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Materials Today Chemistry · 2024 · IF 6.7

A multi-dimensional anti-counterfeiting nanocomposite based on fluorescent CDs and Eu-MOFs with dual function for continuous detection of Cu2+ and Bacillus anthracis

Jian Gou,Yousong Hu,Luxin Xing,Jun Xu,Fengzhi Yue,Lina Zhang,Lei Jia

Traditional luminescent materials for anti-counterfeiting usually adopt encryption of low-level systems with limited security, which seriously hinders their application in preventing counterfeiting and information leakage. Therefore, it is urgent to develop materials for higher-level anti-counterfeiting. In this work, a stimulus-responsive intelligent luminescent material (AC@CDs-Eu-MOFs) was prepared by co-loading green-fluorescence CDs and red-fluorescence Eu-MOFs on Amino clay (AC). 5D security barcodes, which were easy to observe while difficult to clone, were ulteriorly designed based on the nanocomposite owing to the tunable fluorescence by optical stimulation and chemical stimulus. Owing to the large capacity, low cost, and easy authentication, the 5D security barcodes possess enormous potential in optical data storage and multi-dimensional information encryption. In addition, the chemical stimulus-response enables the nanocomposite achievable in detection of Cu 2+ and Bacillus anthracis. Particularly, quantitative determination of copper in environmental water samples could be realized with a detection limit as low as 10.67 nM. Therefore, the material shows potential for detection of environmental pollutants besides advanced anti-counterfeiting.

CAS / MDL: 919-30-2
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2024 · IF 9.4

Novel multi-mode anti-counterfeiting encryption material of CaAl12O19:Eu, Er with multi-color down-conversion luminescence, up-conversion luminescence, dynamic luminescence, and photochromism

Xiaoping Jiang,Yue Guo,Lixi Wang,Qitu Zhang

Multi-mode dynamic anti-counterfeiting materials can provide complex anti-counterfeiting performance and ensure the anti-counterfeiting strategy becomes more secure. Herein, a new type of multi-mode anti-counterfeiting encryption material of CaAl 12 O 19 :Eu, Er with different Er doping concentration was developed by sol–gel method. Interestingly, the CaAl 12 O 19 :Eu, Er phosphor and its composite have multi-mode anti-counterfeiting characteristics of multi-color down-conversion luminescence, up-conversion luminescence, dynamic luminescence, and photochromism. Effect of different Er doping concentration on the down-conversion luminescence, up-conversion luminescence, dynamic luminescence, and photochromism of CaAl 12 O 19 :Eu, Er was systematically investigated, and the relevant mechanisms were discussed. These anti-counterfeiting features can be simultaneously applied in both bright and dark fields, which can achieve high-level anti-counterfeiting in both spatial and temporal dimensions. The CaAl 12 O 19 :Eu, Er phosphors cannot be easily replaced by other materials with the same anti-counterfeiting properties. They display good application foreground in the field of anti-counterfeiting encryption.

CAS / MDL: 5949-29-1
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Materials Science & Engineering C-Materials for Biological Applications · 2018 · IF 5.08

Surface grafting of rare-earth ions doped hydroxyapatite nanorods (HAp:Ln(Eu/Tb)) with hydrophilic copolymers based on ligand exchange reaction: Biological imaging and cancer treatment

Chunning Heng,Xin Zhou,Xiaoyan Zheng,Meiying Liu,Yuanqing Wen,Hongye Huang,Daidi Fan,Junfeng Hui,Xiaoyong Zhang,Yen Wei

Rare-earth ions doped hydroxyapatite nanoparticles (HAp:Ln NPs) have demonstrated to be very promising candidates for biological imaging applications owing to their small size and chemical compositions similar to bone. However, these HAp:Ln NPs with controllable size and morphology should be prepared under hydrothermal treatment with hydrophobic molecules as the protective layers. The hydrophobic nature of these luminescent HAp:Ln NPs largely impeded their applications in biomedical fields. In this study, a novel and effective strategy has been developed for the surface modification of HAp:Ln nanorods through the combination of surface ligand exchange reaction and reversible-addition fragmentation chain transfer (RAFT) polymerization using 2-methacryloyloxyethyl phosphorylcholine (MPC) and itaconic acid (IA) as the monomers. Herein, a small molecule adenosine 5′-monophosphate disodium salt (AMP) that contains a phosphate group and two hydroxyl groups was used to displace the hydrophobic oleic acid on pristine HAp NPs through surface ligand exchange reaction owing to its stronger interaction with HAp NPs. On the other hand, the MPC and IA were introduced on HAp NPs through RAFT polymerization after the chain transfer agent was immobilized on the HAp NPs through the esterification reaction. The poly(IA-MPC) could not only endow the high water dispersibility but also be used for loading anticancer agent cisplatin (CDDP) through coordination interaction. To evaluate their potential biomedical applications, the cell uptake behavior, drug loading capacity and release behavior as well as cell viability of HAp:Ln-AMP-poly(IA-MPC) polymeric composites were examined. We demonstrated that the method developed in this work is very effective for introduction of functional polymers onto HAp:Ln nanorods. The HAp:Ln-AMP-poly(IA-MPC) composites are promising for cell imaging and controlled delivery of CDDP.

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ADVANCED FUNCTIONAL MATERIALS · 2024 · IF 18.5

A“Duet-Insurance” Sensing Strategy by Combining Janus TpMa COF/Eu-doped α-Fe2O3 and Variable-Temperature Excitation for Robust, Visual Indoor Pollution Gas Detection

Yu Bing,Zhao Song,Hongtao Jiang,Xiaoyi Xu,Zhongzheng Yu,Tingting Zhou,Tong Zhang

Water competitive adsorption and limited reaction sites on the micro-scale sensing area of micro-electro-mechanical system (MEMS) sensors are two bottleneck problems that restrict the detection of trace indoor polluted gases, leading to drifting and weak signals. To address this, a “duet-insurance” sensing strategy is proposed to protect and amplify the sensing signal. For the first-level protection, the well-designed double-layer structure consisting of Janus TpMa covalent organic framework (COF)/Eu-doped α-Fe 2 O 3 can resist diffusion of water molecules and facilitate the electron transfer from formaldehyde (CH 2 O) to sensing layers, benefiting from the outer hydrophobic character of Janus TpMa and the strong CH 2 O adsorption capacity of Eu-doped Fe 2 O 3 . For the second-level amplification, the unique variable temperature excitation facilitates the deep penetration of CH 2 O into the active sites across COF layers, enabling signal amplification through thermally actuated carrier modulation. The sensor demonstrates high sensing ability to the CH 2 O, with an ultra-low limit of detection of 794 ppt. Leveraging the novel sensing strategy, a multi-functional, visual sensing system is designed to identify multi-indoor pollution gases by feature signal encoding and color mapping, showcasing the promising potential for MEMS sensors based on Janus TpMa COF/Eu-doped α-Fe 2 O 3 materials.

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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Diglycolamide with long C-chains combined with ether bonds for high loading of Am(III) and Eu(III): Extraction, aggregation, and third-phase formation studies

Xiaoyang Hu,Haowei Xu,Zhuang Wang,Qiao Yu,Xuanhao Huang,Xingyue Liu,Qiang Tian,Songdong Ding

Diglycolamide (DGA) extractants, especially TODGA ( N , N , N′ , N′ ‐tetraoctyl diglycolamide), show significant potential in high-level liquid waste treatment. However, their limited loading capacity for trivalent lanthanides (Lns) and actinides (Ans) often leads to detrimental emulsification or third phase formation, hindering their practical applicability. Herein, TOOEDGA ( N , N , N’ , N’ -tetra(2-(octyloxy)ethyl)diglycolamide), a new DGA extractant with long C-chains combined with ether bonds, exhibits superior extraction performance towards Am 3+ and Eu 3+ in HNO 3 solution compared to TODGA. The factors influencing the formation of a third phase during the extraction process were investigated. It has been shown that TOOEDGA has a greater loading capacity for Lns 3+ and can tolerate a wider concentration range of HNO 3 . Additionally, the aggregation behavior of DGAs in n -dodecane was also studied using dynamic light scattering and small-angle X-ray scattering, revealing that the reverse micelles formed by TOOEDGA are more stable than those formed by TODGA. Moreover, under similar conditions, TOOEDGA molecules do not aggregate further to generate rod-like reverse micelle aggregates like those observed with TODGA, which is beneficial to inhibit the formation of the third phase. Consequently, our results suggest that TOOEDGA holds great promise as an alternative DGA extractant for practical industrial applications.

CAS / MDL: 13746-96-8 10361-93-0
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2019 ·Vol. 411 ·期 7 ·1453-1465 · IF 3.286

Simultaneous detection of fumonisin B1 and ochratoxin A using dual-color, time-resolved luminescent nanoparticles (NaYF4: Ce, Tb and NH2-Eu/DPA@SiO2) as labels

Niazi Sobia,Khan Imran Mahmood,Yan Lv,Khan Muhammad Issa,Mohsin Ali,Duan Nuo,Wu Shijia,Wang Zhouping

A rapid and highly sensitive time-resolved fluorescence (TRF)-based aptasensor for simultaneous recognition of mycotoxins ochratoxin A (OTA) and fumonisin B 1 (FB 1 ) was developed using multi-color, Ln 3+ -doped time-resolved fluorescence nanoparticles (TRF-NPs) (NaYF 4 : Ce, Tb and NH 2 -Eu/DPA@SiO 2 NPs) coupled with complementary strand DNA (cDNA) as luminescence probe and aptamers-conjugated amine-functionalized Fe 3 O 4 magnetic nanoparticles (MNPs) act as a capture probe. Under the optimized conditions, the time-resolved fluorescence intensities at 544 and 618 nm corresponded with Tb 3+ and Eu 3+ , respectively, were used to measure FB 1 ( Y  = 19,177.1 + (− 12,054.4) x , R 2  = 0.9917) and OTA ( Y  = 4138.8 + (− 11,182.6) x , R 2  = 0.9924), respectively. The limits of detection (LODs) for FB 1 and OTA were 0.019 pg mL −1 and 0.015 pg mL −1 , respectively, which were much lower than previously described methods for simultaneous recognition of mycotoxins OTA and FB 1 while detection range varied from 0.0001–0.5 ng mL −1 . This aptasensor was effectively applied to quantity FB 1 and OTA in maize samples and results were compared with ELISA method. This is the first reported time-resolved fluorescence (TRF)-based aptasensor to detect two agriculturally important toxins in the maize. The developed aptasensor has potential to be used for detection of toxins in food safety fields. Graphical abstract

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JOURNAL OF SOLID STATE CHEMISTRY · 2025 · IF 3.5

Electrical Properties and High-Temperature Stability of High-Entropy Pyrochlore Ceramics (La0.2Nd0.2Sm0.2Gd0.2M0.2)2Sn2O7 (M = Eu, Dy, Ho, or Yb) for Negative Temperature Coefficient Thermistor Applications

Xiaohui Li,Pengjun Zhao,Wenwen Kong,Aimin Chang,Bo Gao

Understanding electrical transport mechanisms and key thermal stability factors in high-temperature thermosensitive ceramics is essential for developing highly stable temperature sensors under extreme thermal conditions. This study develops the high-entropy pyrochlore stannates (La 0.2 Nd 0.2 Sm 0.2 Gd 0.2 M 0.2 ) 2 Sn 2 O 7 (M = Eu, Dy, Ho, or Yb) via solid-state synthesis, demonstrating exceptional negative temperature coefficient (NTC) behavior across 300 – 1400 °C. Hall measurements and X-ray photoelectron spectroscopy (XPS) analyses reveal a dual redox mechanism for these ceramics: partial reduction of Sn 4+ to Sn 2+ at B-sites and rare-earth ions (Sm/Eu/Yb) to RE 2+ at A-sites, generating hole-dominated p-type conductivity. The materials exhibit outstanding thermal stability, with resistance drift below 1.96% after 500 hours at 1400 °C, attributed to the entropy-stabilized structure that effectively suppresses lattice disorder transformation. Aging studies further demonstrate that high oxygen vacancy concentrations lead to resistance drifts, as oxygen filling at elevated temperatures oxidizes RE 2+ to RE 3+ , reducing charge carriers and ultimately increasing resistivity. This study elucidates for the first time the hole-dominated conduction mechanism arising from dual-site cation valence changes (Sn/RE) and the regulation effect of oxygen vacancies on high-temperature stability, which provides an important theoretical basis and material design strategy for the development of the next-generation high-temperature NTC sensors with excellent stability.

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International Journal of Minerals Metallurgy and Materials · 2024 ·Vol. 31 ·期 7 ·1651-1658 · IF 5.6

Porous high-entropy rare-earth phosphate (REPO4, RE = La, Sm, Eu, Ce, Pr and Gd) ceramics with excellent thermal insulation performance via pore structure tailoring

Zhang Peixiong,Wang Enhui,Liu Jingjing,Yang Tao,Wang Hailong,Hou Xinmei

Thermal insulation materials play an increasingly important role in protecting mechanical parts functioning at high temperatures. In this study, a new porous high-entropy (La 1/6 Ce 1/6 Pr 1/6 Sm 1/6 Eu 1/6 Gd 1/6 )PO 4 (HE (6RE 1/6 )PO 4 ) ceramics was prepared by combining the high-entropy method with the pore-forming agent method and the effect of different starch contents (0–60vol%) on this ceramic properties was systematically investigated. The results show that the porous HE (6RE 1/6 )PO 4 ceramics with 60vol% starch exhibit the lowest thermal conductivity of 0.061 W·m −1 ·K −1 at room temperature and good pore structure stability with a linear shrinkage of approximately 1.67%. Moreover, the effect of large regular spherical pores (>10 µm) on its thermal insulation performance was discussed, and an optimal thermal conductivity prediction model was screened. The superior properties of the prepared porous HE (6RE 1/6 )PO 4 ceramics allow them to be promising insulation materials in the future.

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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2023 · IF 4.4

Discrimination of Chinese green tea according to tea polyphenols using fluorescence sensor array based on Tb (III) and Eu (III) doped Zr (IV) metal–organic frameworks

Chengxiang Chu,Xianfeng Wang,Yuanyi Deng,Yi Ma,Chengyue Zou,Mei Yang,Huibo Luo,Danqun Huo,Changjun Hou

A facile and rapid fluorescence sensor array based on Tb (III) and Eu (III) doped Zr (IV) metal–organic frameworks was proposed for Chinese green tea discrimination. According to large porosity of Tb@UiO-66-(COOH) 2 and Eu@UiO-66-(COOH) 2 , phenolic hydroxyl groups of tea polyphenols could coordinate with free carboxylic acid groups and was captured into the pores, which led to the disturbance of electronic structure of ligand and inhibited the energy transfer efficiency from ligand to Tb (III) and Eu (III) center, causing the fluorescence quenching effect. Based on Hierarchy Cluster Analysis and Linear Discrimination Analysis, the fluorescence sensor array was employed for successful tea polyphenols classification through the analysis of different fluorescence quenching effect to tea polyphenols. Green tea samples within different categories and grades were also successfully discriminated using this assay according to tea polyphenols, providing a new method for Chinese green tea identification.

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JOURNAL OF ALLOYS AND COMPOUNDS · 2023 · IF 6.2

Synthesis and luminescent properties of Eu(III)/Tb(III) rare earth complex-coated the core-shell structured silica microspheres: Unleashing the potential for white light emission

Jinrong Gao,He Bai,Xiao Ling,Yunjiang Yang,Xinru Liu,Zhipeng Fan,Jinrong Bao,Wenxian Li,Ying Liu,Xiaowei Zhu

A rare earth organic complex, SiO 2 @ATPA-Si-RE (RE = Eu, Tb), exhibiting a core-shell structure, was synthesized using the ligand (HOOC) 2 C 6 H 3 NHCONH(CH 2 ) 3 Si(OCH 2 CH 3 ) 3 (ATPA-Si) to connect the silica microspheres core and coordinate with rare earth ions. The pH value of the reaction was adjusted to produce organic complex shells with thicknesses of 2.0 nm and 5.0 nm, while the SiO 2 core measured a diameter of 125 nm. Luminescence spectra indicated that the emission intensity of the SiO 2 @ATPA-Si-RE (RE = Eu, Tb) core-shell structure was stronger than that of the ATPA-Si-RE organic complex due to a perfect match between the triplet energy level of SiO 2 @ATPA-Si and the excited energy level of rare earth ions (Eu 3+ , Tb 3+ ). Remarkably, the core-shell structure with a 2.0 nm shell thickness possessed a greater emission intensity compared to the 5.0 nm shell thickness. Moreover, these findings unveiled the tunability of luminescence color, ranging from green or red to white, by adjusting the doping ratio of Eu 3+ and Tb 3+ ions and the coating thickness of complexes. Particularly, a warm white light emission, characterized by CIE coordinates (0.389, 0.347), a color rendering index value of 86.7, and a low correlated color temperature value of 3550 K, was achieved using the organic complex with a 2.0 nm thickness coated on SiO 2 microspheres with a doping ratio of Eu 3+ at 0.7 mmol and Tb 3+ at 0.3 mmol. Conversely, the complexes with a 5.0 nm coating thickness and Tb 3+ doping ratio of 0.3 mmol yielded a cold white light emission. These findings demonstrate the potential applications in next-generation lighting industry and display systems.

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INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES · 2015 ·Vol. 16 ·期 7 ·14464-14476 · IF 2.862

Evaluation of the Interactions between Water Extractable Soil Organic Matter and Metal Cations (Cu(II), Eu(III)) Using Excitation-Emission Matrix Combined with Parallel Factor Analysis

Jing Wei,Lu Han,Jing Song,Mengfang Chen

The objectives of this study were to evaluate the binding behavior of Cu(II) and Eu(III) with water extractable organic matter (WEOM) in soil, and assess the competitive effect of the cations. Excitation-emission matrix (EEM) fluorescence spectrometry was used in combination with parallel factor analysis (PARAFAC) to obtain four WEOM components: fulvic-like, humic-like, microbial degraded humic-like, and protein-like substances. Fluorescence titration experiments were performed to obtain the binding parameters of PARAFAC-derived components with Cu(II) and Eu(III). The conditional complexation stability constants (logKM) of Cu(II) with the four components ranged from 5.49 to 5.94, and the Eu(III) logKMvalues were between 5.26 to 5.81. The component-specific binding parameters obtained from competitive binding experiments revealed that Cu(II) and Eu(III) competed for the same binding sites on the WEOM components. These results would help understand the molecular binding mechanisms of Cu(II) and Eu(III) with WEOM in soil environment.Keywords:water extractable organic matter;copper;europium;excitation-emission matrix;parallel factor analysis

CAS / MDL: 10031-53-5
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INORGANIC CHEMISTRY · 2024 · IF 4.3

Amine-Terminated Phenanthroline Diimides as Aqueous Masking Agents for Am(III)/Eu(III) Separation: An Alternative Ligand Design Strategy for Water-Soluble Lanthanide/Actinide Chelating Ligands

Hong Cao,Yu Kang,Bin Li,Yaoyang Liu,Mingjie Bao,Haoyu Li,Yuan Zheng,Ludi Wang,Chaoqun Weng,Xiaoyan Tang,Li Wang,Chao Xu

Selective actinide coordination (from lanthanides) is critical for both nuclear waste management and sustainable development of nuclear power. Hydrophilic ligands used as masking agents to withhold actinides in the aqueous phase are currently highly pursued, while synthetic accessibility, water solubility, acid resistance, and extraction capability are the remaining problems. Most reported hydrophilic ligands are only effective at low acidity. We recently proved that the phenanthroline diimide skeleton was an efficient building block for the construction of highly efficient acid-resistant hydrophilic lanthanide/actinide separation agents, while the limited water solubility hindered the loading capability of the ligand. Herein, amine was introduced as the terminal solubilizing group onto the phenanthroline diimide backbone, which after protonation in acid showed high water solubility. The positively charged terminal amines enhanced the ligand water solubility to a large extent, which, on the other side, was believed to be detrimental for the coordination and complexation of the metal cations. We showed that by delicately adjusting the alkyl chain spacing, this intuitive disadvantage could be relieved and superior extraction performances could be achieved. This work holds significance for both hydrophilic lanthanide/actinide separation ligand design and, concurrently, offers insights into the development of water-soluble lanthanide/actinide complexes for biomedical and bioimaging applications.

CAS / MDL: 10031-53-5
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