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Harnessing the synergy between upconverting nanoparticles and lanthanide complexes in a multi-wavelength responsive hybrid system
摘要: We prepared a hybrid system composed of a continuous film of dinuclear lanthanide complex [Ln2bpm(tfaa)6] (Ln = Tb or Eu) and upconverting nanoparticles (UCNPs) using a straightforward drop-cast methodology. The system displayed visible emission under near-infrared (NIR) excitation, simultaneously stemming from sub-10-nm UCNPs and [Ln2] complexes, the latter species being otherwise directly excitable only using UV-blue radiation. In light of the results of steady-state – including power-dependent – and time-resolved optical measurements, we identified the radiative, primarily ligand-mediated nature of the energy transfer from Tm3+ ions in the UCNPs-to-Ln3+ ions in the complexes. Hyperspectral mapping and electron microscopy observations of the surface of the hybrid system confirmed the continuous and concomitant distribution of UCNPs and lanthanide complexes over the extensive composite films. Key features of the hybrid system are the simultaneous UV-blue and NIR light harvesting capabilities and their ease of preparation. These traits render the presented hybrid system a formidable candidate for the development of photoactivated devices capable to operate under multiple excitation wavelength and to transduce the absorbed light into narrow, well-defined spectral regions.
关键词: hybrid system,complex,energy transfer,lanthanide,films,upconverting nanoparticles,hyperspectral imaging
更新于2025-09-23 15:23:52
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Hot electron-induced electrochemiluminescence at cellulose derivatives-based composite electrodes
摘要: The possibility of using cellulose derivative films as (i) insulating material on metal electrodes or (ii) in composite electrode films on metal to produce hot electron-induced electrochemiluminescence (HECL) was studied. It was shown that the luminophores known to produce HECL at thin insulating film coated cathodes (e.g. Si/SiO2 and Al2O3 electrodes) produced HECL with the present novel electrodes. In the case of composite films consisting of cellulose material doped with conducting carbon particles, the optimal cellulose/carbon black ratios were investigated by measuring the time-resolved HECL (TR-HECL) of an aromatic Tb(III) chelate. In addition to Tb(III) chelate, other well-known labels, fluorescein and Ru(bpy)3 2+ chelate, were demonstrated to produce strong HECL at the present composite electrodes, which are more environmental friendly in disposable assay cartridges as the plastic-based composites we have studied previously. Thus, it is now possible on the present basis to manufacture biodegradable paper-based assay cartridges with HECL detection of labels at biodegradable electrodes. It was shown that the present composite films are stable over wide pH range, and also time-resolved detection of Ru(bpy)3 2+ chelate is possible although its luminescence lifetime if quite short. The calibration curves were measured for presently used aromatic Tb(III) chelate and for Ru(bpy)3 2+. The detection limit (s/n = 3) was 2 · 10?10 M for the Tb(III)-chelate and 4 · 10?9 M for Ru(bpy)3 2+ in time-resolved detection mode. The relative standard deviation for Tb(III)-L1 (n = 5) emission at 10?5 M concentration was 2%. Wide linear range and low detection limits suggests that cellulose based composite electrodes can be used in HECL bioaffinity assays which was finally demonstrated here by an immunometric immunoassay.
关键词: Bioaffinity assays,Cellulose derivatives,Lanthanide electrochemiluminescence,Immunoassays,Electrochemiluminescence,Hot electron electrochemistry
更新于2025-09-23 15:23:52
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Lanthanide complexes with 2-(tosylamino)-benzylidene-N-(aryloyl)hydrazones - universal luminescent materials
摘要: Lanthanide complexes Ln(L1)(HL1) (Ln = Lu, Yb, Er, Gd, Eu, Sm) and Ln(L2)(HL2) (Ln = Lu, Yb, Gd, Eu) with 2-(tosylamino)-benzylidene-N-(aryloyl)hydrazones (H2L1, aryloyl = 2-hydroxybenzoyl; H2L2, aryloyl = Isonicotinoyl) were obtained with the aim to explore them as new luminescent materials. They were found to form monomeric species independently on the aryloyl nature, their crystal structures were determined from single crystal X-ray data (Yb(L2)(HL2)·0.5(C2H5OH)), as well as from powder X-ray data by Rietveld refinement (Eu(L1)(HL1)). Ytterbium complexes exhibited intense luminescence, which allowed using them in host-free OLEDs, which demonstrated remarkable efficiency of NIR electroluminescence (50 μW/W) at low voltage (5V). Special mechanism of europium luminescence quenching allowed using europium complexes as luminescent thermometers, which demonstrated very high sensitivity up to 12%/K. The theory of luminescence thermometry based on three-level system was proposed which allowed predicting sensitivity with high accuracy (error within 20%).
关键词: lanthanide complexes,OLEDs,luminescent thermometry,NIR emission,luminescent materials
更新于2025-09-23 15:23:52
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Recent Trends Concerning Upconversion Nanoparticles and Near-IR Emissive Lanthanide Materials in the Context of Forensic Applications
摘要: Upconversion nanoparticles (UCNPs) are materials that, upon absorbing multiple photons of low energy (e.g. infrared radiation), subsequently emit a single photon of higher energy, typically within the visible spectrum. The physics of these materials have been the subject of detailed investigations driven by the potential application of these materials as medical imaging devices. One largely overlooked application of UCNPs is forensic science, wherein the ability to produce visible light from infrared light sources would result in a new generation of fingerprint powders that circumvent background interference which can be encountered with visible and ultraviolet light sources. Using lower energy, infrared radiation would simultaneously improve the safety of forensic practitioners who often employ light sources in less than ideal locations. This review article covers the development of UCNPs, the use of infrared radiation to visualise fingerprints by the forensic sciences, and the potential benefits of applying UCNP materials over current approaches.
关键词: Upconversion nanoparticles,Fingerprint visualisation,Near-IR emissive lanthanide materials,Forensic applications,NIR emission
更新于2025-09-23 15:22:29
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Chiral Sensing Using Circularly Polarized Luminescence of Bis (phenanthroline dicarboxylic acid) Eu(III) Complex Induced by Allosteric-type Interaction with Amino Acid Molecules
摘要: [Eu(pda)2]- and [Eu(bda)2]- (pda = 1,10-phenanthroline-2,9-dicarboxylic acid; bda = 2,2’ bipyridine 5,5’-dicarboxylic acid) have an achiral D2d structure in crystals. These complexes exhibit circularly polarized luminescence (CPL) in water containing chiral amino acids. In this work, induced CPL of [Eu(pda)2]- and [Eu(bda)2]- in water solutions containing a mixture of D- and L- amino acids were examined. Plots of glum values of the induced CPL as a function of mol-fraction of L- and D- arginine reveal that [Eu(pda2]- favors homo-association ([Eu(pda)2]--(L-arginine)2 or [Eu(pda)2]--(D-arginine)2) over hetero-association {[Eu(pda)2]--(L-arginine)?(D-arginine)}. This suggests that association of an arginine molecule induces a structural change in [Eu(pda)2]- to promote chiral selective association to another arginine, i.e., homo-allosteric association. On the other hand, the system of [Eu(pda)2]- with histidine favors hetero-allosteric association over homo-association. No allosteric effect is recognized in CPL from [Eu(bda)2]-.
关键词: allosteric effect,amino acid,lanthanide complex,circularly polarized luminescence,chiral sensing
更新于2025-09-23 15:22:29
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Surface Functionalisation of Upconversion Nanoparticles with Different Moieties for Biomedical Applications
摘要: Lanthanide ion-doped upconversion nanoparticles (UCNPs) that can convert low-energy infrared photons into high-energy visible and ultraviolet photons, are becoming highly sought-after for advanced biomedical and biophotonics applications. Their unique luminescent properties enable UCNPs to be applied for diagnosis, including biolabeling, biosensing, bioimaging, and multiple imaging modality, as well as therapeutic treatments including photothermal and photodynamic therapy, bio-reductive chemotherapy and drug delivery. For the employment of the inorganic nanomaterials into biological environments, it is critical to bridge the gap in between nanoparticles and biomolecules via surface modifications and subsequent functionalisation. This work reviews the various ways to surface modify and functionalise UCNPs so as to impart different functional molecular groups to the UCNPs surfaces for a broad range of applications in biomedical areas. We discussed commonly used base functionalities, including carboxyl, amino and thiol moieties that are typically imparted to UCNP surfaces so as to provide further functional capacity.
关键词: lanthanide,functionalisation,silanisation,surface modification,ligand engineering,nanoparticles,upconversion
更新于2025-09-23 15:22:29
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Highly -sensitive near infrared luminescent nanothermometers based on binary mixture
摘要: We propose a simple strategy to obtain a luminescence intensity ratio nanothermometer operating in the near infrared range (1000 – 1700 nm) by use of binary mixtures of lanthanide doped Y2O3 selected as 1%Ho - Y2O3 + 1%Er - Y2O3 and 1%Ho - Y2O3 + 1%Nd - Y2O3. All nanoparticles were synthetized by citrate complexation method and thermally annealed at 800 °C. The temperature evolution of the emission properties was monitored in the range of 297 – 472 K and analyzed in terms of emission shape, intensity, dynamics, excitation wavelength, acquisition mode and weight ratio of the binary mixture. A maximum relative sensitivity of 1%K-1 at 297 K was recorded for the 3:1 weight ratio Ho – Y2O3 + Er – Y2O3 binary mixture upon excitation at 536.8 nm. For the more appropriate excitation wavelength for bioimaging applications at 649.7 nm, a relative sensitivity of 0.55 - 0.6 % K-1 was recorded in the relevant physiological temperature range (300 -320 K) for the 3:1 weight ratio Ho – Y2O3 + Er – Y2O3 binary mixture. To the best of our knowledge, our study also represents a first report on the near -infrared luminescence (around 1200 nm) lifetime thermometry for a Ho doped nanoparticle. Comparison with the literature demonstrates that our system represents a promising near-infrared thermometer, with a non-sophisticated and reproducible configuration that is open to multiple optimization routes.
关键词: Lifetime thermometry,Binary mixture,lanthanide doped Y2O3,Near infrared luminescence,Self-referenced nanothermometry
更新于2025-09-23 15:22:29
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[IEEE 2017 5th International Conference on Instrumentation, Communications, Information Technology, and Biomedical Engineering (ICICI-BME) - Bandung, Indonesia (2017.11.6-2017.11.7)] 2017 5th International Conference on Instrumentation, Communications, Information Technology, and Biomedical Engineering (ICICI-BME) - Enhancement of Luminescence Light Yield of Ln <sup>3+</sup> Doped Glass By Oxyfluoride Glass Matrix
摘要: Glass is a good material which received attention for doping lanthanide ions. Glass doped Ln3+ ions can show luminescence, but not too strong light yield. It is well known that the host glass plays an important role in the enhancement. This paper has been described effect of Ln3+ ions (Sm3+, Eu3+ and Dy3+) doped oxyfluoride glass by comparing between oxide and oxyfluoride glasses. For the Sm3+ doped gadolinium calcium phosphate oxyfluoride glass, the highest emission peak was 598 nm under 401 nm excitation. While the emission light yield of oxyfluoride glass was higher than oxide glass due to the reduction of phonon and non-radiative losses. In case of Eu3+ doped oxyfluoride glass, the 612 nm emission under 394 nm excitation was observed. The light yield of oxyfluoride glass also was better than oxide glass. The Dy3+-doped phosphate oxide and oxyfluoride glasses were investigated. The luminescence light yield of oxyfluoride glass was more than oxide glass as well, owing to lower OH group of oxyfluoride glass, which can be confirmed by FTIR measurement. As described earlier, it concludes that the oxyfluoride glass is better than glass matrix when compared with oxide glass to enhance luminescence light yield for Ln3+ ions in glass matrix.
关键词: phonon energy,oxyfluoride glass,oxide glass,lanthanide ions
更新于2025-09-23 15:22:29
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White-Light-Emitting Decoding Sensing for Eight Frequently-Used Antibiotics Based on a Lanthanide Metal-Organic Framework
摘要: Developing multi-selective luminescence sensing technology to differentiate serial compounds is very important but challenging. White-light-emitting decoding sensing based on lanthanide metal-organic frameworks (Ln-MOFs) is a promising candidate for multi-selective luminescence sensing application. In this work, three isomorphic Ln-MOFs based on H3dcpcpt (3-(3,5-dicarboxylphenyl)-5-(4-carboxylphenl)-1H-1,2,4-triazole) ligand, exhibiting red, blue, and green emission, respectively, have been synthesized by solvothermal reactions. The isostructural mixed Eu/Gd/Tb-dcpcpt is fabricated via the in-situ doping of different Ln3+ ions into the host framework, which can emit white light upon the excitation at 320 nm. It is noteworthy that this white-light-emitting complex could serve as a convenient luminescent platform for distinguishing eight frequently-used antibiotics: five through luminescence-color-changing processes (tetracycline hydrochloride, yellow; nitrofurazone, orange; nitrofurantoin, orange; sulfadiazine, blue; carbamazepine, blue) and three through luminescence quenching processes (metronidazole, dimetridazole, and ornidazole). Moreover, a novel method, 3D decoding map, has been proposed to realize multi-selective luminescence sensing applications. This triple-readout map features unique characteristics on luminescence color and mechanism. The mechanism has been systematically interpreted on the basis of the structural analysis, energy transfer and allocation process, and peak fitting analysis for photoluminescence spectra. This approach presents a promising strategy to explore luminescent platforms capable of effectively sensing serial compounds.
关键词: lanthanide,metal-organic framework,multi-selective luminescence sensing,decoding sensing,white light,antibiotics
更新于2025-09-23 15:22:29
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Experimental and numerical investigation to rationalize both near-infrared and mid-infrared spontaneous emission in?Pr3+ doped selenide-chalcogenide fiber
摘要: This contribution reports on detailed experimental and numerical investigations of both near-infrared (NIR) and mid-infrared (MIR) photoluminescence obtained in praseodymium trivalent ion doped chalcogenide-selenide glass fiber. The experimental analysis allows for the identification of the radiative transitions within the praseodymium ion energy level structure to account for the photoluminescent behavior. Numerical analysis is carried out using the rate equations' approach to calculate the level populations. The numerical analysis provides further insight into the nature of the radiative transitions in the Pr3+ ion doped chalcogenide-selenide glass and allows for the identification of the electronic transitions, which contribute to the observed photoluminescence. The numerical results agree well with the experimental results.
关键词: chalcogenide glass fibers,optical fiber modelling,lanthanide doped fibers
更新于2025-09-23 15:22:29