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Journal of Materials Chemistry C · 2024 · IF 5.7

Achieving color-tunable luminescence in CaF2:Eu phosphors for multimode anti-counterfeiting

Linglu Kuang,Feng Zhang,Jian Zhang,Xiaodie Zhu,Xu Tian,Jianxiong Shao,Yichun Liu,Xuhui Xu,Zhichao Liu

Optical materials are widely used in the information coding, display, and anti-counterfeiting fields due to their tunable color. However, the regulation of the color change in a material is mainly achieved by co-doping with different ions to achieve multimode luminescence, which greatly increases the difficulty of material synthesis. Herein, CaF2:Eu with different doping amounts of Eu ions as an anti-counterfeiting material is synthesized in one step by a simple high-temperature solid-state method. The concentration of Eu can adjust the reduction ratio of Eu ions and give the material multicolor emission. Moreover, X-ray-induced ion reduction achieves the multicolor emission of Eu2+ and Eu3+ ions in a single matrix of CaF2:Eu. This achieves radio-photo luminescence (RPL). In addition, the mechano-luminescence (ML) of CaF2: 0.5%Eu has also been confirmed. These findings provide unique insights into the design of highly integrated advanced anti-counterfeiting technologies using multi-stimuli-responsive luminescent materials.

CAS / MDL: 7789-75-5 13765-25-8
研究领域: 光学材料 · 材料科学 · 防伪技术
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Frontiers in Chemistry · 2020 · IF 3.693

Luminescence in Manganese (II)-Doped SrZn2S2O Crystals From Multiple Energy Conversion

Ma Ronghua,Wang Chunfeng,Mao Shaohui,Shao Yonghong,Wang Zhihao,Wang Yu,Peng Dengfeng

Under the excitation of ultraviolet, X-ray, and mechanical stress, intense orange luminescence (Mn2+, 4T1 → 6A1) can be generated in Mn2+-doped SrZn2S2O crystal in orthorhombic space group of Pmn21. Herein, the multiple energy conversion in SrZn2S2O:Mn2+, that is, photoluminescence (PL), X-ray-induced luminescence, and mechanoluminescence, is investigated. Insight in luminescence mechanisms is gained by evaluating the Mn2+ concentration effects. Under the excitation of metal-to-ligand charge-transfer transition, the most intense PL is obtained. X-ray-induced luminescence shows similar features with PL excited by band edge UV absorption due to the same valence band to conduction band transition nature. Benefiting much from trap levels introduced by Mn2+ impurities, the quenching behavior mechanoluminescence is more like the directly excited PL from Mn2+ d-d transitions. Interestingly, this concentration preference leads to varying degrees of spectral redshift in each mode luminescence. Further, SrZn2S2O:Mn2+ exhibits a good linear response to the excitation power, which makes it potential candidates for applications in X-ray radiation detection and mechanical stress sensing.

研究领域: 材料科学 · 光学 · 物理学
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JOURNAL OF LUMINESCENCE · 2023 · IF 3.6

Enhanced X-ray-induced luminescence and afterglow of NaLuF4:Gd3+/Tb3+ nanoparticles with Ca2+ doping

Shaolian Sun,Shan Shao,Wuyang Fan,Wenhu Zhang,Fan Xu,Haoming Wei,Bingqiang Cao,Yangqing Wu

The synthesis of efficient nano-scintillators is of great significance for the development of X-ray imaging and other applications. Here, X-ray excited afterglow rare earth nanoparticles β-NaLuF 4 :Gd 3+ /Tb 3+ are investigated. The X-ray-induced luminescence intensity and afterglow duration of NaLuF 4 :Gd 3+ /Tb 3+ nanoparticles are effectively improved by Ca 2+ doping. The optimal luminescence and afterglow performance are achieved when Ca 2+ doping ratio reaches 10%. The change of crystal field symmetry is the main reason for the improvement of luminescence performance. According to the thermoluminescence curve, it is proved that Ca 2+ doping increases the trap concentration and further enhances the afterglow. This study provides the research basis for the application of persistent luminescence materials in biomedical and other fields.

CAS / MDL: 112-80-1 112-88-9
研究领域: 材料科学 · 医学影像 · 生物医学工程
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Optical Materials Express · 2024 ·Vol. 14 ·期 6 ·1531-1546 · IF 2.8

Dy-Al-Ce codoped silica: a promising yellow laser glass with enhanced resistance to X-ray-induced photodarkening

Zhenghao Li,Zhenghao Li,Xin Li,Yan Sun,Yan Sun,Chongyun Shao,Wei Chen,Wei Chen,Xin Wang,Chunlei Yu,Lili Hu,Malgorzata Guzik,Georges Boulon

To develop Dy doped silica glass with a higher irradiation resistance, which can be adapted to high power violet or blue LD pumped yellow laser fibers, the designed Dy-Al-Ce codoped silica glasses, 0.05Dy2O3-1.5Al2O3-xCe2O3-(98.45-x)SiO2 (x = 0, 0.05, 0.1, 0.25, 0.5), were prepared by the sol-gel method. Their excitation spectra, emission spectra and emission decay curves associated with the yellow emission from 4F9/2 to 6H13/2 of Dy were determined before and after the X-ray irradiation of 1000 Gy. The relation between these spectra and Ce-codoping concentrations is discussed, including the sensitization from Ce to Dy, the reverse energy transfer from Dy to Ce, and especially the X-ray-induced photodarkening, which is detrimental to the 576 nm yellow emission of Dy. The centers that cause the photodarkening are analyzed by electron paramagnetic resonance and radiation induced absorption spectra. It is found that Ce can effectively suppress the Al-oxygen hole center induced by the X-ray across the entire concentration range of Ce-codoping, but a new photodarkening center is generated at higher concentrations of Ce-codoping. Finally, the optimized Ce-codoping concentration of ∼0.1 mol% is used to achieve a promising yellow laser glass of Dy-Al-Ce codoped silica with enhanced irradiation resistance, resulting in its X-ray-induced photodarkening that is only 6% - 14% of that in the Ce-undoped.

研究领域: 光学材料 · 激光物理 · 辐射效应
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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

Metal-organic nanostructure based on TixOy/Ruthenium reaction Units: For CT/MR Imaging-Guided X-ray induced dynamic therapy

Dongsheng Li,Qixuan Dai,Hu Chen,Huirong Lin,Zhixiang Lu,Huili Zheng,Peng Lv,Wei Li,Gang Liu,Chengchao Chu

We report a computed tomography/magnetic resonance (CT/MR) imaging-guided X-ray induced dynamic therapy (XDT) nanotheranostic platform based on Ti x O y /Ru reaction units. A new metal–organic nanostructure (TiZrRu-MON) was prepared via a solvothermal reaction of [Ti 8 Zr 2 O 12 (COO) 16 ] clusters and bipyridine-(COOH) 2 /Ru(II)-bipyridine-(COOH) 2 co-organic ligands. We demonstrate that the cluster can absorb X-ray and transform the energy to Ru(II)-bipyridine-(COOH) 2 with effective reactive oxygen species (ROS) production, which is five times more than TiZr-MON. In addition, Gd(III) ions were anchored to the bipyridine of MON for concurrent CT/MR imaging. Notably, the TiZrRuGd-MON possesses ultrahigh longitudinal relaxivity ( r 1 value up to 53.09 mM −1 ·s −1 at 1.5 T, 7-fold higher than commercial Gd-DTPA). With the guidance of CT/MR dual-mode imaging that provides comprehensive and complementary contrast information, the TiZrRuGd-MON is monitored to accumulate in tumor sites and eliminate tumor with high efficiency under X-ray irradiation. The TiZrRu-MON-based XDT strategy opens a pathway for clinical translational research of cancer theranostics.

研究领域: 医学影像学 · 肿瘤学 · 纳米医学
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JOURNAL OF LUMINESCENCE · 2022 · IF 4.171

Enhanced X-ray-induced luminescence and persistent luminescence of NaLuF4:Tb3+ nanoparticles with Li+ and Gd3+ co-doped

Yangqing Wu,Mei Wang,Shaolian Sun,Shan Shao,Ziyu Pan,Jinkai Li,Haoming Wei,Bingqiang Cao

X-ray excitation photodynamic therapy is a new photodynamic therapy mode that induces tumor cell apoptosis by indirectly stimulating photosensitizer on nanoparticles with X-ray as excitation light source and generating singlet oxygen. It solves the problem of light penetration in traditional photodynamic therapy and realizes the treatment of deep tumors. At present, the weak X-ray-induced luminescence restricts further development of X-ray photodynamic therapy. NaLuF 4 :Li + /Gd 3+ /Tb 3+ rare-earth nanoparticles with uniform size and regular morphology were synthesized by solvothermal method . The X-ray-induced luminescence intensity of NaLuF 4 :Li + /Gd 3+ /Tb 3+ NPs was improved by Li + and Gd 3+ ions co-doping. The light yield of NaLuF 4 :Li + /Gd 3+ /Tb 3+ NPs with 5% Li + ions doping was 1.4 times than that of reference sample due to the change of crystal field symmetry. Furthermore, the effective lifetime of persistent luminescence increased from 221.5 s to 251.9 s after 15% Li + ions doping. The thermoluminescence curves confirmed that the trap concentration was increased after Li + ions doping, which was responsible for enhancing persistent luminescence lifetime . Long persistent luminescence emission laid a foundation for further application in photodynamic therapy.

CAS / MDL: 112-80-1 112-88-9
研究领域: 材料科学 · 医学 · 生物技术
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Inorganic Chemistry Frontiers · 2024 · IF 6.1

Synthesis of Lanthanide-based scintillator@MOF nanocomposites for X-ray-induced photodynamic therapy

Lantian Zhang,Fan Gao,Shiqi Liu,Mei Ju,Chao Sun,Gengzhi Sun,Qiang Ju,Kai Yang,Zhenlan Fang

Multifunctional nanocomposites comprising a set of diverse nanoparticles are highly desirable for realizing on-demand therapy with minimized adverse effects. X-ray-induced photodynamic therapy (X-PDT) has reformed conventional PDT for deep-seated tumor by utilizing penetrating X-rays, but its application faces the challenge of efficiently integrating scintillator with photosensitizer. To this end, core-shell nanocomposites rationally integrating NaGdF4: Tb@NaGdF4: Ce@NaLuF4 nanoparticles with Hf-porphyrin metal–organic frameworks (MOFs) by surface-assisted epitaxial-growth strategy, have been proposed and synthesized for X-PDT. Herein, NaGdF4: Tb@NaGdF4: Ce@NaLuF4 nanoparticles demonstrate strong X-ray attenuation coefficient and bright green light emission, serving as efficient scintillator to activate the photosensitizer. The porphyrin in MOFs can absorb and further be activated by the emission of lanthanide-based scintillator, playing the role of photosensitizer to generate a significant amount of singlet oxygen. Moreover, the uniform nanocomposites with regular core-shell structure enables the maximization of energy transfer between scintillator and MOFs, and inherent pores of MOFs facilitate the diffusion of reactive oxygen species (ROS) out of the MOF interior to boost PDT efficacy. Besides, the existence of heavy atoms such as Gd, Lu, and Hf can significantly enhance the radiation sensitization, facilitating the production of ROS. This work presents a novel strategy for fabricating lanthanide-based scintillator@MOFs nanocomposites for efficient X-PDT and is anticipated to promote the theranostic applications of nanocomposites.

CAS / MDL: 1078-61-1
研究领域: 生物医学工程 · 肿瘤治疗 · 纳米医学
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ACS Nano · 2022 · IF 18.027

Alternative Strategy to Optimize Cerium Oxide for Enhanced X-ray-Induced Photodynamic Therapy

Shikai Liu,Linyang Fang,He Ding,Yangyang Zhang,Wenting Li,Bin Liu,Shuming Dong,Boshi Tian,Lili Feng,Piaoping Yang

The emergence of X-ray-induced photodynamic therapy (X-PDT) holds tremendous promise for clinical deep-penetrating cancer therapy. However, the clinical application of X-PDT in cancer treatment is still limited due to the hypoxic property of cancerous tissue, the inherent antioxidant system of tumor cells, and the difficulty in matching the absorption spectra of photosensitizers. Herein, a versatile core–shell radiosensitizer (SCNPs@DMSN@CeOx-PEG, denoted as SSCP) was elaborately designed and constructed to enhance X-PDT by coating tunable mesoporous silica on nanoscintillators, followed by embedding the cerium oxide nanoparticles in situ. The obtained SSCP radiosensitizer demonstrated a distinct blue-shift in the ultraviolet light region, so that it could perfectly absorb the ultraviolet light converted by the SCNPs core, resulting in the formation of photoinduced electron–hole (e–-h+) pairs separation to generate reactive oxygen species (ROS). In addition, the cerium oxide exhibits high glutathione consumption to heighten ROS accumulation, and catalase-like activity to alleviate the hypoxia, which further enhances the efficiency of radiotherapy. Benefiting from the abundant Lu and Ce elements, the computed tomography imaging performance of SSCP is about 3.79-fold that of the clinical contrast agent (iohexol), which has great potential in both preclinical imaging and clinical translation.

研究领域: 癌症治疗 · 放射学 · 材料科学 · 纳米技术 · 医学成像
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Inorganic Chemistry Frontiers · 2025 · IF 6.4

Smart tri-mode imaging material for on-demand visual encryption and dynamic displays

Xue Yang,Yucheng Li,Yibo Hu,Meng Gu,Yanshuo Han,Guibin Zhai,Jingkun Chen,Naixin Li,Sihan Yang,Kuan Ren,Jingtai Zhao,Jianguo Chen,Yan Zhao,Xuyong Yang,Qianli Li

This study demonstrates the synergistic integration of X-ray-induced radioluminescence (RL), persistent luminescence (PersL) and radio-photoluminescence (RPL) in a single material system, which provides innovative multimodal applications for radiometric information sensing, storage and reading, anti-counterfeiting and imaging. A novel radiation-sensing material, BaMgP2O7:Sm, was prepared using a high temperature solid state method. Under X-ray irradiation, the pale pink phosphor shows distinct luminescence from defects. Under 365 nm ultraviolet (UV) light (bright-field), it emits bright red light, confirming trivalent samarium (Sm3+) reduction to divalent samarium (Sm2+). In dark-field, orange fluorescence appears, indicating defect-mediated charge storage and slow release. Notably, the material enables single-irradiation multiple imaging, effectively overcoming the limitation of conventional materials that only allow single imaging per irradiation event, thereby greatly enhancing information utilization and imaging flexibility. Moreover, the flexible film based on polydimethylsiloxane (BaMgP2O7:Sm@PDMS) demonstrates remarkable tri-mode X-ray detection and imaging capabilities, it has a high spatial resolution of 14.4 lp mm−1, integrating real-time readout, delayed readout, and long-term information storage. BaMgP2O7:Sm enables dynamic anti-counterfeiting via time-dependent luminescence and precise radiation dose monitoring through X-ray responsive emission, these features make it a promising multifunctional material.

CAS / MDL: 12047-27-7
研究领域: 材料科学 · 生物医学工程 · 影像学 · 辐射探测 · 功能材料 · 分子影像
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ACS Nano · 2021 · IF 15.881

Antiangiogenesis Combined with Inhibition of the Hypoxia Pathway Facilitates Low-Dose, X-ray-Induced Photodynamic Therapy

Zhao Jiang,Liangrui He,Xujiang Yu,Zhiwen Yang,Weijie Wu,Xiaoyan Wang,Rihua Mao,Daxiang Cui,Xiaoyuan Chen,Wanwan Li

X-ray-induced photodynamic therapy (XPDT) is overwhelmingly superior in treating deep-seated cancers. However, limitations remain, owing to a combination of the poor scintillation performance of the nanoscintillator, low energy transfer efficiency of the therapeutic nanoplatform, and hypoxic environment presented in the tumor tissue. Collectively, these reduce the curative effect of XPDT. Here, we report a highly efficient, low-dose XPDT realized by systematic optimization from scintillation efficiency, nanoplatform structure, to therapeutic approach. We developed a biocompatible, codoped CaF2 nanoscintillator that emitted sufficiently green radioluminescence that was bright enough to be seen by the naked eye. Using dendrimers as a framework, we built a nanoplatform featuring a dual-core–satellite architecture, which enabled both procedurally and spatially separate dual-loading of therapeutic agents. This strategy allowed for the fabrication of a combined XPDT and antiangiogenic therapy, resulting in a therapeutic system capable of simultaneous tumor attacks. After exposure to ultralow dose radiation, XPDT resulted in marked tumor reduction while the antiangiogenic drug effectively blocked tumor vascularization exacerbated by XPDT-mediated hypoxia, rendering a pronounced synergy effect. This system also showed high biosafety, as the agents adopted had been used clinically and both Ca and F elements were widespread in the human body. Taken together, the findings presented here provided a reference for the construction of complex, multiloading architecture in coordination with structural complexity and functional diversification. This work provided a safer and more robust application of the combined XPDT and antiangiogenesis in future clinical treatment settings.

CAS / MDL: 9004-74-4 2258654-78-1
研究领域: 癌症研究 · 放射肿瘤学 · 纳米技术 · 生物医学工程 · 治疗策略
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Nanoscale · 2022 ·Vol. 14 ·期 13 ·5054-5067 · IF 8.307

Rational design of ROS-responsive nanocarriers for targeted X-ray-induced photodynamic therapy and cascaded chemotherapy of intracranial glioblastoma

Beibei Zhang,Rui Xue,Chunyang Sun

Glioblastoma (GBM) is the most lethal primary intracranial tumor because of its high invasiveness and recurrence. Therefore, nanocarriers with blood–brain barrier (BBB) penetration and transcranial-controlled drug release and activation are rather attractive options for glioblastoma treatment. Herein, we designed a multifunctional nanocarrier (T-TKNPVP) that combined targeted X-ray-induced photodynamic therapy (X-PDT) and cascaded reactive oxygen species (ROS)-boosted chemotherapy. The T-TKNPVP loaded with verteporfin (VP) and paclitaxel (PTX) was self-assembled from an angiopep-2 (Ang) peptide, functionalized Ang-PEG-DSPE and ROS-sensitive PEG-TK-PTX conjugate. After systemic injection, the T-TKNPVP efficiently crossed the BBB and targeted the GBM cells via receptor-mediated transcytosis. Upon X-ray irradiation, they can generate a certain amount of ROS, which not only induces X-PDT but also locoregionally activates PTX release and action by cleaving the TK bridged bonds. As evidenced by 9.4 T MRI and other experiments, such nanocarriers offer significant growth inhibition of GBM in situ and prolong the survival times of U87-MG tumor-bearing mice. Taken together, the designed T-TKNPVP provided an alternative avenue for realizing transcranial X-PDT and X-ray-activated chemotherapy for targeted and locoregional GBM treatment in vivo.

研究领域: 癌症治疗 · 纳米技术 · 神经科学 · 药学 · 放射学
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