod array and a polished TiO₂ ceramic are built by hydrothermal and sintering processes, respectively. The assessment of morphology, viability, gene expression, and protein characterization of the MSCs cultured on the different TiO₂ substrates proves that a TiO₂ nanorod array promotes the osteogenic differentiation of MSCs, while a TiO₂ ceramic with a smooth surface suppresses it. Periodically assembled TiO₂ nanorod array stripes on the smooth TiO₂ ceramic are constructed by a combination of microfabrication and a chemical synthesis process, which realizes the location‐committed osteogenic differentiation of MSCs. A route to control the differentiation of MSCs by a nanostructured surface, which can also control the location and direction of MSCs on the surface of biomaterials with micro‐nano scale surface engineering, is demonstrated.     

Dual Passivation of CsPbI3 Perovskite Nanocrystals with Amino Acid Ligands for Efficient Quantum Dot Solar Cells

Inorganic CsPbI₃ perovskite quantum dot (PQD) receives increasing attention for the application in the new generation solar cells, but the defects on the surface of PQDs significantly affect the photovoltaic performance and stability of solar cells. Herein, the amino acids are used as dual‐passivation ligands to passivate the surface defects of CsPbI₃ PQDs using a facile single‐step ligand exchange strategy. The PQD surface properties are investigated in depth by combining experimental studies and theoretical calculation approaches. The PQD solid films with amino acids as dual‐passivation ligands on the PQD surface are thoroughly characterized using extensive techniques, which reveal that the glycine ligand can significantly improve defect passivation of PQDs and therefore diminish charge carrier recombination in the PQD solid. The power conversion efficiency (PCE) of the glycine‐based PQD solar cell (PQDSC) is improved by 16.9% compared with that of the traditional PQDSC fabricated with Pb(NO₃)₂ treating the PQD surface, owning to improved charge carrier extraction. Theoretical calculations are carried out to comprehensively understand the thermodynamic feasibility and favorable charge density distribution on the PQD surface with a dual‐passivation ligand.     

Clinically Approved Carbon Nanoparticles with Oral Administration for Intestinal Radioprotection via Protecting the Small Intestinal Crypt Stem Cells and Maintaining the Balance of Intestinal Flora

The exploration of an old drug for new biomedical applications has an absolute predominance in shortening the clinical conversion time of drugs for clinical application. In this work, carbon nanoparticles suspension injection (CNSI), the first clinically approved carbon nanoparticles in China, is explored as a new nano‐radioprotective agent for potent intestinal radioprotection. CNSI shows powerful radioprotective performance in the intestine under oral administration, including efficient free radical scavenging ability, good biosafety, high chemical stability, and relatively long retention time. For example, CNSI shows high reactive oxygen species (ROS) scavenging activities, which effectively alleviates the mitochondrial dysfunction and DNA double‐strand breaks to protect the cells against radiation‐induced damage. Most importantly, this efficient ROS scavenging ability greatly helps restrain the apoptosis of the small intestinal epithelial and crypt stem cells, which decreases the damage of the mechanical barrier and thus relieves radiation enteritis. Moreover, CNSI helps remove the free radicals in the intestinal microenvironment and thus maintain the balance of intestinal flora so as to mitigate the radiation enteritis. The finding suggests a new application of clinically approved carbon nanoparticles, which not only promotes the development of new intestinal radioprotector, but also has a great potential for clinical transformation.