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CHEMISTRY OF MATERIALS · 2020 · IF 9.567

Clearable Shortwave-Infrared-Emitting NaErF4 Nanoparticles for Noninvasive Dynamic Vascular Imaging

Hui Li,Xin Wang,Xiaolong Li,Songjun Zeng,Guanying Chen

Nanoprobes with emissions in the tissue-penetrating shortwave infrared (SWIR, 1000–1700 nm) range hold promise for noninvasive angiographic imaging of small animals. However, limited success has been achieved in SWIR-emitting contrast agents beyond 1500 nm that can be cleared out from the body. Here, we describe a class of clearable, 1525 nm-emitting NaErF4-based nanoparticles that enable dynamic vasculature imaging of the whole body at a high spatial resolution (∼58 μm) under biocompatible 808 nm excitation (avoiding the biological heating effect with typically used 980 nm excitation). We made a systematic investigation of the effects of the crystal phase (hexagonal and cubic), the core@shell structure, the lattice mismatch between the core and the shell (NaLnF4, Ln = Y, Lu, or Gd), and the shell thickness on SWIR luminescence. The brightest nanoparticles were determined to be hexagonal (β)-phase core@shell NaErF4@NaYF4 nanoparticles (β-Er@Y-NPs, size 13 nm) that have the lowest core@shell lattice mismatch and a shell thickness of ∼3 nm, presenting SWIR luminescence about ∼180-fold higher than that of the parent core NPs. Intravenous (IV) administration of aqueous β-Er@Y NPs (at a dose of 5 mg/kg) enabled a clear through-skull brain vessel imaging without craniotomy and dynamic vasculature imaging of the whole body. A pharmacokinetic study indicates a near-complete clearance of these core@shell nanoparticles primarily through feces at 14 days post IV injection. Histological studies of internal organ tissues (heart, liver, spleen, lung, and kidney) and blood biochemical analysis demonstrate low toxicities of these NPs. Our results here provide a new class of clearable SWIR-emitting NPs as imaging contrast agents for high-resolution in vivo biological studies.

研究领域: 生物医学工程 · 材料科学 · 影像学
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ACS Applied Nano Materials · 2023 · IF 5.9

NaErF4-Based Nanocarrier for Enhanced Ferroptosis Therapy of Cancer

Jin-Yang Liu,Na Liu,Yue Wu,Xiao-Min Ning,Wen-Chao Zhang,Jing Qian

To improve the treatment efficiency of ferroptosis and accurately monitor the therapy process, we developed small-sized upconversion nanoparticles (UCNPs) by a simple one-step solvothermal method. On this basis, a facile strategy is reported to construct mesoporous SiO2-coated UCNPs as the nanocarrier to load dual drugs of MnO2 and methylene blue (MB) photosensitizer for hypoxic tumor theranostic. Due to the components of high charge elements, the synthetic NaErF4:Yb,Gd,Eu@mSiO2/MnO2/MB@FA (UPSMF/MB, FA = folic acid) exhibited radiosensitization function. Emitting strong red upconversion luminescence (UCL) excited the encapsulated MB to initiate photodynamic therapy (PDT). In addition, UPSMF/MB released green UCL imaging in vivo, so as to trace drug distribution and achieve accurate theranostic. In tumor microenvironment, the loaded MnO2 possessed catalase-like (CAT) catalytic activity, which could effectively decompose excessive H2O2 into O2, thus alleviating hypoxia in the tumor area and promoting PDT and radiotherapy (RT) to generate reactive oxygen species (ROS). Furthermore, MnO2 had excellent glutathione peroxidase (GPx)-like activity, which could effectively decompose intracellular over-expressed glutathione (GSH), thus causing lipid peroxide (LPO) accumulation and inducing ferroptosis. In situ ROS generation by PDT and RT further promoted the accumulation of intracellular LPO. Cytotoxicity assay revealed that the apoptosis rate of UPSMF/MB promoted by RT and PDT was 79.76%, which was 46% higher than that of solo ferroptosis induced by UPSMF. Notably, in vivo results illustrated that the tumor inhibition rate of UPSMF/MB could be increased to 83.4% under the triple effects of RT, PDT, and ferroptosis with negligible side effects to normal tissues. This work paves a way to enhance the efficacy of ferroptosis-based cancer therapy by associating PDT with RT.

研究领域: 癌症研究 · 纳米技术 · 诊疗一体化 · 生物医学工程 · 材料科学
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Nanoscale · 2022 ·Vol. 14 ·期 43 ·16156-16169 · IF 8.307

In-depth insight into the Yb3+ effect in NaErF4-based host sensitization upconversion: a double-edged sword

Yang Wang,Shuai Zhou,Fuyao Sun,Po Hu,Wei Zhong,Jiajun Fu

NaErF4 is the most extensively studied host for self-sensitized upconversion (UC), and Yb3+ is the most commonly used energy absorber. It has been reported that the red luminescence of Er3+ can be enhanced by introducing Yb3+ into the NaErF4 host lattice, where Yb3+ ions serve as trapping centers to confine the excitation energy. Also, it has been pointed out that the Yb3+ doping in the shell of NaErF4-hosted core–shell nanocrystals can further improve the red emission intensity. Conversely, it can be argued that the Yb3+ doping in the shell always results in the luminescence quenching of the NaErF4 core. These imply that the impact of Yb3+ on NaErF4-based host-sensitized UC is rather complicated and must be probed deeply. In this study, we thoroughly discussed the effect of Yb3+ located in the core/shell on the NaErF4-based host sensitization UC and afforded the related mechanism interpretations. In the NaErF4 core nanocrystals, the green-dominated UCL presented an enhancement on increasing the concentration of the Yb3+ dopant owing to the promoted energy harvesting for luminescence. Furthermore, the emission properties of NaErF4:10%Yb shelled with diverse inert layers were also investigated, and the intensity difference of these core-inert shell nanoparticles could be explained by the lattice mismatch and shell thickness. In NaErF4:10%Yb@NaYF4:Yb with variable Yb3+ doping in the shell, the red-dominated UCL was generally weakened with more Yb3+ localized in the shell, which was ascribed to the competition of energy pooling and energy dissipation of Yb3+ in the outer layer. Therefore, Yb3+ ions wield a two-sided influence (termed a “double-edged sword”) on the UC emissions of the Er3+ host. Additionally, we demonstrated the application potential of such UCNPs in water sensing and high-level anti-counterfeiting. This work offers an in-depth insight into the UC mechanism of Yb3+-doped NaErF4 nanocrystals and inspires the engineering of novel luminescent materials with distinguished properties.

研究领域: 材料科学 · 纳米技术 · 光学 · 化学
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JOURNAL OF ALLOYS AND COMPOUNDS · 2019 · IF 4.175

Enhanced single-band red upconversion luminescence of α-NaErF4:Mn nanoparticles by a novel hollow-shell structure under multiple wavelength excitation

Yuefeng Liu,Jun Zhao,Yan Zhang,Huafang Zhang,Zhenlong Zhang,Huiping Gao,Yanli Mao

Upconversion nanoparticles (UCNPs) doped with lanthanide ions have potential applications in biomedical, solar cells and displays. However, the intensity of the upconversion luminescence (UCL) is limited by the surface effects of nanomaterials , lattice defects, etc. Here, a novel α-NaErF 4 hollow nanocube is fabricated by using divalent manganese ions (Mn 2+ ) to substitute trivalent erbium ions (Er 3+ ) in the NaErF 4 matrix. The hollow-shell structure can weaken the luminescence quenching and surface quenching effects, reduce the energy loss of higher energy levels in nanoparticles , and improve the light capture ability of nanoparticles. So the UCL of α-NaErF 4 hollow nanocubes is greatly improved, which is 14, 790 and 1071 times higher than that of the β-NaErF 4 under 808, 980 and 1530 nm laser excitation, respectively, and the emission in the red region is enhanced respectively by 69, 2049 and 2902 times. In particular, the hollow nanocubes emit intense single-band red emission under the three different wavelengths, respectively. Moreover, the magnetization of α-NaErF 4 hollow nanocubes is 2.16 emu g −1 at room temperature, which is larger than that of gadolinium-based materials. Hollow-shell structure, excellent paramagnetism and single-band red upconversion emission excited by various wavelengths will create NaErF 4 :40Mn UCNPs a good application prospect in the biomedical field.

研究领域: 纳米材料 · 生物医学工程 · 光学材料
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ACS Applied Nano Materials · 2022 · IF 6.14

Ti3C2 MXene Nanosheets Functionalized with NaErF4:0.5%Tm@NaLuF4 Nanoparticles for Dual-Modal Near-Infrared IIb/Magnetic Resonance Imaging-Guided Tumor Hyperthermia

Jialin Pan,Meiling Zhang,Gege Fu,Li Zhang,Huimei Yu,Xu Yan,Fangmeng Liu,Peng Sun,Xiaoteng Jia,Xiaomin Liu,Geyu Lu

Although the advent of two-dimensional (2D) MXenes has substantially increased the family of 2D materials and diverse applications, the rational design of MXene-based composites and their specialized applications in theranostic biomedicine remain a challenge. In this work, we developed, for the first time, Ti3C2 MXene nanosheets for near-infrared (NIR)-IIb (1530 nm) and magnetic resonance (MR) imaging-guided photothermal therapy. Surface engineering and functionalization of 2D Ti3C2 MXene nanosheets with NaErF4:0.5%Tm@NaLuF4 (NaErF4) nanoparticles result in NaErF4@Ti3C2 composites that emit in the NIR-IIb region at 1530 nm under 808 nm excitation, conferring NIR-IIb imaging guidance and monitoring capabilities during tumor hyperthermia. Due to the inherent magnetic properties of the Er3+ ions, the NaErF4@Ti3C2 composite can also be used for efficient T2-weighted MR imaging. In particular, based on the high photothermal conversion capability (43.62% at 808 nm irradiation) and photothermal stability, the designed composites were further explored for efficient tumor ablation with an inhibition ratio of 92.9%, which was systematically demonstrated both in vitro and in vivo. No significant nanocomposite toxicity was observed at the injected dose. This work not only expands the performance of MXene-based multifunctional nanostructures but also highlights the promise of their versatile applications in cancer therapy.

研究领域: 材料科学 · 生物医学工程 · 纳米医学 · 癌症治疗
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CERAMICS INTERNATIONAL · 2022 ·Vol. 48 ·期 10 ·14315-14322 · IF 5.532

Effective regulation of upconversion luminescence in NaErF4 and NaErF4@SiO2 core-shell particles

Jie Chen,Yixin Gao,Chao Wang,Yu Yin,Jiaxing Song,Xiaodan Zeng,Zhigang Liu,Haifeng Jiang

Upconversion luminescence materials have gained extensive attentions owing to their unique luminescence characteristics of converting near-infrared excitation to visible light emission. However, how to improve the doping concentration of activator (usually <3 mol%) in traditional sensitizer-activator system is still a great challenge due to the luminescence quenching effect. In this work, NaErF 4 crystals with diverse crystal phases and morphologies were prepared by simple hydrothermal method , constructing a 100% doping concentration system of activator (Er 3+ ). With the increase of F − content, the phase of NaErF 4 transfers from cubic to hexagonal, and the morphology changes from nanospheres to hexagonal microflakes, meanwhile, the upconversion luminescence intensity also increases gradually. In addition, in order to further inhibit the luminescence quenching effect of NaErF 4 bare core, a series of NaErF 4 @SiO 2 core-shell samples with different SiO 2 shell thickness were successfully prepared. Compared with NaErF 4 bare core, the morphology and structure of the NaErF 4 @SiO 2 core-shell samples have no obvious change, but the UC luminescence intensity is significantly enhanced. Interestingly, the change of NaErF 4 crystal phase and SiO 2 shell thickness can both bring about multicolor luminescence. In addition, different from the traditional NaYF 4 :Yb, Er co-doping system, the as-prepared hydrophilic NaErF 4 and NaErF 4 @SiO 2 samples showed a greater red to green ratio (R/G > 1), which may expand their potential applications in biological imaging and sensing fields.

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Advanced Physics Research · 2025 · IF 2.8

Functional Interface Engineering Enables Selective Multicolor Upconversion in NaErF4@NaYF4 Core–Shell Nanocrystals

Juan Ouyang,Ze Zhang,Minghua Shangguan,Haozhang Huang,Yuxuan Qiu,Songbin Liu,Junjun Tan,Xinyu Ye,Bo Zhou

Lanthanide-doped upconversion nanoparticles (UCNPs) have attracted extensive interest in broad frontier fields such as nanophotonics and biomedicine. However, low luminescence intensity, severe nonradiative energy loss, and limited color-tuning capability still urgently need to be addressed. Herein, a functional interface engineering regulation strategy is proposed to achieve a significant enhancement in upconversion luminescence intensity and multicolor output from the NaErF 4 @NaYF 4 core–shell nanocrystals. It is found that adjusting the amount of CF 3 COONa in the precursor during the shell growth is able to modulate lattice defect densities at the interface and thereby tune the energy migration paths and non-radiative transition processes of Er 3+ in the core. This also results in a multicolor tuning from green to yellow, orange, and red under 980 nm excitation, and the overall upconversion luminescence intensity is significantly enhanced by 17.1 times. Moreover, the interface engineering strategy is also applicable to 808 and 1540 nm excitations and the UCNPs with other shells (e.g., NaLuF 4 and NaGdF 4 ). These results provide new insights into the photochromic tuning of highly doped UCNPs and exhibit great promise in multiple anti-counterfeiting, information security, and biosensing and bioimaging.

研究领域: 纳米光子学 · 材料科学 · 生物医学工程 · 光学材料 · 防伪技术 · 生物成像
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CHEMICAL RESEARCH IN CHINESE UNIVERSITIES · 2023 ·Vol. 39 ·期 6 ·1070-1076 · IF 3.1

Improving PSCs’ Short-circuit Current by Adding NaErF4:0.5%Tm@NaLuF4 Up-conversion Nanoparticles Insertion Layer

Liu Deye,Lu Yang,Li Xu,Liu Fengmin,Liu Xiaomin,Lu Geyu

I n this study, we synthesized a core-shell structure of up-conversion nanoparticles (UCNPs) and deposited it on the surface of fluorine-doped tin oxide (FTO). Subsequently, we assembled a series of perovskite solar cells with FTO/UCNPs/c-TiO 2 /mp-TiO 2 /MAPbI 3 /Spiro-OMeTAD/Au structures with an effective area of 0.04 cm 2 . To optimize the devices, we adjusted the concentration of UCNPs precursor. The optimized device showed a power conversion efficiency (PCE) of 16.73% and a short-circuit current density ( J sc ) of 26.94 mA/cm 2 at AM 1.5. These values are 9.20% and 10.47% higher than those of the best performing control device (15.32% for PCE and 24.12 mA/cm 2 for J sc ), respectively. Furthermore, we characterized the perovskite layer, charge transport layer, and perovskite solar cells using various analytical methods. The results showed that the addition of UCNPs not only improved the charge extraction and transfer, but also enhanced the stability of electron transport layer devices. In conclusion, our findings offer a process for optimizing perovskite cells using UCNPs and preliminarily analyzing their principles.

研究领域: 材料科学 · 能源研究
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Laser & Photonics Reviews · 2022 ·Vol. 17 ·期 2 ·2200531 · IF 10.947

Cascaded Photon Confinement-Mediated Orthogonal RGB-Switchable NaErF4-Cored Upconversion Nanoarchitectures for Logicalized Information Encryption and Multimodal Luminescent Anti-Counterfeiting

Shuai Zhou,Yang Wang,Po Hu,Wei Zhong,Hong Jia,Jianrong Qiu,Jiajun Fu

Orthogonal upconversion nanoparticles (UCNPs) have received increasing research attention due to their unique optical performance. However, the establishment of the orthogonal UCNPs emitting primary red/green/blue (RGB) UCL remains a great challenge. Herein, RGB-switchable NaErF 4 -cored core–multishell UCNPs (RGB-UCNPs) are constructed through the coordinative implementation of outside-in cascaded photon harvesting and interfacial energy-transfer (IET) inhibition. By modulating several constructional factors, the power-density-independent red, green, and blue luminescence in high color purity is readily available in the elaborated RGB-UCNPs under 1550, 808, and 980 nm excitations, respectively. Notably, full-color emissions, involving red, yellow, green, cyan, blue, magenta and white, are dynamically implemented in this single architecture through manipulating the excitation power of the combined 1550/808/980 nm lasers. These emission profiles of RGB-UCNPs make them promising in broad photonic applications. As a proof of concept, the viability of the logicalized information encryption strategy and smartphone APP-assisted multimodal luminescent QR code anti-counterfeiting technique is demonstrated, which are both established based on directly useable RGB-UCNPs with assistance of a self-built combined laser system. This work not only opens up a new avenue to gain RGB-switchable UCL and flexible full-color output in a single nanostructure, but also provides enlightenment for developing the application scenarios of multicolor-tunable UCNPs.

CAS / MDL: 12125-01-8 112-80-1
研究领域: 材料科学 · 光学 · 纳米技术
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OPTICAL MATERIALS · 2022 · IF 3.754

Temperature sensing and bioimaging realized in NaErF4:40%Tm@NaYF4 with extremely intense red upconversion and suitable R/G emission ratio

Xiaomin Ning,Na Liu,Jinyang Liu,Yue Wu,Jing Qian,Wenchao Zhang,Wen Gu

The practical application of light thermometer based on the FIR (520/540) has been greatly limited due to the strong absorption of green light by biological tissues. The sensitivity of the temperature sensor located in a biological window (FIR-BW) also needs to be improved. Based on this, we designed and synthesized an upconversion nanoparticles (UCNPs) with suitable R/G ratio and red visual output to prebreaking the limitation of strong absorption of biological tissue, while improving the sensitivity of temperature sensor and in vivo fluorescence imaging. In this paper, NaErF 4 :40%Tm@NaYF 4 , a high efficient red UCNPs with R/G ratio (6.86), is first utilized as an optical thermometer, accomplished through the fluorescence intensity ratio (FIR) of thermally coupled stark sublevels of 4 S 3/2 / 4 F 9/2 (FIR(540/654)). In the studied temperature range, the maximum absolute and relative sensitivity (S a and S r ) is 0.47% K −1 and 2.61% K −1  at 298 K, respectively, which is much higher than most previous reports about FIR-based temperature sensors. Additionally, we investigated the in vivo bioimaging behavior of NaErF 4 :40%Tm@NaYF 4 in detail. The superior biocompatibility, the distribution to the main organs with the blood circulation system, and the bright red fluorescence signals were observed under 980 nm laser radiation . All the results imply that NaErF 4 :40%Tm@NaYF 4 is a promising candidate for optical thermometry and in vivo bioimaging with high sensitivity.

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OPTICAL MATERIALS · 2024 · IF 3.8

Modulated upconversion luminescence of water-dispersed NaErF4@NaYF4 nanoparticles by introducing Tm3+/Ho3+ as energy capture centers under multi-wavelength NIR excitation

Yu Yin,Jie Chen,Rong Liu,Xiaodan Zeng,Wei Zhao,Zhigang Liu,Mingshuo Ma

Water-dispersed red upconversion nanoparticles (UCNPs) have great application prospects in the biomedical field. Thus, a series of Er 3+ -based upconversion nanoparticles (Er-UCNPs) with excellent red upconversion luminescence under three-wavelength NIR excitation (808/980/1550 nm) were prepared by a simple thermal decomposition method, and then further functionalized by PAA to achieve good water dispersibility. Compared with NaErF 4 bare core, the emission intensity of Er-UCNPs samples doping of 0.5%Tm 3+ and 0.5%Ho 3+ as energy capture centers was significantly enhanced, and further improved after coating with NaYF 4 inert shell. Meanwhile, among all Er-UCNPs@NaYF 4 samples, NaErF 4 @NaYF 4 exhibited the highest emission intensity and longest luminescence lifetime due to the efficient suppression of luminescence quenching effect, while NaErF 4 :0.5%Tm 3+ @NaYF 4 showed highest red luminescence purity owing to the energy transfer process between Tm 3+ ( 3 H 5 ) and Er 3+ ( 4 I 13/2 ). The hydrophilic Er-UCNPs@NaYF 4 @PAA samples still maintained good red luminescence under multi-wavelength excitation. The luminescence enhancement mechanism in Er-UCNPs@NaYF 4 was discussed in detail based on spectral characteristics. The as-prepared water-dispersed Er-UCNPs@NaYF 4 @PAA with bright red luminescence under multi-wavelength NIR excitation will have potential applications in targeted therapy and deep tissue imaging.

CAS / MDL: 10025-75-9
研究领域: 生物医学 · 材料科学 · 光学
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TALANTA · 2021 · IF 6.057

A near-infrared light triggered fluormetric biosensor for sensitive detection of acetylcholinesterase activity based on NaErF4: 0.5 % Ho3+@NaYF4 upconversion nano-probe

Xu Zhao,Ling Zhang,Xu Yan,Li Zhang,Yang Lu,Jialin Pan,Meiling Zhang,Chenguang Wang,Hui Suo,Xiaoteng Jia,Xiaomin Liu,Geyu Lu

Acetylcholinesterase (AChE), as an important neurotransmitter , is widely present in the peripheral and central nervous systems. The aberrant expression of AChE could cause diverse neurodegenerative diseases. Herein, we developed a facile and interference-free fluorimetric biosensing platform for highly sensitive AChE activity determination based on a NaErF 4 : 0.5 % Ho 3+ @NaYF 4 nano-probe. This nano-probe exhibits a unique property of emitting bright monochromic red (650 nm) upconversion (UC) emission under multiband (~808, ~980, and ~1530 nm) near-infrared (NIR) excitations. The principle of this detection relies on the quenching of the strong monochromic red UC emission by oxidization products of 3,3′,5,5′-tetramethylbenzidine generated through AChE-modulated cascade reactions . This system shows a great sensing performance with a detection limit (LOD) of 0.0019 mU mL − 1 for AChE, as well as good specificity and stability. Furthermore, we validated the potential of the nano-probe in biological samples by determination of AChE in whole blood with a LOD of 0.0027 mU mL −1 , indicating the potential application of our proposed platform for monitoring the progression of AChE-related disease.

CAS / MDL: 12125-01-8 1310-73-2
研究领域: 生物化学 · 医学诊断 · 纳米技术
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