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NaYF4:Yb/Er
CRYSTENGCOMM · 2018 ·Vol. 20 ·期 14 ·1945-1953 · IF 3.304

Enhanced upconversion luminescence and controllable phase/shape of NaYF4:Yb/Er crystals through Cu2+ ion doping

Kaimin Du,Xia Xu,Shuang Yao,Pengpeng Lei,Lile Dong,Manli Zhang,Jing Feng,Hongjie Zhang

Hexagonal phase (β-) NaYF4:Yb/Er upconversion (UC) microrods doped with Cu2+ ions were prepared via a facile solvothermal method. Simultaneous phase and shape control of NaYF4:Yb/Er crystals with enhanced upconversion luminescence (UCL) was successfully realized by codoping with Cu2+ ions. With an increasing Cu2+ ion concentration in the NaYF4:Yb/Er system, the crystal structure changed from a mixture of α- and β-phases to the pure β-phase and was converted into highly uniform microrods. As for the Cu2+ ion doped β-NaYF4:Yb/Er upconversion microrods, the maximum emission occurs with the sample added with 60 mol% Cu2+ ions and the UCL intensities of the green and red emissions were enhanced 37 and 25 times, respectively. Meanwhile, the possible mechanisms for the enhanced UCL of NaYF4:Yb/Er crystals were also discussed in detail. Moreover, the temperature dependent UCL properties of 60 mol% Cu2+ ion doped β-NaYF4:Yb/Er were studied under 980 nm excitation, which were temperature-sensitive over a wide temperature range from 123 K to 423 K. The change in UCL intensity influenced by temperature was discussed in detail.

研究领域: 材料科学 · 纳米技术 · 光学材料 · 稀土化学 · 生物医学成像
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Journal of Materials Chemistry C · 2018 ·Vol. 6 ·期 38 ·10226-10232 · IF 5.976

Exploiting the silent upconversion emissions from a single β-NaYF4:Yb/Er microcrystal via saturated excitation

M. Yuan,R. Wang,C. Zhang,Z. Yang,W. Cui,X. Yang,N. Xiao,H. Wang,X. Xu

Exploiting new transitions in the visible light range is important in the development of advanced color displays, superior laser materials, and novel optical devices. Here, for the first time, we observed several intensive upconversion (UC) emission bands at 382, 472, 506, 560, and 618 nm from a single β-NaYF4:Yb/Er microcrystal via saturated excitation. Compared to the traditional red (650 nm) and green (545 nm) UC emissions, these new emission bands intensify rapidly as the excitation intensity increases, which leads to full-color UC luminescence in the visible region. Nearly white luminescence was elicited from a single microcrystal with a relatively high excitation power. Moreover, the mechanism of these newly observed UC emissions was elucidated by examining the energy migration. It was also found that these microcrystals exhibit waveguide-transmission characteristics and are transparent to their own UC emissions. These findings provide a basis for further exploration of the silent transitions of other rare-earth-ions and demonstrate the potential for using β-NaYF4:Yb/Er microcrystals in a variety of applications in color display and waveguide-based optical devices.

研究领域: 材料科学 · 光学
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Journal of Materials Chemistry B · 2014 ·Vol. 2 ·期 38 ·6626-6633 · IF 0

Mn2+-doped NaYF4:Yb/Er upconversion nanoparticles with amplified electrogenerated chemiluminescence for tumor biomarker detection

Min Liu,Yuhang Ye,Cheng Yao,Wenbo Zhao,Xiaohua Huang

Chemiluminescence was used as an excitation light source to construct a universal photoelectrochemical platform based on Mn2+-doped NaYF4:Yb/Er upconversion nanoparticles, which greatly improves the electrochemiluminescence intensity and offers more stable cathodic signals compared to pure NaYF4:Yb/Er NPs. Here, we report for the first time the ECL behaviors of Mn2+-doped NaYF4:Yb/Er NPs, which were synthesized via a facile strategy. Mn2+ doping resulted in a 4-fold ECL intensity enhancement of NaYF4:Yb/Er. The characteristics of Mn2+-doped NaYF4:Yb/Er nanocomposites were obtained using transmission electron microscopy (TEM), energy dispersive X-ray spectrometer (EDS), and fluorescence spectra. After all the results had indicated that NaYF4:Yb/Er upconversion nanoparticles were successfully doped with Mn2+, the electrochemiluminescence platform was built. The as-prepared NaYF4:Yb/Er NPs were rendered water-soluble and then employed as ECL emitters for carcinoembryonic antigen (CEA) determination. The results indicated that the modified electrode can be used to determine CEA without interference from non-specific proteins, with a low detection limit of 5.2 pg mL−1. The biosensor can also be used for quantification of the CEA concentration in real samples.

研究领域: 生物医学工程 · 纳米医学
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Nanoscale · 2015 ·Vol. 8 ·期 2 ·1040-1048 · IF 7.394

NaYF4:Yb/Er@PPy core–shell nanoplates: an imaging-guided multimodal platform for photothermal therapy of cancers

Xiaojuan Huang,Bo Li,Chen Peng,Guosheng Song,Yuxuan Peng,Zhiyin Xiao,Xijian Liu,Jianmao Yang,Li Yu,Junqing Hu

Imaging guided photothermal agents have attracted great attention for accurate diagnosis and treatment of tumors. Herein, multifunctional NaYF4:Yb/Er@polypyrrole (PPy) core–shell nanoplates are developed by combining a thermal decomposition reaction and a chemical oxidative polymerization reaction. Within such a composite nanomaterial, the core of the NaYF4:Yb/Er nanoplate can serve as an efficient nanoprobe for upconversion luminescence (UCL)/X-ray computed tomography (CT) dual-modal imaging, the shell of the PPy shows strong near infrared (NIR) region absorption and makes it effective in photothermal ablation of cancer cells and infrared thermal imaging in vivo. Thus, this platform can be simultaneously used for cancer diagnosis and photothermal therapy, and compensates for the deficiencies of individual imaging modalities and satisfies the higher requirements on the efficiency and accuracy for diagnosis and therapy of cancer. The results further provide some insight into the exploration of multifunctional nanocomposites in the photothermal theragnosis therapy of cancers.

研究领域: 生物医学工程 · 肿瘤学 · 纳米医学
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2016 ·Vol. 408 ·期 14 ·3823-3831 · IF 3.125

Mn2+-doped NaYF4:Yb/Er upconversion nanoparticle-based electrochemiluminescent aptasensor for bisphenol A

Guo Xiaofei,Wu Shijia,Duan Nuo,Wang Zhouping

A novel aptasensor labeled with Mn 2+ -doped NaYF 4 :Yb/Er upconversion nanoparticles (NaYF 4 :Yb,Er/Mn UCNPs) was employed in electrogenerated chemiluminescence (ECL) for the sensitive detection of bisphenol A (BPA). The ECL aptasensor was assembled by immobilizing the thiolated aptamers of BPA covalently on a gold nanoparticle (AuNPs)-modified electrode and pairing with complementary DNA labeled with NaYF 4 :Yb,Er/Mn UCNPs. The ECL aptasensor can not only rapidly and accurately detect BPA concentrations from 0.05 to 100 ng/mL with a detection limit of 0.037 ng/mL but also provides a new platform for ECL applications based on the use of upconversion nanoparticles as a promising alternative material. The NaYF4:Yb,Er/Mn UCNPs combining with the BPA aptamer serving as recognition elements create a ECL platform for the sensitive detection of bisphenol A. The change in ECL signals induced by aptamer-target interactions was measured and a significant decrease in intensity was found on interaction with BPA in the concentration range of 0.05 to 100 ng/mL.

研究领域: 分析化学 · 纳米技术 · 环境科学 · 材料科学
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APPLIED SURFACE SCIENCE · 2016 · IF 3.15

Hydrothermal synthesis of superparamagnetic and red luminescent bifunctional Fe3O4@Mn2+-doped NaYF4:Yb/Er core@shell monodisperse nanoparticles and their subsequent ligand exchange in water

Zhenli Qin,Sinan Du,Yang Luo,Zhijian Liao,Fang Zuo,Jianbin Luo,Dong Liu

We report the use of an efficient hydrothermal method to synthesize superparamagnetic and red luminescent bifunctional Fe 3 O 4 @Mn 2+ -doped NaYF 4 :Yb/Er nanoparticles (NPs) with core@shell structures via a seed-growth procedure. Oleic acid coated Fe 3 O 4 (OA-Fe 3 O 4 ) NPs were initially synthesized using a coprecipitation method. The as-synthesized OA-Fe 3 O 4 NPs were then used as seeds, on which the red upconversion luminescent shell (Mn 2+ -doped NaYF 4 :Yb/Er) was formed. Furthermore, hydrophobic to hydrophilic surface modification of the Fe 3 O 4 @Mn 2+ -doped NaYF 4 :Yb/Er NPs was achieved via a ligand exchange method where oleic acid was displaced by a PEG phosphate ligand [PEG   =   poly(ethylene glycol)]. These materials were characterized by means of transmission electron microscopy (TEM), X-ray diffraction (XRD), photoluminescence (PL) spectroscopy, and vibrating sample magnetometry (VSM). The Fe 3 O 4 cores were uniformly coated with a Mn 2+ -doped NaYF 4 :Yb/Er shell, and the bifunctional Fe 3 O 4 @Mn 2+ -doped NaYF 4 :Yb/Er NPs were monodispersed. Furthermore, the Fe 3 O 4 @Mn 2+ -doped NaYF 4 :Yb/Er NPs exhibited a saturated magnetization value of 6.2 emu/g and emitted red luminescence under a 980   nm laser. The obtained bifunctional Fe 3 O 4 @Mn 2+ -doped NaYF 4 :Yb/Er NPs may find potential applications in drug targeting, bioseparation, and diagnostic analysis. The synthetic method may be employed for the preparation of other bifunctional nanomaterials.

CAS / MDL: 9004-74-4 2258654-78-1
研究领域: 材料科学 · 纳米医学 · 生物成像
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RSC Advances · 2013 ·Vol. 3 ·期 33 ·13915-13925 · IF 2.562

Multifunctional photosensitizer-conjugated core–shell Fe3O4@NaYF4:Yb/Er nanocomplexes and their applications in T2-weighted magnetic resonance/upconversion luminescence imaging and photodynamic therapy of cancer cells

Leyong Zeng,Lingchao Xiang,Wenzhi Ren,Jianjun Zheng,Tianhua Li,Bin Chen,Jichao Zhang,Chengwen Mao,Aiguo Li,Aiguo Wu

Due to non-invasive deep imaging and therapy, multifunctional agents of magnetic resonance (MR)/upconversion luminescence (UCL) imaging and photodynamic therapy (PDT) play an important role in clinical diagnosis and treatment of cancers, and also in the assessment of therapy effect. In this paper, tetra-sulfonic phthalocyanine aluminium (AlPcS4) photosensitizers-conjugated Fe3O4@NaYF4:Yb/Er (NPs-AlPcS4) nanocomplexes were synthesized for the T2-weighted MR/UCL imaging and PDT of cancer cells. The PEG-coated Fe3O4@NaYF4:Yb/Er nanoparticles (NPs) with a core–shell structure showed strong T2-weighted MR relaxivity (r2 = 42.131 mM−1 s−1) and UCL emission in the visible region (the bands at about 654–674 nm, 545 nm and 524 nm), and were conjugated successfully with AlPcS4 photosensitizer by electrostatic interaction. By direct observation of XFM and staining with Prussian blue, the element distribution and location of NPs in MCF-7 cells were characterized, respectively. Under irradiation from a 980 nm laser, the death ratio of MCF-7 cells incubated with NPs-AlPcS4 nanocomplexes could be up to about 70%. The results indicated that the as-prepared NPs-AlPcS4 nanocomplexes would be a potential candidate as multifunctional nanoprobes for the dual-modal T2-weighted MR/UCL imaging and PDT of cancers in the future.

研究领域: 生物医学工程 · 肿瘤学 · 材料科学 · 影像医学
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CRYSTAL GROWTH & DESIGN · 2018 · IF 3.972

Reducing Grain Size and Enhancing Luminescence of NaYF4:Yb3+, Er3+ Upconversion Materials

Lihua He,Xiao Zou,Xiang He,Fengying Lei,Na Jiang,Qiaoji Zheng,Chenggang Xu,Yongfu Liu,Dunmin Lin

A variety of NaYF4:Yb/Er upconversion materials were successfully synthesized via a facile hydrothermal method by altering the volume ratios (0:1, 1:1, 2:1, 3:1, 4:1, 5:1) of ethanol to water and various alcohols (methanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, polyethylene glycol, and phemethylol), and the grain size and luminescence of the materials were effectively tailored. The addition of alcohol effectively reduces the grain size of the materials and simultaneously leads to the surprising enhancement of the UC emission. The increase in the volume ratio of EtOH/H2O causes the transformation of the crystal structure of the materials from hexagonal to cubic phase. The particle size of the material with the EtOH/H2O of 2:1 is almost 1000 times smaller than that of the material without EtOH, and the strongest luminescence is observed at the EtOH/H2O of 2:1. The type of alcohol in the solvent exhibits a significant influence on the luminescent properties of the materials. The NaYF4:Yb/Er nanocrystals obtained using different alcohols as solvent possess much a smaller grain size and stronger upconversion luminescence than that using water as solvent, and the NaYF4:Yb/Er materials with n-propyl alcohol exhibit the strongest luminescence intensity. The mechanism of the reduction of grain size and enhancement in the luminescence of the NaYF4:Yb3+, Er3+ upconversion materials has been proposed. This study may suggest a simple method to significantly reduce the grain size and improve the upconversion luminescence properties of NaYF4-based fluorescence material.

研究领域: 材料科学 · 光学 · 纳米技术
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ISRAEL JOURNAL OF CHEMISTRY · 2015 ·Vol. 56 ·期 4 ·242-248 · IF 2.221

Au/NaYF4 : Yb,Er Binary Superparticles: Synthesis and Optical Properties

Junwei Zhao,Jian Wu,Junfei Xue,Qiannan Zhu,Weihai Ni

Graphical Colloidal superparticles (SPs) are nanoparticle (NP) assemblies in the form of colloidal particles. Assembling nanoscopic objects into mesoscopic or macroscopic composite architectures allows for the bottom-up fabrication of functional nanomaterials. In this study, a method for single-step self-assembly synthesis of Au/NaYF 4 : Yb,Er SPs was developed using oil-in-water (O/W) microemulsions to simultaneously encapsulate gold nanoparticles (AuNPs) and NaYF 4 : Yb,Er upconversion nanoparticles (UCNPs) via evaporation at room temperature. The synthesized Au/NaYF 4 : Yb,Er SPs possess good dispersibility and stability. When the number of AuNPs added is increased, the SPs exhibit decreased upconversion luminescence, which can be ascribed to the Förster resonance energy transfer (FRET) from the NaYF 4 : Yb,Er UCNPs to the AuNPs. Time-resolved measurements of the green emission further confirm the existence of a new decay route corresponding to the FRET process. Our research provides a facile and versatile strategy for the synthesis of novel multifunctional nanocomposites with tunable upconversion luminescence properties, which can be of great significance in biological applications.

CAS / MDL: 112-90-3
研究领域: 材料科学 · 纳米技术 · 光学 · 生物医学工程
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JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY · 2021 ·Vol. 101 ·期 1 ·215-226 · IF 2.326

Impinging streams application in mass production of rare earth ions doped upconversion luminescence microparticles

Li Ping,Zhao Liuyong,Wang Song,Zhang Xiaohui,Jiang Huaiyuan,Liu Ruizhen,Zhao Nengchuang,Cheng Jian,Xu Caili,Zhao He,Lyu Renliang

Known as one efficient upconversion luminescent material, Rare-earth ions doped natrium yttrium fluoride NaYF 4 :Yb/Re has broad application prospects. However, due to the limitation of the existing preparation methods, it is difficult to realize industrial production. In this paper, the upconversion luminescence microparticles, rare earth ions doped Natrium Yttrium Fluoride NaYF 4 :Yb/Er, were synthesized productively by impinging stream method. Synthesis conditions were optimized as EDTA: Ln to 0.5 and NaF: Ln to 6 (Ln represents the sum of moles of Y, Yb, and Er), reacting temperature and time to 50 °C and 3 h to obtain a high yield of 99.92% and particle with good monodispersity. To get strong upconversion luminescence, the effect of the calcination temperature and the amount of EDTA were investigated. The bright upconversion emissions by excited with laser radiation at 975 nm were found at 510–690 nm. The higher the calcination temperature, the stronger the luminescence and the strongest luminescence occurs when calcined at 600 °C. And the adding of EDTA will decrease the luminescence intensity. However, the sintering of particles at high temperatures and aggregation of particles without EDTA are unfavorable for the application of the products. Based on the above considerations, the optimal calcination temperature was determined at 450 °C, and the ratio of EDTA: Ln is preferred at 0.5. The impinging stream method to prepare upconversion material has the advantages of being simple in the process and equipment, high in output, low in investment, and convenient to be applied and popularized.

CAS / MDL: 1314-37-0
研究领域: 材料科学 · 化学工程
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ACS Applied Nano Materials · 2022 · IF 6.14

NaYF4:Yb,Er@NaYF4:Yb,Tm and NaYF4:Yb,Tm@NaYF4:Yb,Er Core@Shell Upconversion Nanoparticles Embedded in Acrylamide Hydrogels for Anti-Counterfeiting and Information Encryption

Jian Zhang,Cong Cao,Jinsong Wang,Shiwen Li,Yu Xie

Multicolor upconversion luminescence (UCL) plays an essential role in anti-fake and information encipher. Here, we report a strategy to expand the color-adjustable emission range by regulating the doping concentration of Yb3+ in core@shell (C@S) upconversion nanoparticles (UCNPs) under the excitation of near-infrared (NIR) light at 980 nm and promoting the energy-transfer process. Subsequently, multicolor UCNPs were combined with acrylamide hydrogel to construct a three-dimensional (3D) information code with an adjustable emission color. The encoded information is readable only under 980 nm excitation light and disappears as soon as the excitation light is removed. We adopted three strategies to improve the security: multiple permutations and combinations of different emission light hydrogel blocks, the combination of rich optical information and binary code, and the shape coding of hydrogel blocks. Constructing a complex and changeable coding library significantly guarantees that the data can be enciphered and deciphered by simple light irradiation, and the content can be edited by permutation and combination combined with information coding rules. Therefore, it is expected to provide ideas for developing intelligent anti-counterfeiting materials and devices.

CAS / MDL: 2680-03-7
研究领域: 材料科学 · 光学 · 纳米技术 · 化学 · 安全技术
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Nanomaterials · 2018 ·Vol. 8 ·期 12 ·1023 · IF 3.504

Simultaneous Dual-mode Emission and Tunable Multicolor in the Time Domain from Lanthanide-doped Core-shell Microcrystals

Dandan Ju,Feng Song,Adnan Khan,Feifei Song,Aihua Zhou,Xiaoli Gao,Huimin Hu,Xu Sang,Victor Zadkov

The dual-mode emission and multicolor outputs in the time domain from core-shell microcrystals are presented. The core-shell microcrystals, with NaYF4:Yb/Er as the core and NaYF4:Ce/Tb/Eu as the shell, were successfully fabricated by employing the hydrothermal method, which confines the activator ions into a separate region and minimizes the effect of surface quenching. The material is capable of both upconversion and downshifting emission, and their multicolor outputs in response to 980 nm near-infrared (NIR) excitation laser and 252 nm, and 395 nm ultraviolet (UV) excitation light have been investigated. Furthermore, the tunable color emissions by controlling the Tb3+-Eu3+ratio in shells and the energy transfer of Ce3+→Tb3+→Eu3+were discussed in details. In addition, color tuning of core-shell-structured microrods from green to red region in the time domain could be obtained by setting suitable delay time. Due to downshifting multicolor outputs (time-resolved and pump-wavelength-induced downshifting) coupled with the upconversion mode, the core-shell microrods can be potentially applied to displays and high-level security.Keywords:NaYF4:Yb/Er@NaYF4:Ce/Tb/Eu microrods;dual-mode emission;time-resolved emission spectra;multicolor emission

CAS / MDL: 6381-92-6
研究领域: 材料科学 · 光学
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