Synthesis of monodisperse NaYF4:Yb, Tm@SiO2 nanoparticles with intense ultraviolet upconversion luminescence

In this paper, the NaYF4:Yb, Tm upconversion (UC) nanoparticles (NPs) were synthesized using a solvothermal approach, and the core-shell structured NaYF4:Yb, Tm@SiO2 NPs, coated with a thin layer of SiO2 on the surface of the NaYF4:Yb, Tm NPs, were prepared by a typical St?ber method. X-ray diffraction (XRD), transmission electron microscopy (TEM), and luminescence spectroscopy were applied to characterize these samples. The obtained core-shell structured NaYF4:Yb, Tm@SiO2 NPs exhibited a perfect spherical morphology with narrow size distribution and smooth surfaces. Under 980 nm excitation, NaYF4:Yb, Tm and NaYF4:Yb, Tm@SiO2 samples showed intense ultraviolet UC luminescence, which originated from the 1D2 --> 3H6, 1I6 --> 3F4 transitions of Tm3+. These NPs have great potential for applications as fluorescent labels, imaging probes, optical storage, photodynamic therapy (PDT) in deep tissue, and solid-state lasers.     

原位聚合法制备水溶性高聚物修饰的NaYF4：Yb,Er

采用原位聚合法,以聚丙烯酸（PAA）和聚乙烯吡咯烷酮（PVP）为壳层材料,对NaYF4上转换发光材料表面进行了PAA和PVP的修饰,傅立叶红外吸收光谱和热重分析证明了NaYF4纳米粒子表面有PAA和PVP的存在,透射电镜显示,当反应温度在0℃,丙烯酸单体含量为8.0wt%,反应时间130min时,PAA修饰的纳米粒子微观形貌最佳;当反应温度在60℃,乙烯基吡咯烷酮单体含量在12.0wt%,反应时间在150min的条件下,PVP修饰的纳米粒子微观形貌最佳。上转换荧光测试结果证明,在对材料进行NaYF4无机壳层包覆后再进行水溶性高聚物修饰,能够使其荧光性能保持不变。     

原位聚合法制备聚丙烯酸修饰的ZnS量子点

采用原位聚合法对ZnS量子点表面进行聚丙烯酸(PAA)的修饰。利用XRD、FTIR、TEM、TGA、荧光测试等对ZnS@PAA复合纳米粒子进行系列表征。XRD分析表明,修饰后的ZnS仍为立方晶相。FTIR和TGA结果证明,ZnS纳米粒子表面存在PAA。TEM结果表明,修饰后ZnS@PAA复合纳米粒子在去离子水中分散良好,其直径有所增加,约为28 nm,且呈较明显的核-壳结构。荧光测试发现,修饰PAA前后ZnS@PAA复合纳米粒子的发光特性没有发生明显改变。实验表明,经PAA修饰后,ZnS@PAA复合纳米粒子在水溶液中的分散性和稳定性得到提高,抗氧化性和荧光稳定性也得到了一定的增强。      

Study on NIR optical rewritable film based on dithienylethene and upconversion nanocrystals

Tm3+ and Yb3+ codoped NaYF4 upconversion (UC) nanoparticles (NPs) with intense ultraviolet (UV) fluorescence were synthesized using a solvothermal approach. NIR optical rewritable film incorporated with the UCNPs and dithienylethene (DTE) were performed for optical storage based on the photochromic reaction of DTE induced by the intense UV from themultiphoton UC fluorescence of NaYF4NPs. The photochromic DTE did not exhibit obvious fatigue after repetitious write/erase cycles using NIR/green irradiation.     

NaYF4：Yb,Er红色上转换发光纳米粒子的合成

利用热分解方法在油酸和十八胺的混合溶剂中合成了红色上转换发光的α-NaYF4：Yb,Er纳米粒子,通过X射线衍射（XRD）、透射电镜（TEM）以及980nm激发下的上转换发光光谱等方法进行表征,结果发现,在溶剂油酸和十八胺混合溶剂中,虽然反应时间和温度不同,但产物均为立方相结构且光学性能几乎呈现纯的红色发射光,说明可以在很广泛的范围内合成具有良好的红色上转换发光的NaYF4：Yb,Er纳米粒子。     

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.     

Synthesis and characterization of lanthanide-doped sodium holmium fluoride nanoparticles for potential application in photothermal therapy

Upconversion nanoparticles (UC NPs) in combination with plasmonic materials have great potential for cancer photothermal therapy. Recently, sodium holmium fluoride (NaHoF₄) is being investigated for luminescence and magnetic resonance imaging (MRI) contrast agent. Here, we present successful synthesis of excellent quality doped NaHoF₄ NPs for possible UC luminescence application and coated for possible photothermal therapy application. Synthesized NaHoF₄ nanocrystals were doped with Yb/Er and coated with gold, gold/silica, silver and polypyrrole (PPy). XRD, XPS and TEM were used to determine structure and morphology of the NPs. Strong UC photoluminescence (PL) emission spectra were obtained from the NPs when excited by near-infrared (NIR) light at 980 nm. Cell viability and toxicity of the NPs were characterized using pancreatic and ovarian cancer cells with results showing that gold/silica coating produced least toxicity followed by gold coating.     

NIR Biosensing of Neurotransmitters in Stem Cell‐Derived Neural Interface Using Advanced Core–Shell Upconversion Nanoparticles

Nondestructive neurotransmitter detection and real‐time monitoring of stem cell differentiation are both of great significance in the field of neurodegenerative disease and regenerative medicine. Although luminescent biosensing nanoprobes have been developed to address this need, they have intrinsic limitations such as autofluorescence, scattering, and phototoxicity. Upconversion nanoparticles (UCNPs) have gained increasing attention for various biomedical applications due to their high photostability, low auto‐fluorescent background, and deep tissue penetration; however, UCNPs also suffer from low emission intensities due to undesirable energy migration pathways. To address the aforementioned issue, a single‐crystal core–shell–shell “sandwich” structured UCNP is developed that is designed to minimize deleterious energy back‐transfer to yield bright visible emissions using low power density excitations. These UCNPs show a remarkable enhancement of luminescent output relative to conventional β‐NaYF4:Yb,Er codoped UCNPs and β‐NaYF4:Yb,Er@NaYF4:Yb “active shell” alike. Moreover, this advanced core–shell–shell UCNP is subsequently used to develop a highly sensitive biosensor for the ultrasensitive detection of dopamine released from stem cell‐derived dopaminergic‐neurons. Given the challenges of in situ detection of neurotransmitters, the developed NIR‐based biosensing of neurotransmitters in stem cell‐derived neural interfaces present a unique tool for investigating single‐cell mechanisms associated with dopamine, or other neurotransmitters, and their roles in neurological processes.     

Structural design and synthesis of new MOO3-x interlayer bi-functional nanomaterials for enhanced up-conversion luminescence properties

A novel imaging materials based on bi-functional Fe₃O₄@M_OO_3-x@YF₃:Yb/Er nanoparticles (NPs) with strong up-conversion luminescence and magnetic properties was designed and synthesized by inlaying M_OO_3-x with localized surface plasmon resonance (LSPR) and ferromagnetic property in the bi-functional Fe₃O₄@YF₃:Yb/Er NPs. The morphology, structure and properties of Fe₃O₄@M_OO_3-x@YF₃:Yb/Er NPs are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX), photoluminescence (PL) spectra, UV–Vis-NIR spectrophotometer and superconducting quantum interference devices (SQUID). It was found that the experimental conditions (reaction temperature, reaction time, the mass ratio of core:shell and oxygen pressure in heat treatment) have a certain effect on the oxygen defect concentration of the M_OO_3-x interlayer. XRD also showed the crystal structure of Fe₃O₄, Fe₃O₄@M_OO_3-x and Fe₃O₄@M_OO_3-x@YF₃:Yb/Er NPs. The SEM and TEM results showed that the average grain size of the prepared NPs were 200 nm. The SQUID and PL results showed that the Fe₃O₄@M_OO_3-x@YF₃:Yb/Er NPs have stronger magnetism (14.3 emu/g) and excellent up-conversion luminescence performance (the emission peak at 525 nm is nearly 20 times higher than the corresponding emission intensity of the Fe₃O₄@YF₃:Yb/Er). The Fe₃O₄@M_OO_3-x@YF₃:Yb/Er NPs can be easily used to magnetic resonance and fluorescence dual-mode image-guided visual delivery drug and also increase the accurate diagnosis and treatment effect of malignant tumor.     

Synthesis and characterization of upconverting NaYF4:Er3+, Yb3+ nanocrystals via thermal decomposition of stearate precursor

Er3+-Yb3+ codoped hexagonal NaYF4 nanocrystals were prepared via a method of thermal decomposition of stearate precursor. Their crystal structure, morphologies and photoluminescence (PL) properties were characterized by XRD, SEM, and fluorescence spectra. The hexagonal NaYF4:Er3+, Yb3+ nanocrystals could be well dispersed in cyclohexane to form a clear solution. Under 980 nm excitation, the solution of Er3+-Yb3+ codoped NaYF4 nanocrystals emits bright green upconversion fluorescence.     

色彩可调Yb, Er共掺杂NaYF4上转换荧光材料的 合成及包装防伪应用

采用阴离子表面活性剂柠檬酸三钠和阳离子表面活性剂氯代十六烷基吡啶共同调介下的水热法,合成Yb,Er共掺杂NaYF_4上转换荧光材料(NaYF_4:Yb~(3+),Er~(3+));研究敏化剂Yb~(3+)和激活剂Er~(3+)在NaYF_4中的掺杂原子百分数(掺杂量)对NaYF_4:Yb~(3+),Er~(3+)上转换材料荧光性能的影响;以合成的NaYF_4:Yb~(3+),Er~(3+)为荧光填料,聚乙烯醇(PVA)为基材,通过流延法,制备了一系列不同荧光特性的复合薄膜。研究结果表明:随着Yb~(3+)含量的提高,NaYF_4:Yb~(3+),Er~(3+)上转换材料发光强度先增大后减小,当Yb~(3+)掺杂量为30%时,荧光强度达到最大;另外,随着Yb~(3+)掺杂量从10%提高到98%,绿色荧光与红色荧光强度的比值(绿红比)逐渐减小,上转换材料发光颜色由绿色变为黄色再变为橙色。随着Er~(3+)掺杂量的增加,荧光强度同样先增大后减小,当Er~(3+)掺杂量为1%时,荧光强度达到最大;且Er~(3+)掺杂量的增加同样会使绿红比降低。所制备的复合薄膜透明性好,且具有易调控、易识别、难察觉的上转换荧光特性,预期在包装防伪领域有很好的应用前景。     

NaYF4:Er3+六棱柱的水热合成及上转换发光性能

以氟化钠、硝酸钇、硝酸铒为原料,利用水热法合成NaYF4:Er3+材料。利用X射线粉末衍射仪(XRD)、场扫描电子显微镜(SEM)、红外吸收(FT-IR)以及发光光谱等手段对产物的物相结构、形貌和荧光性能进行分析。结果表明,NaYF4:Er3+为六角棱柱晶体,属于六方晶系,具有P63/m(176)空间点群结构。在980nm光激发下,NaYF4:Er3+展现出强的上转换光,波长在520nm和539nm为绿光发射,对应为Er3+离子的2 H11/2→4/I15/2和4S3/2→4/I15/2跃迁发射,而652nm为红光发射,则对应于Er3+离子的4F9/2→4/I15/2跃迁发射。     

Tailor-made pH-sensitive polyacrylic acid functionalized mesoporous silica nanoparticles for efficient and controlled delivery of anti-cancer drug Etoposide

A multifaceted therapeutic platform has been proposed for controlled delivery of Etoposide (ETS) leading to a synergistic advantage of maximum therapeutic efficacy and diminished toxicity. A state of the art pH responsive nanoparticles (NPs) MSNs-PAA consisting of mesoporous silica nanoparticles core and polymeric shell layers, were developed for controlled release of model anti-cancer drug ETS. Graft onto strategy was employed and amination served as an interim step, laying a vital foundation for functionalization of the MSN core with hydrophilic and pH responsive polyacrylic acid (PAA). MCM-41-PAA were investigated as carriers for loading and regulated release of ETS at different pH for the first time. The PAA-MSNs contained 20.19% grafted PAA as exhibited by thermogravimetric analysis (TGA), which enormously improved the solubility of ETS in aqueous media. The synthesized PAA-MSNs were characterized by various techniques viz, SEM-EDS, TEM, BET, FT-IR and powder XRD. ETS was effectively loaded into the channels of PAA-MSN via electrostatic interactions. The cumulative release was much rapid at extracellular tumor (6.8) and endosomal pH (5.5) than that of blood pH (7.4). Hemolysis study was done for the prepared NPs. MTT assay results showed that the drug-loaded ETS-MCM-41-PAA NPs were more cytotoxic to both prostate cancer cells namely PC-3 and LNCaP than free ETS, which was attributed to their slow and sustained release behavior. The above results confirmed that PAA-MSN hold a great potential as pH responsive carriers with promising future in the field of cancer therapy.     

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.     

纤维状中空结构NaYF4:Yb3+, Er3+上转换材料的 合成及防伪应用

采用水溶性聚合物聚乙烯亚胺(PEI)调介下的水热法,一步合成了具有纤维状中空结构的六方相NaYF4:Yb3+,Er3+上转换荧光材料,并将其作为荧光填料,通过流延成膜法制备了具有上转换荧光性能的壳聚糖/聚乙烯醇(CS/PVA)荧光复合薄膜.探究了PEI配体含量和反应体系pH值对合成的上转换材料的形貌、晶型和荧光性能的影响,以及壳聚糖/聚乙烯醇荧光复合薄膜中荧光填料的最佳掺杂量.研究结果表明,在PEI含量为0.3 g且反应体系pH=5的条件下,合成的产物为具有纤维状中空结构的六方相NaYF4:Yb3+,Er3+.荧光光谱表明,合成的NaYF4:Yb3+,Er3+上转换材料在980 nm激光激发下具有优异的荧光性能.当荧光填料的掺杂质量分数为3.0％时,制备的NaYF4:Yb3+,Er3+/(CS/PVA)荧光复合薄膜具有最佳的透明度和上转换荧光特性.     

Direct imaging the upconversion nanocrystal core/shell structure at the subnanometer level: shell thickness dependence in upconverting optical properties

Lanthanide-doped upconversion nanoparticles have shown considerable promise in solid-state lasers, three-dimensional flat-panel displays, and solar cells and especially biological labeling and imaging. It has been demonstrated extensively that the epitaxial coating of upconversion (UC) core crystals with a lattice-matched shell can passivate the core and enhance the overall upconversion emission intensity of the materials. However, there are few papers that report a precise link between the shell thickness of core/shell nanoparticles and their optical properties. This is mainly because rare earth fluoride upconversion core/shell structures have only been inferred from indirect measurements to date. Herein, a reproducible method to grow a hexagonal NaGdF(4) shell on NaYF(4):Yb,Er nanocrystals with monolayer control thickness is demonstrated for the first time. On the basis of the cryo-transmission electron microscopy, rigorous electron energy loss spectroscopy, and high-angle annular dark-field investigations on the core/shell structure under a low operation temperature (96 K), direct imaging the NaYF(4):Yb,Er@NaGdF(4) nanocrystal core/shell structure at the subnanometer level was realized for the first time. Furthermore, a strong linear link between the NaGdF(4) shell thickness and the optical response of the hexagonal NaYF(4):Yb,Er@NaGdF(4) core/shell nanocrystals has been established. During the epitaxial growth of the NaGdF(4) shell layer by layer, surface defects of the nanocrystals can be gradually passivated by the homogeneous shell deposition process, which results in the obvious enhancement in overall UC emission intensity and lifetime and is more resistant to quenching by water molecules.     

Upconversion in NaYF(4):Yb, Er nanoparticles amplified by metal nanostructures

Upconversion (UC) fluorescence in NaYF(4):Yb, Er nanoparticles amplified by metal nanostructures was compared in two nanostructure geometries: gold nanoshells surrounding nanoparticles and silver nanostructures adjacent to the nanoparticles, both placed on a dielectric silica surface. Enhanced UC luminescence signals and modified lifetimes induced by these two metals were observed in our study. The UC luminescence intensities of green and red emissions were enhanced by Ag nanostructures by a factor of approximately 4.4 and 3.5, respectively. The corresponding UC lifetimes were reduced ～ 1.7-fold and ～ 2.4-fold. In NaYF(4):Yb, Er nanoparticles encapsulated in gold nanoshells, higher luminescence enhancement factors were obtained (～9.1-fold for the green emission and ～ 6.7-fold for the red emission). However, the Au shell coating extended the red emission by a factor of 1.5 and did not obviously change the lifetime of green emission. The responsible mechanisms such as plasmonic enhancement and surface effects are 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.     

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.     

Mechanistic aspects of formation of MgO nanoparticles under microwave irradiation and its catalytic application

This work reports a preparation of Mg(OH)₂ and MgO nanoparticles (NPs) using magnesium acetate in benzylamine and mechanistic study of its formation. The benzylamine acts as a solvent, base, promoter and capping agent in this reaction. The structure and morphology of particles were analyzed by X-ray diffraction pattern (XRD), transmission electron microscopy (TEM), high resolution TEM (HRTEM), selected area energy dispersion (SAED), energy-dispersive X-ray spectroscopy (EDAX), thermogravimetric analysis (TGA), FT-IR, CO₂–temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and Brunauer–Emmett–Teller (BET) surface area analysis techniques. The application of as prepared MgO NPs was used in catalysis as a catalyst for the formylation of amines with recyclability studies of nanocatalyst.