Engineering of Lanthanide‐Doped Upconversion Nanoparticles for Optical Encoding

Lanthanide‐doped upconversion nanoparticles (UCNPs) are an emerging class of luminescent materials that emit UV or visible light under near infra‐red (NIR) excitations, thereby possessing a large anti‐Stokes shift property. Due to their sharp excitation and emission bands, excellent photo‐ and chemical stability, low autofluorescence, and high tissue penetration depth of the NIR light used for excitation, UCNPs have surpassed conventional fluorophores in many bioapplications. A better understanding of the mechanism of upconversion, as well as the development of better approaches to preparing UCNPs, have provided more opportunities to explore their use for optical encoding, which has the potential for applications in multiplex detection and imaging. With the current ability to precisely control the microstructure and properties of UCNPs to produce particles of tunable emission, excitation, luminescence lifetime, and size, various strategies for optical encoding based on UCNPs can now be developed. These optical properties of UCNPs (such as emission and excitation wavelengths, ratiometric intensity, luminescence lifetime, and multicolor patterns), and the strategies employed to engineer these properties for optical encoding of UCNPs through homogeneous ion doping, heterogeneous structure fabrication and microbead encapsulation are reviewed. The challenges and potential solutions faced by UCNP optical encoding are also discussed.     

Electric-Field-Regulated Energy Transfer in Chiral Liquid Crystals for Enhancing Upconverted Circularly Polarized Luminescence through Steering the Photonic Bandgap

Circularly polarized luminescent materials with high dissymmetry factor (g_lum) have been attracting increasing attention due to their distinctive photonic properties. In this work, by incorporating upconversion nanoparticles (UCNPs) and CsPbBr₃ perovskite nanocrystals (PKNCs) into a chiral nematic liquid crystal (N*LC), enhanced upconverted circularly polarized luminescence (UC-CPL) based on a radiative energy transfer (RET) process from UCNPs to CsPbBr₃ PKNCs is successfully implemented. By locating the emission peak of CsPbBr₃ PKNCs at the center of the photonic bandgap of N*LC, the maximum g_lum value of UC-CPL can be amplified to an extremely large value of 1.1. Meanwhile, upconverted emission of UCNPs can be significantly enhanced due to the band edge enhancement effect of the N*LC, subsequently enhancing the emission of the CsPbBr₃ PKNCs through the RET process. In addition, an applied electric field can switch the upconverted emission of the UCNPs, as well as the RET process, enabling an electric-field-controlled UC-CPL switch.     

A Flexi-PEGDA Upconversion Implant for Wireless Brain Photodynamic Therapy

Near-infrared (NIR) activatable upconversion nanoparticles (UCNPs) enable wireless-based phototherapies by converting deep-tissue-penetrating NIR to visible light. UCNPs are therefore ideal as wireless transducers for photodynamic therapy (PDT) of deep-sited tumors. However, the retention of unsequestered UCNPs in tissue with minimal options for removal limits their clinical translation. To address this shortcoming, biocompatible UCNPs implants are developed to deliver upconversion photonic properties in a flexible, optical guide design. To enhance its translatability, the UCNPs implant is constructed with an FDA-approved poly(ethylene glycol) diacrylate (PEGDA) core clad with fluorinated ethylene propylene (FEP). The emission spectrum of the UCNPs implant can be tuned to overlap with the absorption spectra of the clinically relevant photosensitizer, 5-aminolevulinic acid (5-ALA). The UCNPs implant can wirelessly transmit upconverted visible light till 8 cm in length and in a bendable manner even when implanted underneath the skin or scalp. With this system, it is demonstrated that NIR-based chronic PDT is achievable in an untethered and noninvasive manner in a mouse xenograft glioblastoma multiforme (GBM) model. It is postulated that such encapsulated UCNPs implants represent a translational shift for wireless deep-tissue phototherapy by enabling sequestration of UCNPs without compromising wireless deep-tissue light delivery.     

Tunable Resonator‐Upconverted Emission (TRUE) Color Printing and Applications in Optical Security

Lanthanide‐doped nanophosphors are promising in anti‐counterfeiting and security printing applications. These nanophosphors can be incorporated as transparent inks that fluoresce by upconverting near‐infrared illumination into visible light to allow easy verification of documents. However, these inks typically exhibit a single luminescent color, low emission efficiency, and low print resolutions. Tunable resonator‐upconverted emission (TRUE) is achieved by placing upconversion nanoparticles (UCNPs) within plasmonic nanoresonators. A range of TRUE colors are obtained from a single‐UCNP species self‐assembled within size‐tuned gap‐plasmon resonances in Al nanodisk arrays. The luminescence intensities are enhanced by two orders of magnitude through emission and absorption enhancements. The enhanced emissive and plasmonic colors are simultaneously employed to generate TRUE color prints that exhibit one appearance under ambient white light, and a multicolored luminescence appearance that is revealed under near‐infrared excitation. The printed color and luminescent images are of ultrahigh resolutions (≈50 000 dpi), and enable multiple colors from a single excitation source for increased level of security.     

单个纳米颗粒的上转换光谱现象研究

稀土离子掺杂上转换纳米颗粒具有独特的光谱学特征, 在太阳能利用、三维显示和生物医学等众多领域有着广泛的应用价值。然而, 传统基于统计平均效应的上转换纳米颗粒群体性光谱学研究忽视了众多来自单个颗粒的非均一性信息。单颗粒光谱检测成为一种突破上述瓶颈, 获取源自纳米颗粒非均一性本征结构的独特光谱现象, 并实现单个纳米颗粒器件化的有效技术手段。对于单个纳米颗粒电子行为的研究能够揭示来自微结构本身的信息, 甚至能够在没有介质干扰下清晰洞见材料本征结构和外部作用的相互影响, 从而为制备高质量的纳米颗粒提供指导意义。同时, 单颗粒光谱检测也具有在微纳米尺度探索晶体结构各向异性光学特性及一些尚未预见的新型光学现象的强大能力。本文介绍了单个纳米颗粒上转换发光表征的重要性以及常见的几种检测方法。论述了单颗粒上转换发光的一些最新研究成果, 并对未来发展方向进行了展望。     

Integration of IR‐808 Sensitized Upconversion Nanostructure and MoS2 Nanosheet for 808 nm NIR Light Triggered Phototherapy and Bioimaging

Near infrared (NIR) light triggered phototherapy including photothermal therapy (PTT) and photodynamic therapy (PDT) affords superior outcome in cancer treatment. However, the reactive oxygen species (ROS) generated by NIR‐excited upconversion nanostructure is limited by the feeble upconverted light which cannot activate PDT agents efficiently. Here, an IR‐808 dye sensitized upconversion nanoparticle (UCNP) with a chlorin e6 (Ce6)‐functionalized silica layer is developed for PDT agent. The two booster effectors (dye‐sensitization and core–shell enhancement) synergistically amplify the upconversion efficiency, therefore achieving superbright visible emission under low 808 nm light excitation. The markedly amplified red light subsequently triggers the photosensitizer (Ce6) to produce large amount of ROS for efficient PDT. After the silica is endowed with positive surface, these PDT nanoparticles can be easily grafted on MoS₂ nanosheet. As the optimal laser wavelength of UCNPs is consistent with that of MoS₂ nanosheet for PTT, the invented nanoplatform generates both abundant ROS and local hyperthermia upon a single 808 nm laser irradiation. Both the in vitro and in vivo assays validate that the innovated nanostructure presents excellent cancer cell inhibition effectiveness by taking advantages of the synergistic PTT and PDT, simultaneously, posing trimodal (upconversion luminescence/computed tomography (CT)/magnetic resonance imaging (MRI) imaging capability.     

Highly-sensitive multiplexed <Emphasis Type="Italic">in vivo</Emphasis> imaging using pegylated upconversion nanoparticles

Lanthanide-based upconversion nanoparticles (UCNPs) have been widely explored in various fields, including optical imaging, in recent years. Although earlier work has shown that UCNPs with different lanthanide (Ln³⁺) dopants exhibit various colors, multicolor-especially in vivo multiplexed biomedical imaging-using UCNPs has rarely been reported. In this work, we synthesize a series of UCNPs with different emission colors and functionalize them with an amphiphilic polymer to confer water solubility. Multicolor in vivo upconversion luminescence (UCL) imaging is demonstrated by imaging subcutaneously injected UCNPs and applied in multiplexed in vivo lymph node mapping. We also use UCNPs for multicolor cancer cell labeling and realize in vivo cell tracking by UCL imaging. Moreover, for the first time we compare the in vivo imaging sensitivity of quantum dot (QD)-based fluorescence imaging and UCNP-based UCL imaging side by side, and find the in vivo detection limit of UCNPs to be at least one order of magnitude lower than that of QDs in our current non-optimized imaging system. Our data suggest that, by virtue of their unique optical properties, UCNPs have great potential for use in highly-sensitive multiplexed biomedical imaging.      

Lighting Up MicroRNA in Living Cells by the Disassembly of Lock‐Like DNA‐Programmed UCNPs‐AuNPs through the Target Cycling Amplification Strategy

Intracellular microRNAs imaging based on upconversion nanoprobes has great potential in cancer diagnostics and treatments. However, the relatively low detection sensitivity limits their application. Herein, a lock‐like DNA (LLD) generated by a hairpin DNA (H1) hybridizing with a bolt DNA (bDNA) sequence is designed, which is used to program upconversion nanoparticles (UCNPs, NaYF₄@NaYF₄:Yb, Er@NaYF₄) and gold nanoparticles (AuNPs). The upconversion emission is quenched through luminescence resonance energy transfer (LRET). The multiple LLD can be repeatedly opened by one copy of target microRNA under the aid of fuel hairpin DNA strands (H2) to trigger disassembly of AuNPs from the UCNP, resulting in the lighting up of UCNPs with a high detection signal gain. This strategy is verified using microRNA‐21 as model. The expression level of microRNA‐21 in various cells lines can be sensitively measured in vitro, meanwhile cancer cells and normal cells can be easily and accurately distinguished by intracellular microRNA‐21 imaging via the nanoprobes. The detection limit is about 1000 times lower than that of the previously reported upconversion nanoprobes without signal amplification. This is the first time a nonenzymatic signal amplification method has been combined with UCNPs for imaging intracellular microRNAs, which has great potential for cancer diagnosis.     

Particle-size-dependent upconversion luminescence of NaYF4: Yb,Er nanoparticles in organic solvents and water at different excitation power densities

Nano Research - A systematic study of the luminescence properties of monodisperse β-NaYF4: 20% Yb3+, 2% Er3+ upconversion nanoparticles (UCNPs) with sizes ranging from 12–43 nm is...     

An Excitation Navigating Energy Migration of Lanthanide Ions in Upconversion Nanoparticles

Upconversion nanoparticles (UCNPs) doped with lanthanide ions that possess ladder-like energy levels can give out multiple emissions at specific ultra-violet or visible wavelengths irrespective of excitation light. However, precisely controlling energy migration processes between different energy levels of the same lanthanide ion to generate switchable emissions remains elusive. Herein, a novel dumbbell-shaped UCNP is reported with upconverted red emission switched to green emission when excitation wavelength changed from 980 to 808 nm. The sensitizer Yb ions are doped with activator Er ions and energy modulator Mn ions in NaYF₄ core nanocrystal coated with an inner NaYF₄:Yb shell to generate red emission after harvesting 980 nm excitation light, while an outer NaNdF₄:Yb shell is coated to form a dumbbell shape to generate green emission upon 808 nm excitation. Such specially designed UCNPs with switchable green and red emissions are further explored for imaging of latent fingerprint and detection of explosive residues in the fingerprint simultaneously. This work suggests a novel research interest in fine-tuning of upconversion emissions through precisely controlling energy migration processes of the same lanthanide activator ion. Furthermore, use of these nanoparticles in other applications such as simultaneous dual-color imaging or orthogonal bidirectional photoactivation can be explored.     

稀土上转换发光纳米材料的制备及生物医学应用研究进展

荧光探针技术已经被广泛应用于生物成像、生物标记、生物检测、免疫分析等生物医学领域。传统荧光标记材料,如有机荧光染料、荧光蛋白和半导体量子点,目前面临诸多应用局限,如发光强度不稳定、检测灵敏度低、生物毒性高、自荧光强等。有鉴于此,人们开发了La系金属离子掺杂的稀土上转换发光纳米材料作为新型生物标记材料,该材料受近红外光激发后发出近红外或可见光范围内的高能量光子。这种带有特殊光学性质及良好生物相容性的荧光标记材料克服了传统荧光标记材料的缺点,从而成为材料科学与生物医学交叉领域的研究热点。综述了稀土纳米材料上转换功能的特殊物理机制及其制备和表面修饰方法的研究进展。在此基础上介绍了稀土上转换纳米材料在生物成像、检测、载药、即时诊断器件开发等生物医学工程中的应用。     

Silica shell-assisted synthetic route for mono-disperse persistent nanophosphors with enhanced in vivo recharged near-infrared persistent luminescence

Near-infrared (NIR) persistent-luminescence nanoparticles have emerged as a new class of background-free contrast agents that are promising for in vivo imaging.The next key roadblock is to establish a robust and controllable method for synthesizing monodisperse nanoparticles with high luminescence brightness and long persistent duration.Herein,we report a synthesis strategy involving the coating/etching of the SiO2 shell to obtain a new class of small NIR highly persistent luminescent ZnGa2O4∶Cr3+,Sn4+ (ZGOCS) nanoparticles.The optimized ZGOCS nanoparticles have an excellent size distribution of ～15 nm without any agglomeration and an NIR persistent luminescence that is enhanced by a factor of 13.5,owing to the key role of the SiO2 shell in preventing nanoparticle agglomeration after annealing.The ZGOCS nanoparticles have a signal-to-noise ratio ～3 times higher than that of previously reported ZnGa2O4∶Cr3+ (ZGC-1) nanoparticles as an NIR persistent-luminescence probe for in vivo bioimaging.Moreover,the persistent-luminescence signal from the ZGOCS nanoparticles can be repeatedly re-charged in situ with external excitation by a white lightemitting diode;thus,the nanoparticles are suitable for long-term in vivo imaging applications.Our study suggests an improved strategy for fabricating novel high-performance optical nanoparticles with good biocompatibility.     

Binary Nanoparticle Superlattices for Plasmonically Modulating Upconversion Luminescence

Engineering a facile and controllable approach to modulate the spectral properties of lanthanide‐doped upconversion nanoparticles (UCNPs) is always an ongoing challenge. Herein, long‐range ordered, distinct two‐dimensional (2D) binary nanoparticle superlattices (BNSLs) composed of NaREF₄:Yb/Er (RE = Y and Gd) UCNPs and plasmonic metallic nanoparticles (Au NPs), including AB, AB₃, and AB₁₃ lattices, are fabricated via a slow evaporation‐driven self‐assembly to achieve plasmonic modulation of upconversion luminescence (UCL). Optical measurements reveal that typical red–green UCL from UCNPs can be effectively modulated into reddish output in BNSLs, with a drastically shortened lifetime. Notably, for AB₃‐ and AB₁₃‐type BNSLs with more proximal Au NPs around each UCNP, modified UCL with fine‐structured spectral lineshape is observed. These differences could be interpreted by the interplay of collective plasmon resonance introduced by 2D periodic Au arrays and spectrally selective energy transfer between UCNPs and Au. Thus, fabricating UCNP‐Au BNSLs with desired lattice parameters and NP configurations could be a promising way to tailor the UCL through controlled plasmonic modulation.     

Temperature modulation of concentration quenching in lanthanide-doped nanoparticles for enhanced upconversion luminescence

Nano Research - The doping concentration of lanthanide ions is important for manipulating the luminescence properties of upconversion nanoparticles (UCNPs). However, the serious concentration...     

Phytotoxicity,Translocation, and Biotransformation of NaYF4 Upconversion Nanoparticles in a Soybean Plant

The increasing uses of rare‐earth‐doped upconversion nanoparticles (UCNPs) have obviously caused many concerns about their potential toxicology on live organisms. In addition, the UCNPs can be released into the environment, then transported into edible crop plants, and finally entered into food chain. Here, the soybean is chosen as a model plant to study the subchronic phytotoxicity, translocation, and biotransformation of NaYF₄ UCNPs. The incubation with UCNPs at a relative low concentration of 10 μg mL^?1 leads to growth promotion for the roots and stems, while concentration exceeding 50 μg mL^?1 brings concentration‐dependent inhibition. Upconversion luminescence imaging and scanning electron microscope characterization show that the UCNPs can be absorbed by roots and parts of the adsorbed UCNPs are then transported through vessels to stems and leaves. The near‐edge X‐ray absorption fine structure spectra reveal that the adsorbed NaYF₄ nanoparticles are relatively stable during a 10 d incubation. Energy‐dispersive X‐ray spectrum further indicates that a small amount of NaYF₄ is dissolved/digested and can transform into Y‐phosphate clusters in roots.     

Synthesis of ligand-free colloidally stable water dispersible brightly luminescent lanthanide-doped upconverting nanoparticles

The synthesis using the thermal decomposition of metal trifluoroacetates is being widely used to prepare oleate-capped lanthanide-doped upconverting NaYF(4):Er(3+)/Yb(3+) nanoparticles (Ln-UCNPs). These nanoparticles have no inherent aqueous dispersibility and inconvenient postsynthesis treatments are required to render them water dispersible. Here, we have developed a novel and facile approach to obtain water-dispersible, ligand-free, brightly upconverting Ln-UCNPs. We show that the upconversion luminescence is affected by the local environment of the lanthanide ions at the surface of the Ln-UCNPs. We observe a dramatic difference of the integrated upconverted red:green emission ratio for Ln-UCNPs dispersed in toluene compared to Ln-UCNPs dispersed in water. We can enhance or deactivate the upconversion luminescence by pH and H/D isotope vibronic control over the competitive radiative and nonradiative relaxation pathways for the red and green excited states. Direct biofunctionalization of the ligand-free, water-dispersible Ln-UCNPs will enable myriad new opportunities in targeting and drug delivery applications.     

Photon Upconverted Circularly Polarized Luminescence via Triplet–Triplet Annihilation

Circularly polarized luminescent materials are of increasing attention due to their potential applications in advanced optical technologies, such as chiroptical devices and optical sensing. Recently, in all reported circularly polarized luminescent materials, high‐energy excitation results in low‐energy or downconverted circularly polarized luminescence (CPL) emission. Although photon upconversion—i.e., the conversion of low‐energy light into higher‐energy emission, with a wide variety of applications—has been widely reported, the integration of photon upconversion and CPL in one chiral system to achieve higher‐energy CPL emission has never been reported. Herein, a brief review is provided of recent achievements in photon‐upconverted CPL via the triplet–triplet annihilation mechanism, focusing on the amplified dissymmetry factor g_lum through energy transfer process and dual upconverted and downconverted CPL emission through chirality and energy transfer process.     

Recent Advances in Upconversion Nanoparticles‐Based Multifunctional Nanocomposites for Combined Cancer Therapy

Lanthanide‐doped upconversion nanoparticles (UCNPs) have the ability to generate ultraviolet or visible emissions under continuous‐wave near‐infrared (NIR) excitation. Utilizing this special luminescence property, UCNPs are approved as a new generation of contrast agents in optical imaging with deep tissue‐penetration ability and high signal‐to‐noise ratio. The integration of UCNPs with other functional moieties can endow them with highly enriched functionalities for imaging‐guided cancer therapy, which makes composites based on UCNPs emerge as a new class of theranostic agents in biomedicine. Here, recent progress in combined cancer therapy using functional nanocomposites based on UCNPs is reviewed. Combined therapy referring to the co‐delivery of two or more therapeutic agents or a combination of different treatments is becoming more popular in clinical treatment of cancer because it generates synergistic anti‐cancer effects, reduces individual drug‐related toxicity and suppresses multi‐drug resistance through different mechanisms of action. Here, the recent advances of combined therapy contributed by UCNPs‐based nanocomposites on two main branches are reviewed: i) photodynamic therapy and ii) chemotherapy, which are the two most widely adopted therapies of UCNPs‐based composites. The future prospects and challenges in this emerging field will be also discussed.     

上转换荧光光子晶体薄膜的制备及包装防伪应用

以热分解法制备的蓝色荧光NaYF4:Yb3+,Tm3+上转换纳米颗粒为核,外延生长一层具有钝化表面缺陷、增强荧光效果的NaYF4壳层,制备得到核壳上转换纳米颗粒(CSNPs).利用反相微乳液法在CSNPs上包覆一层修饰3-(三甲氧基甲硅基)甲基丙烯酸丙酯(MPS)的SiO2,实现上转换纳米颗粒亲水改性的同时,赋予其可参与加成聚合的双键.将CSNPs@SiO2-MPS与苯乙烯单体通过乳液聚合共聚形成镧系掺杂NaYF4/PS复合微球.通过垂直沉积法,利用镧系掺杂NaYF4/PS复合微球自组装构建上转换荧光光子晶体(UCPC)薄膜,并探讨其在包装防伪中的应用.结果表明:该上转换荧光光子晶体薄膜,在可见光下从特定角度可以观察到明显的粉色结构色,在980 nm激光照射下可观察到蓝色荧光,这两种模态下的光学特性可隐藏信息,预期在信息保护、包装防伪等领域有广阔的应用前景.     

用于包装防伪的稀土上转换发光材料

目的 从增强稀土离子发光的角度考察上转换发光调控及性能,综述稀土发光材料在光学防伪领域的应用,以期为上转换材料与包装材料的功能化研究提供参考。方法 检索近几年文献,介绍上转换发光纳米材料的发光机理、发光性能及调控、光学材料打印技术的研究进展。结果 稀土掺杂的上转换发光纳米材料表现出优异的发光性能,但随着粒径减小,纳米颗粒出现发光效率、量子产量低的问题。利用纳米颗粒表面钝化、表面等离子体耦合、与有机配体结合和外场调节等手段,可以使发光材料的发光效能显著增强。利用喷墨打印、丝网印刷、纳米压印光刻和气溶胶喷印等技术,可以使稀土掺杂的上转换发光纳米材料被打印成多样的防伪图案,在光学防伪、信息存储与标记等领域具有重大应用潜力,有望成为新型功能包装材料。结论 在光学材料合成技术、光学调控和打印技术的共同推动下,稀土掺杂上转换发光纳米材料因其特殊的光学特性,有望为功能化包装防伪技术作出贡献。