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RSC Advances · 2017 ·Vol. 7 ·期 60 ·37929-37937 · IF 3.108

Core@shell Fe3O4@Mn2+-doped NaYF4:Yb/Tm nanoparticles for triple-modality T1/T2-weighted MRI and NIR-to-NIR upconversion luminescence imaging agents

Yang Luo,Sinan Du,Wei Zhang,Zhengfang Liao,Fang Zuo,Shengtao Yang

Core@shell structures of Fe3O4@Mn2+-doped NaYF4:Yb/Tm nanoparticles (NPs) with multifunctional properties were prepared using a hydrothermal route with a seed-growth procedure. The effect of Mn2+ ions on the phase, shape, and upconversion luminescence (UCL) of Fe3O4@Mn2+-doped NaYF4:Yb/Tm NPs was explored using X-ray diffraction, transmission electron microscopy, dynamic light scattering, and photoluminescence spectroscopy. Furthermore, hydrophobic to hydrophilic surface modification of the Fe3O4@Mn2+-doped NaYF4:Yb/Tm NPs was achieved by coating the NPs with an amphiphilic polymer (poly(maleic anhydride-alt-1-octadecene) (C18PMH)) modified with amine-functionalized methyl ether poly(ethylene glycol). Then, the NIR-to-NIR UCL ascribed to the Tm3+ ions, T1-weighted MRI ascribed to the Mn2+ ions, and T2-weighted MRI ascribed to the Fe3O4 core of the hydrophilic Fe3O4@Mn2+-doped NaYF4:Yb/Tm NPs were evaluated. The results indicate that Mn2+ doping is an effective method to control the size/shape and improve the UCL intensity of Fe3O4@Mn2+-doped NaYF4:Yb/Tm NPs, which are promising as imaging agents for NIR-to-NIR UCL and T1/T2-weighted MRI in biomedical research.

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APPLIED SURFACE SCIENCE · 2016 · IF 3.15

Hydrothermal synthesis of superparamagnetic and red luminescent bifunctional Fe3O4@Mn2+-doped NaYF4:Yb/Er core@shell monodisperse nanoparticles and their subsequent ligand exchange in water

Zhenli Qin,Sinan Du,Yang Luo,Zhijian Liao,Fang Zuo,Jianbin Luo,Dong Liu

We report the use of an efficient hydrothermal method to synthesize superparamagnetic and red luminescent bifunctional Fe 3 O 4 @Mn 2+ -doped NaYF 4 :Yb/Er nanoparticles (NPs) with core@shell structures via a seed-growth procedure. Oleic acid coated Fe 3 O 4 (OA-Fe 3 O 4 ) NPs were initially synthesized using a coprecipitation method. The as-synthesized OA-Fe 3 O 4 NPs were then used as seeds, on which the red upconversion luminescent shell (Mn 2+ -doped NaYF 4 :Yb/Er) was formed. Furthermore, hydrophobic to hydrophilic surface modification of the Fe 3 O 4 @Mn 2+ -doped NaYF 4 :Yb/Er NPs was achieved via a ligand exchange method where oleic acid was displaced by a PEG phosphate ligand [PEG   =   poly(ethylene glycol)]. These materials were characterized by means of transmission electron microscopy (TEM), X-ray diffraction (XRD), photoluminescence (PL) spectroscopy, and vibrating sample magnetometry (VSM). The Fe 3 O 4 cores were uniformly coated with a Mn 2+ -doped NaYF 4 :Yb/Er shell, and the bifunctional Fe 3 O 4 @Mn 2+ -doped NaYF 4 :Yb/Er NPs were monodispersed. Furthermore, the Fe 3 O 4 @Mn 2+ -doped NaYF 4 :Yb/Er NPs exhibited a saturated magnetization value of 6.2 emu/g and emitted red luminescence under a 980   nm laser. The obtained bifunctional Fe 3 O 4 @Mn 2+ -doped NaYF 4 :Yb/Er NPs may find potential applications in drug targeting, bioseparation, and diagnostic analysis. The synthetic method may be employed for the preparation of other bifunctional nanomaterials.

CAS / MDL: 9004-74-4 2258654-78-1
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SEPARATION AND PURIFICATION TECHNOLOGY · 2021 · IF 7.312

Preparation of EDTA modified chitooligosaccharide/sodium alginate/Ca2+ physical double network hydrogel by using of high-salinity oilfield produced water for adsorption of Zn2+, Ni2+ and Mn2+

Haoyu Yue,Zhijie Shang,Pan Xu,Dongyue Feng,Xinxue Li

A novel EDTA functionalized chitooligosaccharide/sodium alginate/Ca 2+ physical double network hydrogel (ECSDNH) was prepared by using of high-salinity oilfield produced water. The formation and structure of ECSDNH were characterized by FT-IR and SEM. Various factors, including EDTA functionalized chitooligosaccharide content, pH of solution, initial concentration of heavy metal ions, temperature and contact time, were thoroughly investigated to explore their effect on adsorption capacity of ECSDNH. The obtained results showed that ECSDNH had higher adsorption capacity for Zn 2+ , Ni 2+ and Mn 2+ . The maximum adsorption capacities of Zn 2+ , Ni 2+ and Mn 2+ were 160.19 mg/g, 72.67 mg/g and 52.43 mg/g at 298 K, respectively. The pseudo-second-order kinetic model and Langmuir isotherm model fit the experimental data fairly well. The thermodynamic parameters of the adsorption, Δ H ° , Δ S ° , and Δ G ° , were also calculated. In addition, the ECSDNH still had higher removal efficiency for three metal ions after three adsorption-regeneration cycles, indicating its potential application for removing heavy metal ions from wastewater.

CAS / MDL: 7320-34-5 10039-32-4
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MICROCHEMICAL JOURNAL · 2026 · IF 5.2

A Mn2+-gated conformational switch-activated fluorescent biosensor for Mucin-1 detection based on a 3D porous Fe3O4@ZIF-90 interface and DNAzyme walker-mediated CRISPR-Cas13a cascade

Lingsong Lu,Bei Liu

3D porous Fe 3 O 4 @ZIF-90 interface provides high-density DNA loading sites. • Mn 2+ -gated DNAzyme walker ensures a low-background controllable assay. • DNAzyme walker and CRISPR-Cas13a cascade enable dual signal amplification. • The biosensor demonstrated high accuracy and specificity in human serum samples. The precise quantification of Mucin-1 (MUC1) is vital for the early diagnosis and therapeutic monitoring of epithelial malignancies. In this study, a fluorescent biosensing platform based on a 3D porous metal-organic framework (MOF) and a cascaded signal amplification strategy was developed for MUC1 detection, driven by a target-induced conformational switch and Mn 2+ -dependent catalytic DNAzyme walking. Porous Fe 3 O 4 @ZIF-90 nanocomposites were used to construct the sensing interface, which co-immobilized dormant DNAzyme/aptamer duplexes and a high-density layer of substrate DNA (sub-DNA), serving as a robust platform for the subsequent walking process. Upon specific MUC1 recognition, the aptamer preferentially captures the target MUC1. The thermodynamic driving force induces the dissociation of the MUC1/aptamer complex, liberating the DNAzyme engine. Following magnetic separation to eliminate matrix interferences, the addition of Mn 2+ triggers the processive inter-molecular migration of the DNAzyme walker across the sub-DNA immobilized 3D porous Fe 3 O 4 @ZIF-90 interface via successive hybridization and site-specific cleavage of internal riboadenosine (rA) junctions. This inter-molecular walking process generates a high flux of trigger strands, which subsequently activates the CRISPR-Cas13a system for a robust trans -cleavage of dual-labeled fluorophore-quencher (FQ) reporters. The resulting degradation of FQ reporter enables sensitive MUC1 quantification through exponential fluorescence recovery. By synergizing the structure advantages of the 3D MOF with this cascaded signal amplification, the biosensor achieved a wide linear range from 0.37 nM to 500 nM with a low detection limit of 17.2 pM. Furthermore, the biosensor exhibited reliable specificity and recovery (102.28%–106.94%) in complex human serum assays. The proposed strategy effectively minimizes non-specific background leakage, demonstrating promising potential for the ultra-sensitive detection of MUC1 in complex biological matrices. Schematic presentation of the fluorescent biosensor for the determination of Mucin-1 based on a 3D porous Fe 3 O 4 @ZIF-90 interface and DNAzyme walker-mediated CRISPR-Cas13a cascade. Download: Download high-res image (117KB) Download: Download full-size image

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TALANTA · 2020 · IF 5.339

Persistent luminescence nanorod based luminescence resonance energy transfer aptasensor for autofluorescence-free detection of mycotoxin

Yuan-Yuan Jiang,Xu Zhao,Li-Jian Chen,Cheng Yang,Xue-Bo Yin,Xiu-Ping Yan

Serious ochratoxin A (OTA) contamination necessitates the development of rapid, sensitive and selective analytical methods for its determination in food safety. Herein, we report a persistent luminescence resonance energy transfer (LRET) based aptasensor for the autofluorescence-free detection of OTA. OTA aptamer functionalized persistent luminescence nanorod (PLNR) Zn 2 GeO 4 :Mn 2+ and the aptamer complementary DNA modified gold nanoparticle (AuNP) were used as the donor and the acceptor, respectively. The developed LRET aptasensor integrated the advantages of the long-lasting persistent luminescence of PLNR, the high selectivity of aptamer and the low probe background of LRET sensors, allowing autofluorescence-free detection of OTA in biological samples with high sensitivity and selectivity. The developed LRET aptasensor gave an excellent linearity in the range of 0.01–10 ng mL −1 , the detection limit of 3 pg mL −1 and the precision of 2.7% (RSD, n  = 11) at 1 ng mL −1 level. The applicability of the developed aptasensor was demonstrated by analyzing beer samples for OTA with the recoveries of 92.3%–104%.

研究领域: 分析化学 · 食品安全 · 纳米技术 · 毒理学
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Journal of Materials Chemistry C · 2024 · IF 5.7

In situ preparation of highly luminescent Sb3+/Mn2+ co-doped Cs2KInCl6 lead-free double perovskites in a PVDF matrix and application to white light emitting diodes and anti-counterfeiting

Yongrun Dong,Wen Li,Tao Huang,Shuaigang Ge,Linghang Kong,Chuang Ning,Zequan Li,Wei Gao,Bingsuo Zou

Recently, lead-free double perovskites have been regarded as a promising alternative to lead halide perovskites due to their wide emission band, and environmental protection and stability properties, and are expected to become a series of rising star materials in the lighting field. However, currently, the growth of most lead-free double perovskites occurs in the strong acid environment, which not only brings high cost and environment risk, but also makes it hard to realize large-scale applications with powder products. Herein, we apply a strategy of in situ synthesis of lead-free double perovskites in a polymer matrix by using a small amount of precursors and relatively friendly DMSO solvent to obtain efficiently luminescent Sb3+/Mn2+ co-doped Cs2KInCl6/PVDF composite films in a large-area. The co-doping of Mn2+/Sb3+ into this inorganic double perovskite matrix makes microcrystals with good crystallinity and size distribution in this polymer. The as prepared co-doping composite film with Mn/Sb feeding ratio 16 : 1 shows the brightest white light emission under 320 nm excitation, with a photoluminescence quantum yield (PLQY) as high as 86.98%. The energy transfer (E-T) from the charge-transfer band to the triplet self-trapped exciton (STE) around Sb3+ and then to the ferromagnetic (FM) coupled Mn2+ pair 3d state was confirmed by the temperature-dependent PL spectra and density functional theory calculations. Finally, a single-compound white light emitting diode with chromatic coordinates of (0.31, 0.33) and fluorescent anti-counterfeiting labels could be fabricated based on this composite film with the best white emission. This work provides a new strategy for the application of lead-free double perovskites in the fields of lighting and anti-counterfeiting.

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INORGANIC CHEMISTRY COMMUNICATIONS · 2024 · IF 4.4

Metal (Mn2+, Co2+ and Cd2+) ions induced differentiation in mixed-ligands MOFs constructed from H3btb and H2bdc: Highly porous Structures, new topology nets and two-step gate-opening behaviors

Jie Wang,Ya-Nan Yu,Rou Huang,Ce Wang,Zheng Yin

Mix-ligands strategy is highly efficient for the rational construction of MOFs with particular structure motifs and high porosity, yet challenging and requiring matching in hierarchical coordination assembly and synergetic crystallization. The solvothermal reactions of 1,3,5-tris[4-carboxyphenyl]benzene (H 3 btb) and 1,4-benzenedicarboxylic acid (H 2 bdc) with different 3d metal ions , generated highly porous mixed-ligands MOFs of [(CH 3 ) 2 NH 2 ] 2 [Mn 3 (btb) 2 (bdc)]·12DMF·3MeOH ( Mn-btb-bdc ) having anionic 3D frameworks constructed from linear [Mn 3 (COO) 8 ] nodes, [Co 4 (btb) 2 (bdc)(H 2 O) 3 ]·15DMF·7H 2 O ( Co-btb-bdc ) processing neutral frameworks constituted by linear [Co 3 (COO) 6 (H 2 O) 4 ] and paddle-wheel [Co 2 (COO) 4 (H 2 O) 2 ] nodes, as well as one single-ligand MOFs of [(CH 3 ) 2 NH 2 ][Cd(btb)(H 2 O)]·8DMF ( Cd-btb-2fold ) exhibiting 2-fold interpenetrated ths net frameworks due to the unsuccessful introduce of the coexisted bdc ligand. Two new topology net of 2,3,8-connected net with point symbol of (4 2 ·6) 2 (4 4 ·6 6 ·8 12 ·10 5 ·12)(6) and 2,3,4,6-connected net with Point Symbol of (4·8 2 ) 4 (4 2 ·8 11 ·10 2 ) 2 (8 4 ·12 2 )(8 2 ) were found for Mn-btb-bdc and Co-btb-bdc . All these three MOFs are highly porous with void fractions of 60.9%, 52.2% and 61.4%, stemming from 3D-penetrated, 3D-penetrated and 1D channels, respectively. Such structural differentiations are attributed to the diversified electronic structure and coordination preference of different 3d metal ions, as well as the solvent template and temperature effects. Two-steps gate-opening behaviour in gas sorption isotherms was found in the flexible Mn-btb-bdc MOFs.

CAS / MDL: 10026-22-9
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Inorganic Chemistry Frontiers · 2019 ·Vol. 6 ·期 10 ·2837-2849 · IF 5.934

Mixing the valence control of Eu2+/Eu3+ and energy transfer construction of Eu2+/Mn2+ in the solid solution (1 − x)Ca3(PO4)2–xCa9Y(PO4)7 for multichannel photoluminescence tuning

Peipei Dang,Dongjie Liu,Guogang Li,Sisi Liang,Hongzhou Lian,Mengmeng Shang,Jun Lin

Recently, controllable photoluminescence tuning by devising a solid solution framework, adjusting the valence mixing of Eu2+/Eu3+ and designing efficient energy transfer between activator ions has been extensively investigated and reported due to its significant advantages in the improvement and regulation of the luminescence performances of white light-emitting diodes (W-LEDs). In this study, we designed a series of novel Eu2+-doped (1 − x)Ca3(PO4)2–xCa9Y(PO4)7 (x = 0–1.0) isostructural solid solution phosphors with a β-Ca3(PO4)2-type structure, and powder samples were prepared via the traditional high-temperature solid-state reaction process. The crystal field variation around the Eu2+ ions causes superposition of linear luminescence and induces optical property tuning with a change in the solid solution ratio, x, values. Besides the high-energy emission peak at 418 nm in Ca3(PO4)2:0.03Eu2+, another low-energy emission peak at 486 nm was observed with the formation of the solid solution. Moreover, the corresponding high-energy emission peaks shifted from 418 to 430 nm, and the luminescence intensity of the low-energy emission at 486 nm increased with an increase in x, which was attributed to the combined effect of crystal field splitting of the local lattice and superposition of linear luminescence. In addition, tunable emission across the whole white light region could be realized by constructing a solid solution and adjusting the overall Eu concentration in (1 − x)Ca3(PO4)2–xCa9Y(PO4)7:Eu (x = 0.5, 0.7, 0.9, and 1.0), and the corresponding luminescence mechanisms have been proposed and discussed in detail. In the pursuit of precise color tuning, we also tested the Eu2+ → Mn2+ energy transfer in different compositions (x = 0.2, 0.5, 0.7, and 0.9) of the solid solution phosphors, and successive emission tuning from the blue and cyan range and then the red range was successfully achieved. Finally, the temperature-dependent photoluminescence and decay time were revealed systematically, and the corresponding mechanisms for the thermal quenching behavior have been discussed. This study provides a new perspective for color tuning originating from the simultaneous isostructural solid solution, valence mixing of Eu2+/Eu3+ and efficient energy transfer.

研究领域: 材料科学 · 光学材料 · 无机化学 · 固体物理 · 发光学
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Nanomaterials · 2018 ·Vol. 8 ·期 7 ·466 · IF 3.504

Role of Mn2+ Doping in the Preparation of Core-Shell Structured Fe3O4@upconversion Nanoparticles and Their Applications in T1/T2-Weighted Magnetic Resonance Imaging, Upconversion Luminescent Imaging and Near-Infrared Activated Photodynamic Therapy

Yang Luo,Wei Zhang,Zhengfang Liao,Shengnan Yang,Shengtao Yang,Xinhua Li,Fang Zuo,Jianbin Luo

Core-shell (C/S) structured upconversion coated Fe3O4nanoparticles (NPs) are of great interest due to their potential as magnetic resonance imaging (MRI) and upconversion luminescent (UCL) imaging agents, as well as near-infrared activated photodynamic therapy (PDT) platforms. When C/S structured Fe3O4@Mn2+-doped NaYF4:Yb/Er NPs were prepared previously, well-defined C/S-NPs could not be formed without the doping of Mn2+during synthesis. Here, the role of Mn2+doping on the synthesis of core-shell structured magnetic-upconversion nanoparticles (MUCNPs) is investigated in detail. Core-shell-shell nanoparticles (C/S/S-MUCNPs) with Fe3O4as the core, an inert layer of Mn2+-doped NaYF4and an outer shell consisting of Mn2+-doped NaYF4:Yb/Er were prepared. To further develop C/S/S-MUCNPs applications in the biological field, amphiphilic poly(maleic anhydride-alt-1-octadecene) (C18PMH) modified with amine functionalized methoxy poly(ethylene glycol) (C18PMH-mPEG) was used as a capping ligand to modify the surface of C/S/S-MUCNPs to improve biocompatibility. UCL imaging, T1-weighted MRI ascribed to the Mn2+ions and T2-weighted MRI ascribed to the Fe3O4core of C/S/S-MUCNPs were then evaluated. Finally, chlorine e6 (Ce6) was loaded on the C/S/S-MUCNPs and the PDT performance of these NPs was explored. Mn2+doping is an effective method to control the formation of core-shell structured MUCNPs, which would be potential candidate as multifunctional nanoprobes for future T1/T2-weighted MR/UCL imaging and PDT platforms.Keywords:Mn2+;Fe3O4;upconversion;core-shell-shell;MR/UCL imaging;PDT platforms

CAS / MDL: 9004-74-4 2258654-78-1
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