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ACS Applied Materials & Interfaces · 2024 · IF 8.3

Enhancing Persistent Luminescence through Synergy between Optimal Electron Traps and Dye Sensitization

Zi-Jin Wei,Chang Yin,Mengjie Sun,Kai Long,Zhouyu Zhang,Zichao Yan,Wei Wang,Zhi Yuan

Due to their unique afterglow ability, long-wavelength-light rechargeable persistent luminescence (PersL) nanoparticles (PLNPs) have been emerging as an important category of imaging probes. Among them, ZnGa2O4:0.6% Cr3+ (ZGC) PLNPs have gained widespread recognition due to the ease of synthesis and uniform morphology. Unfortunately, the limited absorption arising from the low molar extinction coefficient of Cr3+ results in relatively low afterglow intensity and rapid decay after long-wavelength LED light irradiation. Herein, we discovered a strategy that boosting dye-sensitization performance was able to effectively amplify the PersL signal under white LED light. Specifically, Dil served as a highly efficient sensitizer for Cr3+, promoting the absorption of the excitation light. By adjusting the Pr dopant concentrations, ZGCP0.5 PLNPs with optimal trap densities were obtained, which showed the highest PersL intensity and dye-sensitized performance. Strikingly, ZGCP0.5-Dil PLNPs exhibited a 24.3-fold enhancement in intensity and a 2-fold prolongation of decay time over bare ZGC PLNPs through the synergy effect of optimal electron traps and dye sensitization. Photostable ZGCP0.5-Dil PLNPs enabled imaging of the HepG2 tumor and effectively guided tumor surgical resection verified by the H&E staining analysis. This strategy could be a significant reference in other dye-sensitization PLNPs to enhance longer-wavelength rechargeable PersL.

研究领域: 材料科学 · 生物医学工程 · 光学成像
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Materials Today Chemistry · 2024 · IF 6.7

Tailoring traps in Eu2+ activated persistent phosphors for multilevel information storage and encryption

Chaoyang Jia,Dangli Gao,Zhigang Wang,Xiangyu Zhang,Sining Yun,Jin Zhong Zhang,Xiaojun Wang

Persistent luminescence (PersL) phosphors, identified as ideal candidates, hold immense promise for information storage and encryption. However, practical storage and encryption technology using these phosphors remains uncommon due to their weak luminescence intensity and the inconvenience of light sources used in encryption and decryption processes. Here, we have developed Sr 2 MgSiGeO 7 :Eu 2+ ,Mn 2+ ,Dy 3+ phosphor with a super-long PersL beyond 100 h, the higher charge storage capacity and PersL efficiency (17 %) than commercial SrAl 2 O 4 :Eu,Dy phosphors by introduction of co-dopant Mn 2+ . This phosphor exhibits rapid and efficient charging capability when exposed to various light sources such as sunlight, light-emitting diode, mobile phone and computer screen. To explain the high charge storage capacity and super-long PersL, we propose a novel trap mechanism based on hole-electron defect pair trap structures. Notably, this phosphor as an anti-counterfeiting material demonstrates high-order encryption by the adding specific information writing process via temperature management. This study provides a new paradigm for future design of PersL phosphors and luminescent anti-counterfeiting.

研究领域: 材料科学 · 光学工程
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JOURNAL OF RARE EARTHS · 2025 · IF 7.2

Persistent scintillators for X-ray repetitive imaging with stable energy traps

Yuan Wang,Peng Zhang,Xu Tian,Daiyuan Liu,Jian Zhang,Zhichao Liu,Xiuxia Yang,Jie Yu,Jianxiong Shao,Xuhui Xu

Scintillator is a key material for the development of X-ray detectors, which has a promising application in medical imaging, security inspection and industrial non-injury detection. The majority of scintillators currently used in imaging are real-time imaging scintillators, which can cause ionization radiation damage to biological subjects or detection equipment during the imaging process and require complex, highly sensitive detection systems. Therefore, exploring stable, environmentally friendly scintillator materials that can achieve delayed imaging is of significance in the field of imaging. Herein, we developed an X-ray time-lapse imaging scintillator, Sr 2 Al 6 O 11 :Dy 3+ phosphor, which generates stable traps by X-ray irradiation, thus endowing it with excellent persistent luminescence and information storage properties (>42 d). Moreover, traps constructed by X-ray can be repeatedly refilled (>40 times) under UV light and carriers are released in the form of mechanical or thermal excitation when refilling is complete. By constructing the traps in the phosphor during X-ray excitation and using it for repetitive imaging, the detection limit is 74.78 nGy/s, and the spatial imaging resolution is as high as 16 lp/mm. This discovery provides a new idea for the development of time-delayed X-ray scintillator.

研究领域: 材料科学 · 医学影像 · 辐射检测
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CERAMICS INTERNATIONAL · 2024 · IF 5.1

Persistent luminescent NaYTi2O6: Cr activated in the near-infrared bio-imaging window as a self-luminescent ceramic coating for visible Ti-implant in vivo

Gulizhabaier Abulipizi,Yuxin Wang,Yanlun Fang,Yicheng Xu,Chaomin Qu,Ziang Zong,Leping Ding,Zimin Yu,Juanjuan Zhou,Zhanjun Li

Most of near-infrared (NIR) persistent luminescence (PersL) materials can only be activated by ultra violet-visible light illumination or X-ray irradiation, which hinders their advanced biomedical applications. Herein, NaYTi 2 O 6 : Cr, with a typical double-metal perovskite structure, is developed with ∼758 nm emission after being excited by 700 nm light within the NIR bio-imaging window. This NIR-to-NIR PersL property can be repeatedly charged by 700 nm NIR illumination in situ and in vivo . The anti-cite disorder of Na + -Y 3+ pair and relatively low bandgap of NaYTi 2 O 6 matrix are the vital factors of this property. NaYTi 2 O 6 : Cr has great potential to be applied as a functional ceramic coating in designing self-luminescent medical Ti-implants, so that it can be imaged in vivo by using NIR PersL imaging rather than conducting risky X-ray fluoroscopy imaging. This conceptual work not only provides a NIR-to-NIR PersL biomaterial but also is significant in designing visible medical implants.

CAS / MDL:
研究领域: 材料科学 · 生物医学工程 · 医学影像学
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NATURE · 2021 ·Vol. 590 ·期 7846 ·410-415 · IF 49.962

High-resolution X-ray luminescence extension imaging

Ou Xiangyu,Qin Xian,Huang Bolong,Zan Jie,Wu Qinxia,Hong Zhongzhu,Xie Lili,Bian Hongyu,Yi Zhigao,Chen Xiaofeng,Wu Yiming,Song Xiaorong,Li Juan,Chen Qiushui,Yang Huanghao,Liu Xiaogang

Current X-ray imaging technologies involving flat-panel detectors have difficulty in imaging three-dimensional objects because fabrication of large-area, flexible, silicon-based photodetectors on highly curved surfaces remains a challenge 1 , 2 , 3 . Here we demonstrate ultralong-lived X-ray trapping for flat-panel-free, high-resolution, three-dimensional imaging using a series of solution-processable, lanthanide-doped nanoscintillators. Corroborated by quantum mechanical simulations of defect formation and electronic structures, our experimental characterizations reveal that slow hopping of trapped electrons due to radiation-triggered anionic migration in host lattices can induce more than 30 days of persistent radioluminescence. We further demonstrate X-ray luminescence extension imaging with resolution greater than 20 line pairs per millimetre and optical memory longer than 15 days. These findings provide insight into mechanisms underlying X-ray energy conversion through enduring electron trapping and offer a paradigm to motivate future research in wearable X-ray detectors for patient-centred radiography and mammography, imaging-guided therapeutics, high-energy physics and deep learning in radiology.

CAS / MDL: 12036-41-8
研究领域: 医学影像学 · 材料科学 · 量子力学 · 放射学
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CHEMICAL ENGINEERING JOURNAL · 2020 · IF 10.652

Simultaneous realization of persistent luminescence and CT dual-mode imaging by x-ray recharged Bi2Ga4O9:Cr nanoprobes in depth-independent tumors

Li Jinlei,Guo Jiaqing,Li Hao,Qu Junle,Song Jun

Synthesis of excellent imaging nanoparticles plays a critical role in disease detection. Here, novel Bi 2 Ga 4 O 9 :Cr (BGOC) nanoparticles were synthesized for persistent luminescence and computed tomography dual-mode imaging. The Cr 3+ ions in the BGOC luminescent nanoparticles were coped as the luminescent center, and the afterglow emission was located in the first biological imaging window. Bi 3+ ions served as the computed tomography (CT) imaging contrast agent. The NH 2 groups were modified on the surface of the nanoparticles to make them highly biocompatible, and folic acid molecules were modified to facilitate the specificity. This modification facilitated simultaneous persistent luminescence and CT imaging in tumor-bearing mice due to the overexpression of the folic acid molecules’ receptors. Furthermore, instead of visible light, x-rays were used as the excitation light source to activate the BGOC-folic acid nanoprobes and realize long time and high sensitivity imaging of tumors in vivo because of their capacity for deep tissue penetration. Therefore, such nanoprobes can provide a promising depth-independent detection mode for high sensitivity diagnosis and long-term monitoring of diseases.

研究领域: 生物医学工程 · 影像医学
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ACS Applied Nano Materials · 2022 · IF 6.14

Long-Persistent Luminescence from Double Self-Defect States in Undoped Cs3In2Cl9 Nanocrystals for Bioimaging and Display Technologies

Shuang Yang,Wen-hui Guo,Zhenyu Tang,Zehao Zhang,Haoqing Guo,Yinan Lao,Bo Qu,Lixin Xiao,Jun-jie Shi,Zhijian Chen

A long-persistent luminescence (LPL) material based on lead-free perovskite nanocrystals (Cs3In2Cl9 NCs) was synthesized by hot injection at 175 °C. Based on X-ray diffraction and theoretical calculations, the crystal structure of Cs3In2Cl9 NCs belongs to the trigonal space group R3̅c. The Cs3In2Cl9 NC powder emits white light at a peak wavelength of 430 nm with a full width at half maximum (FWHM) of about 118 nm and a photoluminescence quantum yield (PLQY) of 26.3%. The lifetime of its LPL is ∼1 s at 300 K and ∼10 s at 77 K. To explain the mechanism of LPL in Cs3In2Cl9, double self-defect states (DSDS) were proposed. To the best of our knowledge, this is the first time to obtain LPL in undoped lead-free perovskites. It promotes the application of perovskites and the explanation of the mechanism of LPL.

研究领域: 材料科学 · 光学 · 纳米技术
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JOURNAL OF LUMINESCENCE · 2023 · IF 3.6

Enhanced persistent luminescence of MgGeO3: Yb3+ nanoparticles via substitution of Ge4+ by Ga3+ ions for biological applications

Yaling Lin,Jie Hu,Yongwei Guo,Qilin Zou,Dejian Chen,Kunyuan Xu,Sisi Liang,Xiaodong Yi,Hongyu Lu,Shi-Bin Wang,Haomiao Zhu

The emission of persistent luminescence nanoparticles (PLNPs) is in the second near infrared region (NIR-II, 1000–1700 nm), considered as ideal fluorescence imaging materials because of their special characteristic consist of no autofluorescence, weak scattering and deep tissue penetration depth in biological tissues. However, it is still a great challenge to enhance their persistent luminescence intensity. Herein, we reported a new MgGe 0.8 Ga 0.2 O 3 : Yb 3+ (MGGO: Yb 3+ ) PLNPs, which were synthesized through solvothermal liquid-solid-solution and salt microemulsion method. We found that partially replacing Ge 4+ with Ga 3+ ions in MgGeO 3 host can increase the density of traps, thus significantly improving the NIR-II persistent luminescence intensity of Yb 3+ ions (the decay time is more than 33 min). Moreover, X-ray could be used to repeatedly stimulate the NIR-II persistent emission of MGGO: Yb 3+ , which is pivotal for deep tissues long term imaging. The optical penetration length of Yb 3+ ions persistent luminescence was assessed to be 3.9 mm via capping tissue. The above results reveal that MGGO: Yb 3+ PLNPs are promising material to be applied to deep-tissue imaging field.

研究领域: 材料科学 · 生物医学工程 · 光学成像
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SENSORS AND ACTUATORS B-CHEMICAL · 2023 · IF 8.4

Dual-responsive persistent luminescence nanoflowers for glutathione detection and imaging

Xiang Chen,Haiyang Zhang,Xiaoye Liang,Lingling Li

Glutathione (GSH) is one of the important substances to maintain the redox balance in vivo, accurate monitoring of its changes is conducive to the early diagnosis and treatment of related diseases. Herein, we reported a two-in-one nanoflower-structured sensing platform (ZCGO@MnO 2 ) with luminescence resonance energy transfer (LRET) property and oxidase-like activity for dual-mode detection of GSH. The sensor consisted of persistent luminescence nanoparticles (PLNPs) with near-infrared emission and manganese dioxide (MnO 2 ) with luminescence quenching ability and oxidase-like activity. The addition of GSH could reduce MnO 2 to Mn 2+ , resulting in the recovery of persistent luminescence and inhibition of oxidase-like activity, then achieving persistent luminescence and colorimetric dual-mode signal outputs. The sensor utilized the persistent luminescence of PLNPs to eliminate the background interference of the complex biological matrix, improved the signal-to-noise ratio (S/N) of detection and took advantage of dual-mode sensing to improve the accuracy of detection, showing excellent analytical performance. Besides, the sensor was capable of monitoring changes in intracellular GSH levels through bioimaging . This work provides new ideas for the design of sensors in complex samples and broadens the application of PLNPs in the field of biosensing.

研究领域: 分析化学 · 生物医学工程 · 纳米科技
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Materials Chemistry Frontiers · 2020 ·Vol. 5 ·期 3 ·1468-1476 · IF 6.788

Infrared-photostimulable and long-persistent ultraviolet-emitting phosphor LiLuGeO4:Bi3+,Yb3+ for biophotonic applications

Hao Cai,Zhen Song,Quanlin Liu

Photodynamic therapy needing ultraviolet (UV) in deep tissue is hindered due to the low biological tissue penetration ability of UV light. Here, we demonstrate a persistent ultraviolet-emitting phosphor, LiLuGeO4:Bi3+,Yb3+, which can be re-stimulated by near infrared (NIR) light. Yb3+-doping significantly enhances the trap density without changing the thermoluminescence peak positions. The phosphor can be effectively activated by a 254 nm lamp and exhibits prominent persistent luminescence peaking at 350 nm. The decay time can be recorded much longer than 15 h. This phosphor exhibits simulated in vivo photostimulated persistent luminescence after a longtime decay by using in vitro NIR light penetrating biological tissue. Combined with CaAlSiN3:Eu2+, red persistent luminescence from Eu2+ is obtained. LiLuGeO4:Bi3+,Yb3+ makes up the shortage of excellent UVA persistent phosphors. It is expected to have potential applications as an in vivo renewable excitation source to trigger photosensitizers or fluorescent probes when used for biophotonic applications.

研究领域: 材料科学 · 生物光子学 · 医学
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Journal of Materials Chemistry C · 2021 ·Vol. 9 ·期 41 ·14730-14739 · IF 7.393

Development of ultraviolet-B long-lived persistent phosphors in Pr3+-doped garnets

Shao Yan,Yanjie Liang,Jingwei Liu,Dongxun Chen,Shihai Miao,Jianqiang Bi,Kangning Sun

Inorganic luminescent materials that emit in the ultraviolet-B (UVB) region (280–320 nm) have gained considerable attention in recent years because of the growing demands for applications in photochemistry and photomedicine. However, most of the available UVB phosphors are photoluminescent, for which continuous external excitation is essential. This common but very inconvenient luminescence form hinders the further development of UVB luminescence technology. Here, we report the design and development of a series of Pr3+-doped garnet-based UVB persistent phosphors by combining conduction band engineering, the vacuum referred binding energy (VRBE) diagram and persistent energy transfer control. The developed UVB persistent phosphors can not only be charged using a standard 254 nm UV lamp but also natural sunlight, leading to an intense and long-lasting UVB afterglow of more than 60 h. Besides, the persistent luminescence properties and trap charging and detrapping processes are comprehensively investigated using persistent luminescence excitation spectra and thermoluminescence experiments to uncover the possible luminescence mechanism in these phosphors. More importantly, the unique UVB persistent light emission from these garnet phosphors can be clearly imaged and recorded using a UVB camera in a bright indoor-lighting environment because of the zero-background noise from indoor ambient light, indicating that these UVB persistent phosphors have important application potential for optical tagging and optical data storage in a bright environment.

研究领域: 无机材料科学 · 光物理学 · 生物医学工程
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CERAMICS INTERNATIONAL · 2022 · IF 5.532

One-step construction of bifunctional nanoprobes for NIR afterglow and T2-weighted MR imaging

Yaqi Zhu,Jian Yang,Mingwei Wang,Yangqi Meng,Rongyun Jiang,Hancheng Zhu,Duanting Yan,Chunguang Liu,Changshan Xu,Yuxue Liu

In this study, spinel-phase Zn 2 Ga 3- x Fe 3+ x Ge 0.75 O 8 ( x  = 0, 0.002, 0.004, 0.02, 0.04, 0.08, 0.2) and Zn 2 Ga 2.98- x Fe 3+ x Cr 0.02 Ge 0.75 O 8 ( x  = 0, 0.0004, 0.001, 0.002 0.003, 0.004) nanoparticles were prepared by one-step hydrothermal method in combination with vacuum annealing. For ZGGO: Fe 3+ nanoparticles , the near infrared (NIR) emissions (∼725 nm) originate from the 4 T 1 ( 4 G)→ 6 A 1 ( 6 S) transition of Fe 3+ occupying octahedral and tetrahedral sites of Ga 3+ . Furthermore, their afterglow time is more than 15 min and Fe 3+ doping will influence the generation of antisite defects pair ( Ga Zn 0 − Zn Ga ′ GaZn0−ZnGa′ ). For Cr 3+ and Fe 3+ co-doped ZGGO nanoparticles with average size of ∼46 nm, the NIR persistent luminescence around ∼700 nm, originating from the 2 E→ 4 A 2 and 4 T 2 → 4 A 2 transitions of Cr 3+ , can be observed and the afterglow time exceeds 850 min. With the increase of Fe 3+ concentration, the afterglow intensity decreases due to the decreased number of ( Ga Zn 0 − Zn Ga ′ GaZn0−ZnGa′ ) defects and deeper traps. In particular, autofluorescence-free imaging and MR imaging were successfully realized by using ZGGO: Cr 3+ , Fe 3+ 0.002 nanoparticles dispersed in the simulated biological fluid environments (H 2 O, SLS and HSA). Their clear afterglow images can be acquired within 3 min after the stoppage of the UV irradiation and their transversal relaxivity (r 2 ) is in the range of 227–140 mM −1 s −1 , which is close to the conventional Feridex T 2 agent (108 mM −1 s −1 ). Our results suggest that ZGGO: Cr 3+ , Fe 3+ nanoprobes have potential applications in the diagnosis and therapy of disease.

研究领域: 材料科学 · 医学影像学 · 生物医学工程
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