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.     

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.     

通过热场和电场实现镧系离子掺杂铁电纳米复合材料上转换发光的可逆增强（英文）

调节镧系离子发光特性在传感、多彩显示、信息传递、防伪等领域具有重要意义.发光调控通常采用调控化学组分来实现,然而化学调控法不利于发展多模式检测、多重信息防伪等.本研究以镧系离子掺杂铁电纳米复合材料为研究对象,在热场和电场两种外部环境刺激下实现增强发光.在热场激励下样品呈现反猝灭现象,升温有效地增强了镧系离子的上转换近红外发光.同时基质中的铁电微晶晶格具有机电软弹性;通过电场调节镧系离子周围的晶体场结构实现了显著的发光增强,这种调控具有优异的可逆性和非易失性.本研究表明,可以通过热场和电场调控镧系离子掺杂多功能无机铁电体纳米复合材料的发光性质,这为设计高度集成的发光传感器件和智能设备提供了重要参考,特别是发展先进的多模式检测材料.     

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.     

Security printing of covert quick response codes using upconverting nanoparticle inks

Counterfeiting costs governments and private industries billions of dollars annually due to loss of value in currency and other printed items. This research involves using lanthanide doped β-NaYF(4) nanoparticles for security printing applications. Inks comprised of Yb(3+)/Er(3+) and Yb(3+)/Tm(3+) doped β-NaYF(4) nanoparticles with oleic acid as the capping agent in toluene and methyl benzoate with poly(methyl methacrylate) (PMMA) as the binding agent were used to print quick response (QR) codes. The QR codes were made using an AutoCAD file and printed with Optomec direct-write aerosol jetting(?). The printed QR codes are invisible under ambient lighting conditions, but are readable using a near-IR laser, and were successfully scanned using a smart phone. This research demonstrates that QR codes, which have been used primarily for information sharing applications, can also be used for security purposes. Higher levels of security were achieved by printing both green and blue upconverting inks, based on combinations of Er(3+)/Yb(3+) and Tm(3+)/Yb(3+), respectively, in a single QR code. The near-infrared (NIR)-to-visible upconversion luminescence properties of the two-ink QR codes were analyzed, including the influence of NIR excitation power density on perceived color, in term of the CIE 1931 chromaticity index. It was also shown that this security ink can be optimized for line width, thickness and stability on different substrates.     

Lanthanide‐Doped Photoluminescence Hollow Structures: Recent Advances and Applications

Lanthanide‐doped nanomaterials have attracted significant attention for their preeminent properties and widespread applications. Due to the unique characteristic, the lanthanide‐doped photoluminescence materials with hollow structures may provide advantages including enhanced light harvesting, intensified electric field density, improved luminescent property, and larger drug loading capacity. Herein, the synthesis, properties, and applications of lanthanide‐doped photoluminescence hollow structures (LPHSs) are comprehensively reviewed. First, different strategies for the engineered synthesis of LPHSs are described in detail, which contain hard, soft, self‐templating methods and other techniques. Thereafter, the relationship between their structure features and photoluminescence properties is discussed. Then, niche applications including biomedicines, bioimaging, therapy, and energy storage/conversion are focused on and superiorities of LPHSs for these applications are particularly highlighted. Finally, keen insights into the challenges and personal prospects for the future development of the LPHSs are provided.     

On The Latest Three‐Stage Development of Nanomedicines based on Upconversion Nanoparticles

Following the “detect‐to‐treat” strategy, by biological engineering, the emerging upconversion nanoparticles (UCNPs) have become one of the most promising inorganic nanomedicines, and their biomedical applications have gradually shifted from multimodal tumor imaging to highly efficient cancer therapy. The past few years have witnessed a three‐stage development of UCNP‐based nanomedicines. On one hand, UCNPs can optimize each clinical treatment tool (chemotherapy, photodynamic therapy (PDT), radiotherapy (RT)) by controlled drug delivery/release, near‐infrared (NIR)‐excited deep PDT, and radiosensitization, respectively, all of which contribute greatly to the optimized treatment efficacy along with minimized side effects. On the other hand, several individual treatments can be “smartly” integrated into a single UCNP‐based nanotheranostic system for multimodal synergetic therapy, which can further improve the overall therapeutic effectiveness. Especially, UCNPs provide more‐effective strategies for overcoming tumor hypoxia, thus leading to an ideal treatment efficacy for complete eradication of solid tumors. Finally, the critical issues regarding the future development of UCNPs are discussed to promote the clinic‐translational applications of UCNP‐based nanomedicines, as well as realization of our “one drug fits all” dream.     

Tuning upconversion through energy migration in core-shell nanoparticles

Photon upconversion is promising for applications such as biological imaging, data storage or solar cells. Here, we have investigated upconversion processes in a broad range of gadolinium-based nanoparticles of varying composition. We show that by rational design of a core-shell structure with a set of lanthanide ions incorporated into separated layers at precisely defined concentrations, efficient upconversion emission can be realized through gadolinium sublattice-mediated energy migration for a wide range of lanthanide activators without long-lived intermediary energy states. Furthermore, the use of the core-shell structure allows the elimination of deleterious cross-relaxation. This effect enables fine-tuning of upconversion emission through trapping of the migrating energy by the activators. Indeed, the findings described here suggest a general approach to constructing a new class of luminescent materials with tunable upconversion emissions by controlled manipulation of energy transfer within a nanoscopic region.     

Combinatorial discovery of lanthanide-doped nanocrystals with spectrally pure upconverted emission

Nanoparticles doped with lanthanide ions exhibit stable and visible luminescence under near-infrared excitation via a process known as upconversion, enabling long-duration, low-background biological imaging. However, the complex, overlapping emission spectra of lanthanide ions can hinder the quantitative imaging of samples labeled with multiple upconverting probes. Here, we use combinatorial screening of multiply doped NaYF(4) nanocrystals to identify a series of doubly and triply doped upconverting nanoparticles that exhibit narrow, spectrally pure emission spectra at various visible wavelengths. We then developed a comprehensive kinetic model validated by our extensive experimental data set. Applying this model, we elucidated the energy transfer mechanisms giving rise to spectrally pure emission. These mechanisms suggest design rules for electronic level structures that yield robust color tuning in lanthanide-doped upconverting nanoparticles. The resulting materials will be useful for background-free multicolor imaging and tracking of biological processes.     

Minimizing the Heat Effect of Photodynamic Therapy Based on Inorganic Nanocomposites Mediated by 808 nm Near‐Infrared Light

Photodynamic therapy (PDT) based on photosensitizers (PSs) constructed with nanomaterials has become popular in cancer treatment, especially oral carcinoma cell. This therapy is characterized by improved PS accumulation in tumor regions and generation of reactive oxygen species (ROS) for PDT under specific excitation. In the selection of near‐infrared (NIR) window, 808 nm NIR light because it can avoid the absorption of water is particularly suitable for the application in PDT. Hence, multiband emissions under a single 808 nm near‐infrared excitation of Nd³⁺‐sensitized upconversion nanoparticles (808 nm UCNPs) have been applied for the PDT effect. 808 nm UCNPs serve as light converter to emit UV light to excite inorganic PS, graphitic carbon nitride quantum dots (CNQDs), thereby generating ROS. In this study, a nanocomposite consisting UCNPs conjugated with poly‐l ‐lysine (PLL) to improve binding with CNQDs is fabricated. According to the research results, NIR‐triggered nanocomposites of 808 nm UCNP‐PLL@CNs have been verified by significant improvement in ROS generation. Consequently, 808 nm UCNP‐PLL@CNs exhibit high capability for ROS production and efficient PDT in vitro and in vivo. Moreover, the mechanism of PDT treatment by 808 nm UCNP‐PLL@CNs is evaluated using the cell apoptosis pathway.     

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.     

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。     

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.     

Emerging ≈800 nm Excited Lanthanide‐Doped Upconversion Nanoparticles

Lanthanide‐doped upconversion nanoparticles can tune near‐infrared light to visible or even ultra‐violet light in emissions. Due to their unique photophysical and photochemical properties, as well as their promising bioapplications, there has been a great deal of enthusiastic research performed to study the properties of lanthanide‐doped upconversion nanoparticles in the past few years. Despite the considerable progress in this area, numerous challenges associated with the nanoparticles, such as a low upconversion efficiency, limited host materials, and a confined excitation wavelength, still remain, thus hindering further development with respect to their applications and in fundamental science. Recently, innovative strategies that utilize alternative sensitizers have been designed in order to engineer the excitation wavelengths of upconversion nanoparticles. Here, focusing on the excitation wavelength at ≈800 nm, recent advances in the design, property tuning, and applications of ≈800 nm excited upconversion nanoparticles are summarized. Benefiting from the unique features of ≈800 nm light, including deep tissue penetration depth and low photothermal effect, the ≈800 nm excited upconversion nanoparticles exhibit superior potential for biosensing, bioimaging, drug delivery, therapy, and three dimensional displays. The critical aspects of such emerging nanoparticles with regards to meeting the ever‐changing needs of future development are also discussed.     

Preparation of lanthanide doped CdS, ZnS quantum dots in natural polysaccharide template and their optical properties

Employing a biomimic method using polysaccharide as template, luminescent lanthanide ions doped CdS and ZnS quantum dots (QDs) were prepared. According to the results of TEM and absorbance, nanocrystals with an average size of 6 nm were formed under mild condition without any toxic and expensive agent applied. Differentiating from the un-doped CdS and ZnS QDs prepared in polysaccharide template, the lanthanide doped QDs exhibited obvious dopant emission in their photoluminescence spectrum. It was also found that the dopant PL became more prominent with increasing lanthanide doping concentration, while the highest PL intensity was obtained at a doping level of 1% for both of CdS and ZnS QDs. When different lanthanide ions were introduced into the CdS QDs in polysaccharide template, varied emission wavelength were able to be obtained. This study provides an easy, mild and environmental friendly alternative method to prepare doped quantum dots. In addition, the bioactivity and processabilities endowed by the polysaccharide template may expand the applications potential of this type of optical materials.     

Controllable synthesis of NaYF(4) : Yb,Er upconversion nanophosphors and their application to in vivo imaging of Caenorhabditis elegans

β-NaYF(4) : Yb,Er upconversion nanoparticles (UCNPs) can emit bright green fluorescence under near-infrared (NIR) light excitation which is safe to the body and can penetrate deeply into tissues. The application of UCNPs in biolabeling and imaging has received great attention recently. In this work, β-NaYF(4) : Yb,Er UCNPs with an average size of 35 nm, uniformly spherical shape, and surface modified with amino groups were synthesized by a one-step green solvothermal approach through the use of room-temperature ionic liquids as the reactant, co-solvent and template. The as-prepared UCNPs were introduced into Caenorhabditis elegans (C. elegans) to achieve successful in vivo imaging. We found that longer incubation time, higher UCNP concentration and smaller UCNP size can make the in vivo fluorescence of C. elegans much brighter and more continuous along their body. The worms have no apparent selectivity on ingestion of the UCNPs capped with different capping ligands while having similar size and shape. The next generation of worms did not show fluorescence under excitation. In addition, low toxicity of the nanoparticles was demonstrated by investigating the survival rates of the worms in the presence of the UCNPs. Our work demonstrates the potential application of the UCNPs in studying the biological behavior of organisms, and lays the foundation for further development of the UCNPs in the detection and diagnosis of diseases.     

New Strategy: Molten Salt-Assisted Synthesis to Enhance Lanthanide Upconversion Luminescence

Lanthanide-doped upconversion luminescent materials (LUCMs) have attracted much attention in diverse practical applications because of their superior features. However, the relatively weak luminescence intensity and low efficiency of LUCMs are the bottleneck problems that seriously limit their development. Unfortunately, most of the current major strategies of luminescence enhancement have some inherent shortcomings in their implementation. Here, a new and simple strategy of molten salt-assisted synthesis is proposed to enhance lanthanide upconversion luminescence for the first time. As a proof-of-concept, a series of rare earth oxides with obvious luminescence enhancement are prepared by a one-step method, utilizing molten NaCl as the high-temperature reaction media and rare earth chlorides as the precursors. The enhancement factors at different reaction temperatures are systematically investigated by taking Yb³⁺/Er³⁺ co-doped Y₂O₃ as an example, which can be enhanced up to more than six times. In addition, the molten salts are extended to all alkali chlorides, indicating that it is a universal strategy. Finally, the potential application of obtained UCL materials is demonstrated in near-infrared excited upconversion white light-emitting diodes (WLEDs) and other monochromatic LEDs.     

Double‐Targeting Explosible Nanofirework for Tumor Ignition to Guide Tumor‐Depth Photothermal Therapy

This study reports a double‐targeting “nanofirework” for tumor‐ignited imaging to guide effective tumor‐depth photothermal therapy (PTT). Typically, ≈30 nm upconversion nanoparticles (UCNP) are enveloped with a hybrid corona composed of ≈4 nm CuS tethered hyaluronic acid (CuS‐HA). The HA corona provides active tumor‐targeted functionality together with excellent stability and improved biocompatibility. The dimension of UCNP@CuS‐HA is specifically set within the optimal size window for passive tumor‐targeting effect, demonstrating significant contributions to both the in vivo prolonged circulation duration and the enhanced size‐dependent tumor accumulation compared with ultrasmall CuS nanoparticles. The tumors featuring hyaluronidase (HAase) overexpression could induce the escape of CuS away from UCNP@CuS‐HA due to HAase‐catalyzed HA degradation, in turn activating the recovery of initially CuS‐quenched luminescence of UCNP and also driving the tumor‐depth infiltration of ultrasmall CuS for effective PTT. This in vivo transition has proven to be highly dependent on tumor occurrence like a tumor‐ignited explosible firework. Together with the double‐targeting functionality, the pathology‐selective tumor ignition permits precise tumor detection and imaging‐guided spatiotemporal control over PTT operation, leading to complete tumor ablation under near infrared (NIR) irradiation. This study offers a new paradigm of utilizing pathological characteristics to design nanotheranostics for precise detection and personalized therapy of tumors.     

Surfactant effects on efficiency enhancement of infrared-to-visible upconversion emissions of NaYF4:Yb-Er

Infrared-to-visible rare earth doped upconversion phosphors that convert multiple photons of lower energy to higher energy photons offer a wide range of technological applications. The brightness (i.e., emission intensities) and energy efficiency of phosphors are important performance characteristics that determine which applications are appropriate. Optical efficiency can be used as a measure of the upconversion emission performance of these rare earth doped phosphors. In this work, hexagonal-phase NaYF(4):Yb-Er was synthesized using the hydrothermal method in the presence of surfactants like trioctylphosphine, polyethylene glycol monooleate, and polyvinylpyrrolidone. The upconversion emission optical efficiencies of NaYF(4):Yb-Er were measured to quantify and evaluate the effects of surface coatings and accurately reflect the brightness and energy efficiency of these phosphors. Polyvinylpyrrolidone-modified NaYF(4):Yb-Er particles were found to be ~5 times more efficient and brighter than the unmodified particles. The difference in efficiency was attributed to reduced reflectance losses at the particle-air interface via refractive index mismatch reduction between the core NaYF(4):Yb-Er particles and air using polyvinylpyrrolidone as a surfactant.     

上转换发光材料La(OH)3∶Er3+/Yb3+的制备及在染料敏化太阳能电池中的应用

针对N719染料仅可吸收可见光这一局限,本研究旨在通过引入上转换发光材料并将其应用于染料敏化太阳能电池的光阳极来拓宽光谱吸收范围,提高光的捕获率,进而达到提高电池光电转换效率的目的。首先,采用水热合成法以不同pH值的先驱体溶液,成功制备了Yb~(3+)/Er~(3+)双掺杂La(OH)_3粉末,然后将适量合成的稀土发光粉掺入TiO_2纳米浆料中,采用刮涂法成膜制备光阳极,并将其组装成染料敏化太阳能电池。研究结果表明,稀土发光粉的加入拓宽了光谱吸收范围,在其掺杂量达到3%时,电池的短路电流密度Jsc提高到17.72mA·cm-2,最终获得了8.3%的光电转换效率。