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ACS Applied Materials & Interfaces · 2025 · IF 8.2

Unusual Single Band 803 nm Persistent Luminescence of Tm-Doped Calcium Titanate Charged in the Near-Infrared Bio-Imaging Window

Gulizhabaier Abulipizi,Juanjuan Zhou,Chaomin Qu,Leping Ding,Ziang Zong,Yanlun Fang,Zimin Yu,Xingyuan Shi,Fanwen Yang,Zhanjun Li

Lanthanide-doped materials were developed with interesting near-infrared (NIR) persistent luminescence (PersL) properties after X-ray irradiation but are limited by poor charging ability based upon biocompatible red light. In this study, CaTiO3:Tm (CTT) was found to emit an unusual single band PersL at ∼800 nm, which was rechargeable by red-NIR light excitation (∼650 to 720 nm). Moreover, blue or deep red light could charge more intense PersL than UV light in CTT, which was quite different from all the other known lanthanide-activated NIR PersL materials. An upconverting-energy transfer PersL mechanism was proposed based on the upconverting property of Tm3+ and its energy transfer to Ti3+ in the CaTiO3 matrix. The interaction of Tm3+ and Ti3+ in CaTiO3 quite possibly played an important role in the unusual PersL process of CTT, which avoided the band-pass transition of the CaTiO3 matrix. By comparison with a series of Tm-doped phosphors, CaTiO3 was found to be an optimal PersL matrix to generate the unique PersL properties of Tm3+. The in situ charged NIR PersL imaging of a medical stent implant in the neck of a chicken model was demonstrated. This study reveals the unusual PersL properties of CTT and will promote advanced biomedical applications of rare-earth-doped PersL biomaterials.

CAS / MDL: 3087-36-3 6192-12-7
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Journal of Materials Chemistry C · 2025 · IF 5.1

Upconversion phosphors ofCaLaAl3O7:RE3+/Yb3+ (RE=Tm, Ho) and their multifunctional applications for multi-color anti-counterfeiting and laser displays

Shan shan Zhao,He-He Dong,Weichang Li,Lei Zhang,Shikai Wang,Chun Yu,Hu Li

Upconversion emission materials have many advantages, such as narrowband sharp line emission, excellent photochemical stability, and long lifespan. In particular, under 980 nm invisible laser-beam irradiation, materials with visible light upconversion luminescence have vital application value in optical anti-counterfeiting and laser displays. In this study, a library of upconversion phosphors of CaLaAl3O7:RE3+/Yb3+ (RE=Tm, Ho) was produced through a high-temperature solid-state reaction method. The powders exhibited different color emissions under different excited wavelengths. Under 980 nm laser excitation, Tm3+/Yb3+ co-doped phosphors exhibited upconversion emission of 474 nm blue light, which was attributed to the 1G4→3H6 transition of Tm3+, and the fitting slope of the upconversion luminescence intensity vs. laser-pump power density was n450-500=2.83, which indicated the three-photon absorption upconversion process. Additionally, Ho3+/Yb3+ co-doped phosphors had the strongest red emission at 660 nm, originating from the 5F4/5S2→5I8 transition of Ho3+, which belongs to the two-photon absorption process. Subsequently, the changes in chromaticity coordinates of the prepared samples were analyzed under different light excitations, and different light color emissions were observed. The color purities of Ho3+/Yb3+ and Tm3+/Yb3+ co-doped samples were 99.9% and 65.4%, respectively. Finally, we verified the practical application value of the prepared powder in the fields of multi-color luminescence optical anti-counterfeiting and laser displays. The results show that the produced phosphors have vital application potential in information security protection, optical data storage, and 3D laser displays.

研究领域: 材料科学 · 光学工程
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RSC Advances · 2013 ·Vol. 3 ·期 48 ·26367-26375 · IF 2.562

Visible-light sensitized sol–gel-based lanthanide complexes (Sm, Yb, Nd, Er, Pr, Ho, Tm): microstructure, photoluminescence study, and thermostability

Lining Sun,Yannan Qiu,Tao Liu,Hongshang Peng,Wei Deng,Zhijuan Wang,Liyi Shi

The homogeneously transparent hybrid gels (Ln–N–P-gel, Ln = Sm, Yb, Nd, Er, Pr, Ho, Tm) containing lanthanide complexes (by using dinaphthoylmethane (dnm) as the primary ligand and 1,10-phenanthroline (phen) as the synergic ligand) via the in situ approach have been prepared. The dnm ligand was synthesized and adopted with the aim to sensitize the lanthanide ions with visible light. The properties of Ln–N–P-gels were investigated by Fourier-transform infrared (FT-IR), diffuse reflectance (DR), scanning electron micrographs (SEM), fluorescence spectra and thermogravimetric analyses. The results reveal that the lanthanide complexes are successfully in situ synthesized in the corresponding Ln–N–P-gels. Under the excitation of visible-light, the Ln–N–P-gels showed the respective visible (Sm3+) and near-infrared (Sm3+, Yb3+, Nd3+, Er3+, Pr3+, Ho3+, Tm3+) luminescence. The near-infrared (NIR) luminescence of Sm3+, Pr3+, Ho3+, and Tm3+ complexes sensitized by visible-light had been rarely reported previously, which is highly desired for biomedical and photonics applications. Based on the relevant energy levels, a model was proposed to explain the visible-NIR luminescence of the Ln–N–P-gels based on the visible-light excitation.

研究领域: 材料科学 · 光学 · 生物医学工程
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CRYSTENGCOMM · 2021 ·Vol. 23 ·期 21 ·3892-3900 · IF 3.545

Temperature-dependent upconversion luminescence multicolor tuning and temperature sensing of multifunctional β-NaYF4:Yb/Er@β-NaYF4:Yb/Tm microcrystals

Dandan Ju,Xiaoli Gao,Shouchao Zhang,Yang Li,Wenjing Cui,Yinhui Yang,Mingyan Luo,Shujing Liu

Temperature is one of the physical parameters that affects the emission luminescence properties of upconversion (UC) materials. Temperature-dependent emission color tuning and good temperature sensitivity in multifunctional β-NaYF4:Yb/Er@β-NaYF4:Yb/Tm microcrystals were achieved under 980 nm excitation. Based on the different emission bands (blue, green and red bands) and spectral sensitivities of the core–shell structured microcrystals to temperature, intense white-light emission was obtained at room temperature and a real-time naked-eye recognizable emission color change from white to the purplish-pink region was realized with the temperature increasing from 300 to 500 K. Furthermore, optical temperature sensing properties of the sample with good sensitivity (from 0.0034 to 0.0044 K−1) were investigated by using a fluorescence intensity ratio between 521 nm (2H11/2 → 4I15/2 transition) and 540 nm (4S3/2 → 4I15/2 transition) in the temperature range from 300 to 500 K. The results indicate that the sample has high sensitivity in a relatively wide range of temperature intervals, especially in the low temperature region. We believe that the multifunctional core–shell structured microcrystals exhibit promising applications in white-light emitting diodes, the anti-counterfeiting field, and temperature sensing.

CAS / MDL: 6381-92-6
研究领域: 材料科学 · 光学
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JOURNAL OF ALLOYS AND COMPOUNDS · 2020 · IF 4.65

Effect of different transition metal fluorides TMFx (TM=Nb, Co, Ti) on hydrogen storage properties of the 3NaBH4-GdF3 system

Tianping Huang,Jianxin Zou,Huabing Liu,Wenjiang Ding

Three kinds of transition metal fluorides TMF x (TM = Nb, Co, Ti) were introduced into the 3NaBH 4 -GdF 3 hydrogen storage system via mechanical milling. Their effects on the hydrogen storage behaviors of 3NaBH 4 -GdF 3 were systematically investigated by means of DSC and volumetric methods. All TMF x exhibited promoting effect on hydrogen desorption properties of 3NaBH 4 -GdF 3 to different degrees, especially when NbF 5 or TiF 3 was added. For example, the hydrogen desorption peak temperature was decreased by 17 °C with doping 3 mol% of NbF 5 . Besides, TiF 3 improved also the hydrogen absorption capacity and reversibility of 3NaBH 4 -GdF 3 . Based on XRD analyses, the role of TMF x on the dehydrogenation and the promoting effect of TiF 3 on the reversibility of 3NaBH 4 -GdF 3 were clarified. This work helped to understand the combination effect of rare earth metal fluoride (GdF 3 ) and transition metal fluorides on the reversible hydrogen storage properties of NaBH 4 .

CAS / MDL: 13765-26-9 16940-66-2
研究领域: 材料科学 · 化学工程
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JOURNAL OF LUMINESCENCE · 2015 · IF 2.719

An optical FRET inhibition sensor for serum ferritin based on Mn2+-doped NaYF4:Yb,Tm NIR luminescence up-conversion nanoparticles

ShaoZhen Wang,Jianguo Zhang,Hongqi Chen,Lun Wang

A new serum ferritin (SF) biosensor based on fluorescence resonance energy transfer (FRET) from Mn 2+ -doped NaYF 4 :Yb,Tm up-converting rare-earth nanophosphors (UCNPs, donor) to gold nanorods (GNRs, acceptor) was developed in the near-infrared (NIR) region. The as-prepared Mn 2+ -doped NaYF 4 :Yb,Tm UCNPs exhibited a strong emission at 807   nm in the NIR region and were modified with poly-(acrylic acid) (PAA) before conjugating with anti-SF (Ab 1 ). The negatively charged donor (Ab 1 -UCNPs) and the positively charged acceptor (GNRs) were mixed in close proximity due to electrostatic interactions, which quenched the fluorescence emission of the Mn 2+ -doped NaYF 4 :Yb,Tm UCNPs. However, added SF combines with the anti-SF because the binding affinity between SF and Ab 1 is stronger than the electrostatic interactions. Thus, the acceptor separated from the donor, and the fluorescence was restored. Under optimal conditions, the restored fluorescence exhibited a linear relationship with SF concentrations ranging from 0.23 to 16.88   ng/mL and a limit of detection as low as 0.12   ng/mL. The proposed method was also used to monitor SF in human serum samples.

研究领域: 生物化学 · 纳米医学 · 分析化学
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ANALYTICAL CHEMISTRY · 2013 · IF 5.695

Incorporation of Computed Tomography and Magnetic Resonance Imaging Function into NaYF4:Yb/Tm Upconversion Nanoparticles for in Vivo Trimodal Bioimaging

Ji-Wei Shen,Cheng-Xiong Yang,Lu-Xi Dong,Hao-Ran Sun,Kai Gao,Xiu-Ping Yan

Rational design and fabrication of multimodal imaging nanoprobes are of great significance for in vivo imaging. Here we report the fabrication of a multishell structured NaYF4:Yb/Tm@NaLuF4@NaYF4@NaGdF4 nanoprobe via a seed-mediated epitaxial growth strategy for upconversion luminescence (UCL), X-ray computed tomography (CT), and magnetic resonance (MR) trimodal imaging. Hexagonal phase NaYF4:Yb/Tm is used as the core to provide UCL, while the shell of NaLuF4 is epitaxially grown on the core not only to provide an optically inert layer for enhancing the UCL but also to serve as a contrast agent for CT. The outermost NaGdF4 shell is fabricated as a thin layer to give the high longitudinal relaxivity (r1) desired for MR imaging. The transition shell layer of NaYF4 not only provides an interface to facilitate the formation of NaGdF4 shell but also inhibits the energy transfer from inner upconversion activator to surface paramagnetic Gd3+ ions. The fabricated multishell structured nanoprobe shows intense near-infrared UCL, high r1 value of 3.76 mM–1 s–1, and in vitro CT contrast effect. The multishell structured nanoprobe offers great potential for in vivo UCL/CT/MR trimodal imaging. Further covalent bonding of folic acid makes the multishell structured nanoprobe promising for in vivo targeted UCL imaging of tumor-bearing mice.

研究领域: 生物医学工程 · 材料科学 · 影像医学
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Chemistry-An Asian Journal · 2022 ·Vol. 17 ·期 14 ·e202200161 · IF 4.839

Multimodal Imaging and Synergetic Chemodynamic/Photodynamic Therapy Achieved Using an NaGdF4,Yb,Er@ NaGdF4,Yb,Tm@NaYF4@Fe-MOFs Nanocomposite

Bo Ling,Yaguang Wang,Ruo Mi,Di Wang,Hongqi Chen,Xiaohu Li,Ye Zhang,Lun Wang

Graphical NaGdF 4 ,Yb,Er@NaGdF 4 ,Yb,Tm@NaYF 4 core@shell@shell three-layer structure of upconversion nanoparticles coated with Fe−TCPP metal-organic frameworks nanocomposite was designed and constructed for multimodal imaging and synergetic chemodynamic therapy/photodynamic therapy of tumors. Here, NaGdF 4 ,Yb,Er@NaGdF 4 ,Yb,Tm@NaYF 4 core@shell@shell three-layer structure of upconversion nanoparticles (UCNPs) coated with Fe−Tetrakis (4-carboxyphenyl) porphine (TCPP) metal-organic frameworks (Fe-MOFs) nanocomposite (UCNPs@MOFs) was designed and constructed for multimodal imaging and synergetic chemodynamic therapy (CDT)/photodynamic therapy (PDT) of tumors. The UCNPs@MOFs were successfully applied for tumor cells imaging in vitro and in vivo in near-infrared (NIR) region. The doped Gd was used as contrast agent for the magnetic resonance imaging (MRI) of mouse tumors. The luminescence in the UV-vis region was absorbed by the Fe-MOFs to produce singlet oxygen ( 1 O 2 ) for PDT. The Fe 3+ doped in the MOFs can catalyze H 2 O 2 to produce oxygen and hydroxyl radical (⋅OH). Hydroxyl radical is used in CDT and cooperates with the 1 O 2 of PDT. Based on the CDT/PDT synergistic effects, the UCNPs@MOFs nanocomposite had obviously enhanced tumor inhibitory efficiency in vivo. These results described that the asprared UCNPs@MOFs nanocomposite have great potential in the effective multimodal imaging and treatment of tumors.

研究领域: 生物医学工程 · 纳米医学 · 肿瘤学
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CRYSTENGCOMM · 2023 ·Vol. 25 ·期 38 ·5452-5460 · IF 3.1

Upconversion luminescence and temperature sensing properties of Yb2(MoO4)3:Ln3+ (Ln = Ho, Tm, Er) phosphors based on energy transfer

Huimin Du,Yunhao Liang,Xingzuo Liu,Yue Deng,Jie Yang,Jun Yang,Shanshan Hu

Yb2(MoO4)3:Ln3+ (Ln = Ho, Tm, Er) phosphors were synthesized by a hydrothermal method with further calcination. The crystal structure and morphology of the samples were characterized by X-ray diffraction and scanning electron microscopy. The effects of rare earth ion interaction in the Yb2(MoO4)3:Ln3+ phosphors on the upconversion (UC) luminescence properties and energy transfer process at different doping concentrations were discussed. It is concluded that by doping Ho3+, Tm3+, and Er3+ in the Yb2(MoO4)3 host, the phosphors emit orange-yellow, blue and green light, respectively, and the energy transfer from Yb3+ → Ho3+/Er3+ and Yb3+ → Tm3+ is a two and three photon process, respectively. Under the excitation of a 980 nm laser, by changing the Ho3+/Tm3+ ratio in doped Yb2(MoO4)3, we have realized the transition of phosphors from cold white light to warm white light. The temperature sensitivity of the 2H11/2 and 4S3/2 energy levels of Yb2(MoO4)3:Er3+ in the range of 323–573 K was studied by the FIR technology. The experimental results show that the maximum absolute sensitivity was 0.0081 K−1 at 573 K and the maximum relative sensitivity was 0.01 K−1 at 323 K. Compared with other materials, the Er3+ doped Yb2(MoO4)3 phosphor is an excellent optical temperature sensing material.

研究领域: 材料科学 · 光学
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JOURNAL OF CHROMATOGRAPHY B-ANALYTICAL TECHNOLOGIES IN THE BIOMEDICAL AND LIFE SCIENCES · 2024 · IF 2.8

Streamlined on-column refolding and purification of nanobodies from inclusion bodies expressed as fusion proteins

Yiwen Zhang,Yang Guo,Liang Song,Wenshuai Liu,Rui Nian,Xiying Fan

This study introduces an efficient on-column refolding and purification method for preparing nanobodies (Nbs) expressed as inclusion bodies and fusion proteins. The HisTrap TM FF system was successfully employed for the purification of the fusion protein FN1-ΔI-CM-2D5. The intein ΔI-CM cleavage activity was activated at 42 °C, followed by incubation for 4 h. Leveraging the remarkable thermal stability of Nbs, 2D5 was further purified through heat treatment at 80 °C for 1h. This method yielded up to 107.2 mg of pure 2D5 with a purity of 99.2 % from just 1L of bacterial culture grown in a shaker flask. Furthermore, this approach successfully restored native secondary structure and affinity of 2D5. Additionally, the platform was effectively applied to the refolding and purification of a polystyrene-binding nanobody (B2), which exhibited limited expression in the periplasmic and cytoplasmic spaces of E. coli . This endeavor resulted in the isolation of 53.2 mg of pure B2 Nb with a purity exceeding 99.5 % from the same volume of bacterial culture. Significantly, this approach restored the native secondary structure of the Nbs, highlighting its potential for addressing challenges associated with expressing complex Nbs in E. coli . Overall, this innovative platform provides a scientifically rigorous and reproducible method for the efficient preparation of Nbs, offering a valuable tool for antibody research and development.

CAS / MDL: 151-21-3
研究领域: 生物技术 · 蛋白质工程 · 分子生物学 · 抗体研究
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JOURNAL OF PHYSICAL CHEMISTRY B · 2012 · IF 3.696

Folic Acid-Conjugated LaF3:Yb,Tm@SiO2 Nanoprobes for Targeting Dual-Modality Imaging of Upconversion Luminescence and X-ray Computed Tomography

Jiebing Ma,Peng Huang,Meng He,Liyuan Pan,Zhijun Zhou,Lili Feng,Guo Gao,Daxiang Cui

Development of multimodal contrast agents for in vivo simultaneous multimodality imaging is an emerging interdiscipline that is paving the avenue toward the goal of personalized medicine. Herein, folic acid-conjugated silica-modified LaF3:Yb,Tm upconversion nanoparticles (UCNPs@SiO2-FA) with high La content in a single particle were strategically designed and prepared for simultaneously targeting dual-modality imaging of upconversion luminescence (UCL) and X-ray computed tomography (CT). LaF3 UCNPs were synthesized by a novel oleic acid (OA)/ionic liquid (IL) two-phase system. Afterward, a folic acid molecule was covalently anchored on the surface of UCNPs with a silane coupling agent. The UCNPs@SiO2-FA exhibits good stability, water dispersibility and solubility, low cytotoxicity, good biocompatibility, highly selective targeting, excellent X-ray attenuation, and UCL emission under excitation at 980 nm. In vivo UCL and CT images of mice show the UCNPs@SiO2-FA can be used in targeting dual-modality imaging. These results suggest that the as-prepared nanoprobe is a good candidate with excellent imaging and targeting ability for targeting dual-modality imaging of UCL and CT.

研究领域: 生物医学工程 · 纳米医学 · 分子影像学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2021 · IF 7.312

An innovative technique for the separation of ion-adsorption high yttrium rare earth ore by Er (III) / Tm (III) grouping first

Yaxing Han,Ji Chen,Yuefeng Deng,Tianchi Liu,Hailian Li,Deqian Li

The current separation technique of ion-adsorption high yttrium (Y) rare earth ore (high-yttrium ore) using 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (P507) and naphthenic acid (NA) has been confronted with low separation efficiency and high acid consumption. This is a consequence of the low selectivity and the difficulty of complete stripping of heavy rare earths (HREEs). Therefore, an innovative separation technique of high-yttrium ore was proposed. The leachate of high-yttrium ore was firstly divided into Erbium (Er) / Thulium (Tm) groups with P507-isooctanol followed by separating Y (III) from the high Y-enrichment of Er (III) group with sec -octylphenoxy acetic acid (CA12)-tri- n -butyl phosphate (TBP). The basic thermodynamics experiments and cascade extraction simulations were conducted to verify the feasibility of this technology. The results show that P507-15vol% isooctanol is superior to P507 in both stripping ability and separation selectivity of HREEs. The first cascade extraction for Er (III) / Tm (III) grouping with P507-15vol% isooctanol was simulated successfully, reducing acid consumption but obtaining high purity products. In theory, the second cascade extraction simulation designed for separating Y (III) with CA12-TBP could not only improve the separation ability between Y (III) and light rare earths (LREEs) but also shorten the extraction stages and reduce the production costs. All these results revealed that this two-step separation process probably provided a promising application prospect for separating high-yttrium ore.

研究领域: 冶金工程 · 稀土化学 · 分离科学与技术 · 资源加工工程 · 湿法冶金 · 萃取分离
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