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OPTICAL MATERIALS · 2019 · IF 2.687

Optical-magnetic bifunctional sub-20 nm β-NaYF4:Yb3+/Er3+@NaGdF4:Yb3+/Nd3+@NaGdF4 core-shell-shell nanoparticles triggered by 808 nm light

Huazhen Liao,Song Ye,Yanling Shi,Deping Wang

Small size optical-magnetic bifunctional upconversion nanoparticles (UCNPs) that can be effectively triggered by 808 nm exhibit distinct advantages of improved tissue penetrating depth, minimized overheating effect, possible for multimodal imaging and high clearance rate, which therefore are considered as desirable candidates for bioapplications. In this research, the 808 nm triggered sub-20 nm β-NaYF 4 :Yb 3+ /Er 3+ @NaGdF 4 :Yb 3+ /Nd 3+ @NaGdF 4 active-core@active-shell@inert-shell structured UCNPs with optical and magnetic bifunctional properties were developed by seed-mediated growth method with NaOA as sodium source instead of the generally used NaOH. Through optimizing Nd 3+ doping concentration and outermost NaGdF 4 inert-shell thickness, the optical-magnetic bifunctional core-shell-shell structured UCNPs exhibited strong UC emission intensity and improved magnetic property . Furthermore, the core-shell-shell NPs were validated to be no cytotoxicity by cell viability assessment. Therefore, this research may open a general avenue for the synthesis of small size multifunctional UCNPs for practical bioapplications without overheating.

研究领域: 纳米材料科学 · 生物医学工程
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Nature Photonics · 2024 · IF 32.3

High-brightness transition metal-sensitized lanthanide near-infrared luminescent nanoparticles

Ming Jiang,Chen Ying,Miao Han,Fan Yong,Wang Shangfeng,Chen Zihan,Guo Zhenhao,Guo Zhixiu,Qi Luyin,Wang Xusheng,Yun Baofeng,Pei Peng,He Haisheng,Zhang Hongxin,Tang Yun,Zhao Dongyuan,Wong Gary Ka-Leung,Bünzli Jean-Claude G.,Zhang Fan

The demand for near-infrared (700–1,700 nm) materials in optical communications, laser sources and biological imaging applications has led to extensive research on lanthanide-doped nanoparticles, owing to their nanostructure modulation and interface property tunability. However, the low molar extinction coefficient of conventional lanthanide sensitizers limits the brightness of lanthanide near-infrared nanoparticles for applications in low-power excitation scenarios. Here we introduce Na 3 CrF 6 , a new crystalline nanoparticle that serves as both sensitizer and host for high-brightness near-infrared emission from lanthanide activators (Er 3+ , Tm 3+ , Yb 3+ or Nd 3+ ). We demonstrate an increase in brightness of up to 370 times compared with the most intense conventional lanthanide-sensitized nanoparticles. This discovery is also validated for other lanthanide-doped nanoparticles sensitized with low-cost transition metals (Mn 2+ or Ni 2+ ). Our transition metal-based nanoparticles represent a powerful toolbox to enable high signal-to-noise-ratio labelling and imaging with low-power excitation sources such as white light-emitting diode or persistent luminescence materials. This work paves the way for next-generation high-brightness near-infrared luminescence systems, suited for a wide range of low-illumination excitation applications.

CAS / MDL: 67-56-1 2923-18-4
研究领域: 材料科学 · 光学 · 纳米技术 · 生物医学工程
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Laser & Photonics Reviews · 2025 · IF 10

Room-Temperature and Ultrafast Synthesis of Sub-4 nm Yb3+/Nd3+ Ions-Doped CaMoO4 Nanocrystals with Near-Infrared Photoluminescence Quantum Yield of 40%

Mengxin Liu,Jiejun Pan,Xinan Shi,Bingsuo Zou,Daocheng Pan

Rare-earth doped metal oxide nanocrystals with high visible luminescence have been widely used in lighting and display applications owing to their low toxicity, and excellent thermal and chemical stability. However, the room-temperature preparation of near-infrared (NIR) luminescent rare-earth doped metal oxide nanocrystals remains a challenge. Herein, sub-4 nm Yb 3+ /Nd 3+ -doped CaMoO 4 nanoparticles are prepared by a facile room-temperature ligand-assisted coprecipitation method, which can be completed within 1 min under ambient conditions. Short-chain butyric acid and butylamine as binary ligands play a crucial role in the synthesis of NIR luminescent nanoparticles. The as-prepared nanocrystals can be well dispersed in organic solvents such as chloroform since they are capped with butyric acid and butylamine. The energy transfers from MoO 4 2 − ${\rm MoO}^{2-}_{4}$ ions to Yb 3+ and Nd 3+ ions are systematically investigated in CaMoO 4 :Yb 3+ and CaMoO 4 :Nd 3+ nanoparticles, respectively. More importantly, this ultrafast and room-temperature synthesis strategy is particularly suitable for the large-scale preparation of Yb 3+ /Nd 3+ -doped CaMoO 4 nanoparticles (≈23 g) with NIR emission, which provides new ideas and possibilities for the commercial production of extremely small and NIR-emitting nanophosphors.

研究领域: 材料科学 · 光学
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CERAMICS INTERNATIONAL · 2024 · IF 5.1

Role of host matrix on NIR emission and ratiometric thermometry properties in Nd3+/Yb3+ co-doped CaGd2(MO4)4 (M = W, Mo) phosphors

Chunyang Zhang,Yifan Wang,Zexiong Wang,Shilong Zhao,Ruoshan Lei,Shiqing Xu

The development of ultrasensitive thermometric phosphors has become an active area of research due to their appealing applications in the contactless temperature detection field. Herein, the scheelite-related compounds—CaGd 2 (WO 4 ) 4 : Nd 3+ , Yb 3+ and CaGd 2 (MoO 4 ) 4 : Nd 3+ , Yb 3+ , which exhibit high sensing capacity—are successfully prepared and systematically characterized. The X-ray diffraction analysis reveals that CaGd 2 (WO 4 ) 4 : Nd 3+ , Yb 3+ exhibits the monoclinic structure, whereas CaGd 2 (MoO 4 ) 4 : Nd 3+ , Yb 3+ is in the tetragonal phase. The maximum phonon cut-off energy of CaGd 2 (WO 4 ) 4 : Nd 3+ , Yb 3+ is 929 cm −1 , slightly larger than that of CaGd 2 (MoO 4 ) 4 : Nd 3+ , Yb 3+ (904 cm −1 ). Irradiated by 980 nm laser, PL spectra consist of the Nd 3+ : 4 F j → 4 I 9/2 (j = 7/2, 5/2, 3/2) and Yb 3+ : 2 F 5/2  →  2 F 7/2 emissions located in the near-infrared (NIR) range. Negative and positive thermal quenching behaviors are observed for the emissions of Nd 3+ (754, 802, and 868 nm) and Yb 3+ (1008 nm), respectively, attributed to the cooperative effects of the phonon-assisted energy transfer process of Yb 3+ → Nd 3+ and excited state absorption process of Nd 3+ . Moreover, the host material can affect the luminescence properties, thermal enhancement factor of the NIR anti-Stokes emission, and thermal sensing performance of the Nd 3+ -Yb 3+ pair. Consequently, CaGd 2 (MoO 4 ) 4 : Nd 3+ , Yb 3+ exhibits higher sensing sensitivity (S r-max  = ∼6.00%K −1 ) than CaGd 2 (WO 4 ) 4 : Nd 3+ , Yb 3+ (S r-max  = ∼5.56%K −1 ). This study provides useful information for the construction of high-performance ratiometric thermometers based on the inverse thermal dependence of the NIR emissions of Nd 3+ and Yb 3+ ions.

研究领域: 材料科学 · 光学
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BIOMATERIALS · 2016 · IF 8.387

808 nm Light-triggered and hyaluronic acid-targeted dual-photosensitizers nanoplatform by fully utilizing Nd3+-sensitized upconversion emission with enhanced anti-tumor efficacy

Zhiyao Hou,Kerong Deng,Chunxia Li,Xiaoran Deng,Hongzhou Lian,Ziyong Cheng,Dayong Jin,Jun Lin

The current near-infrared (NIR) light-induced photodynamic therapy (PDT) can enhance the tissue penetration depth to trigger photosensitizers (PSs) far from the surface. NIR-mediated PDT is still challenged by overheating effect on normal tissues, limited tumor selectivity and low reactive oxygen species (ROS) yields. Here we construct a dual-agent photosensitizing nanoplatform by combining UV-blue upconversion emitting NaYF 4 :Yb/ [email protected] 4 : [email protected] 4 : [email protected] 4 (labeled as UCNPs) multi-shell nanocrystals with titanium dioxide (TiO 2 , UV-light-excited PS) and hypocrellin A (HA, blue-light-excited PS), which can induce cancer cell apoptosis by 808 nm light-triggered and hyaluronic acid (Hyal)-targeted PDT. In this construction strategy, the crystallized TiO 2 shells on the surface of UCNPs can play dual roles as UV-light excited PS and conjugation site for Hyal, and then Hyal is served as targeting-ligand as well as the carrier of HA simultaneously. The step-by-step reactive mode of loading PSs and modifying targeting-ligands is a controllable and ordered design based on the use of one intermediate product as the reaction site for the next component. The Nd 3+ -sensitized UCNPs with quenching reduction layer can efficiently convert 808 nm NIR light to UV-blue emission for simultaneous activation of two PSs with enhanced intracellular ROS generation. Through the in vitro and in vivo experiment results, the dual-photosensitizers nanoplatform presents enhanced anti-tumor efficacy by effective targeting cellular uptake and taking full advantage of upconversion emission, which may make a major step toward next generation of NIR-mediated PDT.

研究领域: 纳米技术 · 生物医学工程 · 癌症研究 · 药学科学
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Nanoscale · 2018 ·Vol. 10 ·期 22 ·10641-10649 · IF 7.233

808 nm-light-excited upconversion nanoprobe based on LRET for the ratiometric detection of nitric oxide in living cancer cells

Han Wang,Yi Liu,Zhaohui Wang,Man Yang,Yueqing Gu

NO (nitric oxide) has dual functions in cancer, promoting carcinogenesis in low concentrations and inducing tumor cell apoptosis at high concentrations. The dual-edged-sword functions of NO make it particularly appealing to develop a sensitive and specific chemical probe for its detection. However, most NO sensors suffer from poor Stokes shifts and are limited by ultraviolet (UV) or visible light excitation, which render it difficult to avoid the intrinsic background signal. In this study, an 808 nm laser-excited Nd3+-sensitized upconversion nanoprobe based on LRET (luminescence resonance energy-transfer) for NO detection was constructed for the first time. This probe was composed of Nd3+-sensitized core–shell upconversion nanoparticles (540 nm and 660 nm emission) as the energy donor and RhBs as the acceptor. In the presence of NO, RhBs was converted into Rhodamine B and its strong absorption subsequently quenched the 540 nm fluorescence of UCNPs, while the emission at 660 nm remained constant. The ratiometric detection of the fluorescence at 540 nm, as compared to 660 nm, can precisely respond to the difference in NO levels with a detection limit of 0.21 μM. Importantly, compared with conventional UCNPs excited at 980 nm, the 808 nm light excitation led to lower water absorption and deeper tissue penetration, thus avoiding overheating and allowing for long-term biological imaging. This strategy has been perfectly applied to detecting the NO levels in living cells to differentiate the tumor cells from normal cells based on varied intracellular NO concentration. Further, the nanosystem realized the real-time monitoring of NO during treatment with NO donor drugs, which could inspire the future application of this probe to guide NO therapy.

研究领域: 生物化学 · 纳米技术 · 癌症生物学 · 光学成像
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APPLIED SURFACE SCIENCE · 2021 · IF 6.707

Investigating the effect of Nd3+ dopant and the formation of g-C3N4/BiOI heterostructure on the microstructural, optical and photoelectrocatalytic properties of g-C3N4

P. Velusamy,M. Sathiya,Yunpeng Liu,Shanhu Liu,R. Ramesh Babu,Mohamed Aly Saad Aly,E. Elangovan,Haibo Chang,Liqun Mao,Ruimin Xing

A two-step thermal poly-condensation and hydrothermal method is used to prepare noble metal-free nano-heterostructure of neodymium (Nd)-doped graphitic carbon nitride (g-C 3 N 4 ) and bismuth oxyiodide (BiOI). The synthesised Nd- doped g-C 3 N 4 /BiOI heterostructure shows high electron-hole separation. Moreover, a fast charge transport at the heterojunction is noted and further leads to low charge recombination rate. Consequently, the synthesised heterostructure overcomes the high charge recombination rate of g-C 3 N 4 . This work reports the effect of Nd- doping and the formed heterojunction on the structural, optical, electrical conductivity and photoelectrochemical (PEC) properties of the heterostructure. Moreover, introducing Nd dopant into g-C 3 N 4 enhances visible light absorption of g-C 3 N 4 . The optimal hetero-nanostructure (5.0 wt% Nd doped g-C 3 N 4 /BiOI) shows high photocurrent density (15.50 mA/cm 2 ) and hydrogen evolution rate (288 μmol h −1 cm −2 ) under visible light (λ ≥ 420 nm) illumination when compared to other wt.% of Nd doped g-C 3 N 4 and heterostructure. Additionally, the low emission features obtained from the photoluminescence studies and the heterojunction visually observed by HRTEM strongly emphasise that the formation of heterostructure leads to low recombination of charge carriers. Doping and forming heterostructure is shown to be an effective, controllable and an optimal approach to improve the PEC water splitting performance of g-C 3 N 4 .

研究领域: 材料科学 · 光催化
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JOURNAL OF SOLID STATE CHEMISTRY · 2012 · IF 2.159

Novel light-conversion hybrids of SBA-16 functionalized with rare earth (Eu3+, Nd3+, Yb3+) complexes of modified 2-methyl-9-hydroxyphenalenone and 1,10-phenanthroline

Yan-Jing Gu,Bing Yan,Xiao-Fei Qiao

Novel rare earth complex-functionalized mesoporous SBA-16-type hybrid materials are synthesized by the co-condensation of modified 2-methyl-9-hydroxyphenalenone (MHPOSi), from modified 3-(triethoxysilyl)-propyl isocyanate (TEPIC), and tetraethoxysilane (TEOS) in the presence of Pluronic F127 as a template. These inorganic–organic mesoporous hybrids are characterized by FT-IR spectra, small-angle X-ray diffraction (SAXRD), N 2 adsorption–desorption measurements, thermal analysis and spectroscopy. Their photophysical properties, which show novel light conversion properties, are discussed in detail. The Eu 3+ hybrid system shows ultraviolet excitation and visible emission, and the Nd + and Yb 3+ hybrids exhibit visible excitation and NIR emission.

研究领域: 材料科学 · 光学
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ACS Applied Materials & Interfaces · 2013 · IF 5.008

Near Infrared and Visible Luminescence from Xerogels Covalently Grafted with Lanthanide [Sm3+, Yb3+, Nd3+, Er3+, Pr3+, Ho3+] β-Diketonate Derivatives Using Visible Light Excitation

Lining Sun,Yannan Qiu,Tao Liu,Jin Z. Zhang,Song Dang,Jing Feng,Zhijuan Wang,Hongjie Zhang,Liyi Shi

A series of ternary lanthanide β-diketonate derivatives covalently bonded to xerogels (named as Ln-DP-xerogel, Ln = Sm, Yb, Nd, Er, Pr, Ho) by doubly functionalized alkoxysilane (dbm-Si) was synthesized in situ via a sol-gel process. The properties of these xerogel materials were investigated by Fourier-transform infrared (FT-IR) spectroscopy, field-emission scanning electron microscopy (FE-SEM), diffuse reflectance (DR) spectroscopy, thermogravimetric analyses, and fluorescence spectroscopy. The data and analyses suggest that the lanthanide derivatives have been covalently grafted to the corresponding xerogels successfully. Of importance here is that, after excitation with visible light (400–410 nm), the xerogels all show characteristic visible (Sm3+) as well as near-infrared (NIR; Sm3+, Yb3+, Nd3+, Er3+, Pr3+, Ho3+) luminescence of the corresponding Ln3+ ions, which is attributed to the energy transfer from the ligands to the Ln3+ ions via an antenna effect. Exciting with visible light is advantageous over UV excitation. Furthermore, to the best of our knowledge, it is the first observation of NIR luminescence with visible light excitation from xerogels covalently bonded with the Sm3+, Pr3+, and Ho3+ derivatives. Compared to lanthanide complexes (Ln = Er, Nd, Yb) functionalized periodic mesoporous organosilica (PMO) materials that exhibit similar optical properties reported in our previous work, the Ln-DP-xerogel (Ln = Sm, Yb, Nd, Er, Pr, Ho) in this case offer advantages in terms of ease of synthesis and handling and potentially low cost for emerging technological applications. Development of near-infrared luminescence of the lanthanide materials with visible light excitation is of strong interest to emerging applications such as chemosensors, laser systems, and optical amplifiers.

研究领域: 材料科学 · 光学
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ACS Omega · 2022 · IF 4.132

Simultaneous Observation of Visible Upconversion and Near-Infrared Downconversion in SrF2:Nd3+/Yb3+/Er3+ Nanocrystals and Their Application for Detecting Metal Ions under Dual-Wavelength Excitation

Linxuan Wang,Weiqiang Yang,Liang Li,Shuai Hu,Maohui Yuan,Zining Yang,Kai Han,Hongyan Wang,Xiaojun Xu

In this work, a sequence of Nd3+, Yb3+, and Er3+ tridoped SrF2 nanocrystals (NCs) is synthesized by a hydrothermal method. Both the efficient near-infrared downconversion luminescence (DCL) and visible upconversion luminescence (UCL) of the Er3+ and Nd3+ ions are simultaneously observed and systematically demonstrated under dual-wavelength excitation (808 and 980 nm continuous-wave lasers). Subsequently, the SrF2:Nd3+/Yb3+/Er3+ (15/4/0.2 mol %) NCs with the strongest luminescence were utilized for detecting the metal ion concentrations under 808 nm excitation. The results reveal that both the UCL and DCL gradually decrease as the metal ion concentrations increase, and high sensitivity is obtained for Cu2+ ions with a detection limit of 0.22 nM (∼650 nm) and 0.63 nM (∼976 nm). In addition, these SrF2:Nd3+/Yb3+/Er3+ NCs are further demonstrated to achieve a solid-state display under 980 nm excitation, exhibiting obvious “red” and “green” patterns by varying the doping rare earth ion concentrations.

研究领域: 材料科学 · 光学 · 分析化学
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Nanoscale · 2014 ·Vol. 6 ·期 24 ·14799-14809 · IF 6.739

LaF3:Ln mesoporous spheres: controllable synthesis, tunable luminescence and application for dual-modal chemo-/photo-thermal therapy

Ruichan Lv,Guixin Yang,Fei He,Yunlu Dai,Shili Gai,Piaoping Yang

In this report, uniform LaF3:Ln mesoporous spheres have been synthesized by a facile and mild in situ ion-exchange method using yolk-like La(OH)3:Ln mesoporous spheres as templates, which were prepared through a self-produced bubble-template route. It was found that the structures of the final LaF3:Ln can simply be tuned by adding a polyetherimide (PEI) reagent. LaF3:Ln hollow mesoporous spheres (HMSs) and LaF3:Ln flower-like mesoporous spheres (FMSs) were obtained when assisted by PEI and in the absence of PEI. The up-conversion (UC) luminescence results reveal that the doping of Nd3+ ions in LaF3:Ln can markedly influence the UC emissions of the products. It is interesting that an obvious thermal effect is achieved due to the energy back-transfer from Tm3+ to Nd3+ ions under 980 nm near-infrared (NIR) irradiation. The LaF3:Yb/Er/Tm/Nd HMSs show good biocompatibility and sustained doxorubicin (DOX) release properties. In particular, upon 980 nm NIR irradiation, the photothermal effect arising from the Nd3+ doping induces a faster DOX release from the drug release system. Moreover, UC luminescence images of LaF3:Yb/Er/Tm/Nd HMSs uptaken by MCF-7 cells exhibit apparent green emission under 980 nm NIR irradiation. Such a multifunctional carrier combining UC luminescence and hyperthermia with the chemotherapeutic drugs should be of high potential for the simultaneous anti-cancer therapy and cell imaging.

CAS / MDL: 25952-53-8 6066-82-6
研究领域: 材料科学 · 纳米技术 · 生物医学工程 · 癌症治疗
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JOURNAL OF MATERIALS CHEMISTRY · 2011 ·Vol. 22 ·期 6 ·2632-2640 · IF 5.101

Lanthanide dopant-induced formation of uniform sub-10 nm active-core/active-shell nanocrystals with near-infrared to near-infrared dual-modal luminescence

Daqin Chen,Yunlong Yu,Feng Huang,Hang Lin,Ping Huang,Anping Yang,Zhaoxing Wang,Yuansheng Wang

We present a novel strategy involving the lanthanide dopant-induced formation of ultrasmall (sub-10 nm) uniform Ln3+:BaF2/Ln3+:SrF2 active-core/active-shell architectures. The lanthanide ions doped in the shell are demonstrated to play a key role to retard the growth of the core/shell nanocrystals. Particularly, adopting ∼3 nm Tm3+,Yb3+:BaF2 nanocrystals as cores prepared by a solvothermal reaction, growth of Gd3+,Nd3+:SrF2 shells is successfully induced on the surfaces of these cores through a thermal decomposition process, forming ∼7 nm highly uniform and monodisperse Tm3+,Yb3+:BaF2/Gd3+,Nd3+:SrF2 active-core/active-shell nanocubes. In this architecture, the Gd3+,Nd3+:SrF2 shell not only benefits the enhancement of the near-infrared to near-infrared upconversion luminescence of the Tm3+,Yb3+:BaF2 core, but also acts as the host to realize the near-infrared to near-infrared downconversion luminescence of Nd3+ dopants and the paramagnetism of Gd3+ ones. Importantly, the doping of Tm3+/Yb3+ and Nd3+ into the core and shell respectively effectively suppresses the adverse energy transfer from Tm3+ to Nd3+ as well as from Nd3+ to Yb3+, resulting in lessening of the quenching for both Tm3+ upconversion and Nd3+,Yb3+ downconversion emissions. These hydrophobic core/shell nanocrystals are further converted into hydrophilic ones using thioglycolic acid as the surface ligand. The sub-10 nm water-soluble active-core/active-shell architectures with near-infrared to near-infrared dual-modal luminescence and proper paramagnetism may find potential applications in biomedical imaging and detection.

研究领域: 材料科学 · 纳米技术 · 生物医学工程 · 光学
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