Boosting Photoluminescence of Rare-Earth-Based Double Perovskites by Isoelectronic Doping of ns2 Metal Ions.

Doping of ns2 metal ions as an energy transfer (ET) bridge can significantly elevate the photoluminescence properties. Nonetheless, the fundamental influence of ns2 metal ions on the local lattice structures remains unclear, hindering the advancement of functional materials. Herein, Sb3+ doped rare earth double perovskites is employed as a typical case to demonstrate this issue. It is found that the isoelectronic doping of Sb3+ ions not only enhances the ET efficiency but also changes their localized electronic and lattice structures. Both density functional theory (DFT) and Judd-Ofelt (J-O) theory calculations provide unambiguous evidence that the isoelectronic doping of Sb3+ ions enables a more localized charge density in the [LnCl6]3- (Ln: Lanthanide) octahedron and reduces the symmetry of the environment around the Ln3+, facilitating the radiative transition rates of Ln3+ while enhancing their ET efficiency. Compared with Cs2NaScCl6:Ln3+, the ET efficiency of Cs2NaScCl6:Sb3+/Ln3+ is enhanced by 1.5-fold, reaching up to 98.3%. To the best of available knowledge, this work is the first to unravel the intrinsic mechanism of enhanced ET process enabled by isoelectronic doping via DFT and J-O theory. This research sheds light on understanding the mechanism of photophysics and rational design of the functional perovskite materials.

Longitudinal and Transverse 1H Nuclear Magnetic Resonance Relaxivities of Lanthanide Ions in Aqueous Solution up to 1.4 GHz/33 T.

The longitudinal and transverse nuclear magnetic resonance relaxivity dispersion (NMRD) of 1H in water induced by the paramagnetic relaxation enhancement (PRE) of dissolved lanthanide ions (Ln3+) can become very strong. Longitudinal and transverse 1H NMRD for Gd3+, Dy3+, Er3+ and Ho3+ were measured from 20 MHz/0.47 T to 1382 MHz/32.5 T, which extended previous studies by a factor of more than two in the frequency range. For the NMRD above 800 MHz, we used a resistive magnet, which exhibits reduced field homogeneity and stability in comparison to superconducting and permanent NMR magnets. These drawbacks were addressed by dedicated NMRD methods. In a comparison of NMRD measurements between 800 MHz and 950 MHz performed in both superconducting and resistive magnets, it was found that the longitudinal relaxivities were almost identical. However, the magnetic field fluctuations of the resistive magnet strongly perturbed the transverse relaxation. The longitudinal NMRDs are consistent with previous work up to 600 MHz. The transverse NMRD nearly scales with the longitudinal one with a factor close to one. The data can be interpreted within a PRE model that comprises the dipolar hyperfine interactions between the 1H and the paramagnetic ions, as well as a Curie spin contribution that is dominant at high magnetic fields for Dy3+, Er3+ and Ho3+. Our findings provide a solid methodological basis and valuable quantitative insights for future high-frequency NMRD studies, enhancing the measurement accuracy and applicability of PRE models for paramagnetic ions in aqueous solutions.

Ultrasensitive and Adjustable Nanothermometers Based on Er3+-Sensitized Core@Shell Nanoparticles for Use in the First Biological Window.

In recent years, intensive research has focused on lanthanide-doped nanoparticles (NPs) used as noncontact temperature sensors, particularly in nanomedicine. These NPs must be capable of excitation and emission within biological windows, where biological materials usually show better transparency for radiation. In this article, we propose that NPs sensitized with Er3+ ions can be applied as temperature sensors in biological materials. We synthesized the NPs through a reaction in high-boiling solvents and confirmed their crystal structure and the formation of core@shell NPs by using X-ray diffraction, high-resolution transmission electron microscopy, and element distribution mapping within the NPs. NaErF4@NaYF4, NaYF4:12.5% Er3+, 2.5% Tm3+@NaYF4, NaYF4:7.5% Er3+@NaYF4, and NaYF4:12.5% Er3+, 2.5% Ho3+@NaYF4 exhibited intense upconversion (UC) emission under 1532 nm laser excitation detectable also in the whole human blood. We propose that this UC results from energy transfer between Er3+ ions and from Er3+ to Tm3+ or Ho3+ codopants. To determine the mechanism of UC, we measured the dependence of the emission band intensities on the laser power densities. Importantly, we also analyzed the temperature-dependent emission of the NPs within the 295-360 K range. Based on the collected emission spectra, we calculated the luminescence intensity ratios (LIRs) of the emission bands to assess their potential for optical temperature sensing. The temperature-sensing properties varied with the concentration of Er3+ ions and the presence of additional Tm3+ or Ho3+ codopants. Depending on the NP composition and the emission bands used for luminescence ratio calculations, the maximum relative temperature sensitivity ranged from 4.55%·K-1 to 1.12%·K-1, with temperature resolution between 0.05 and 2.53 K at room temperature. Finally, as proof of using NPs as temperature sensors in biomedicine, we successfully measured the temperature-dependent emission of NaYF4:7.5% Er3+@NaYF4 NPs dispersed in whole blood under 1532 nm excitation. We demonstrated that the ratio of Er3+ ion emission bands changes with temperature, indicating that these NPs have potential applications in temperature sensing within biological environments. We also confirmed the properties of NPs as temperature sensors by measuring the temperature reading uncertainty and the repeatability of the LIR readings during heating-cooling cycles, thereby confirming the excellent properties of the studied systems as temperature sensors.

Rise and Decay of Photoluminescence in Upconverting Lanthanide-Doped Nanocrystals.

Nanocrystals (NCs) doped with lanthanides are capable of efficient photon upconversion, i.e., absorbing long-wavelength light and emitting shorter-wavelength light. The internal processes that enable upconversion are a complex network of electronic transitions within and energy transfer between dopant centers. In this work, we study the rise and decay dynamics of upconversion emission from ß-NaYF4 NCs codoped with Er3+ and Yb3+. The rise dynamics of the red and green upconverted emissions are nonlinear, reflecting the nonlinear nature of upconversion and revealing the mechanisms that populate the emitting states. The excited-state decay dynamics are nonexponential. We unravel the underlying decay pathways using photonic experiments. These reveal the contributions of different upconversion pathways visually, as each pathway exhibits a distinct response to systematic variation of the local density of optical states. Moreover, the effect of the local density of optical states on core-only NCs is qualitatively different from core-shell NCs. This is due to the different balance between feeding and decay of the electronic levels that produce upconverted emission. The understanding of the upconversion dynamics provided here could lead to better imaging and sensing methods relying on upconversion lifetimes or guide the rational optimization of the dopant concentrations for brighter upconversion.

Synthesis and Characterizations of Novel bi-ligand TbEu(cpioa)phen Phosphors with High Quantum Efficiency for WLED Applications.

The hydrothermal method was employed to synthesize a novel bi-ligands LnMOF: Ln(cpioa)phen. The secondary ligand 1, 10-phen serves as a bridging agent to further facilitate energy transfer between Ln ions and the primary ligand H3cpioa. A comparison between Ln(cpioa) MOFs (Ln: Tb3+, Eu3+) and Ln(cpioa)phen MOFs (Ln: Tb3+, Eu3+) reveals that addition of the secondary ligand significantly improves the emission intensity by as high as almost 34 times. After detailed structural study, it is found that different Ln ions have the similar coordination in the Ln(cpioa)phen MOF. In addition, the chromaticity of Ln(cpioa)phen MOFs can be easily tuned by the amounts of doping Ln ions. La0.974Tb0.0255Eu0.0005(cpioa)phen MOF has a white emission with a CIE coordinate of (0.323, 0.343). Characterizations of corresponding LED devices show that device based on Ln(cpioa)phen MOF has better photoluminescence performances, which indicates that Ln(cpioa)phen MOF has great potential of for WLED applications.

An Eu (III)-functionalized covalent organic framework fluorescent probe for specific detection of Flumequine based on pore restriction and antenna effect.

The overuse of quinolone antibiotics has led to a series of health and environmental issues. Herein, we combine the distinct luminescence properties of Eu3+ with the unique structure of covalent organic frameworks (COFs) to develop a precise and sensitive fluorescent probe for detecting Flumequine (Flu) in water. Eu3+ is thoroughly anchored into the channels of COFs as recognition sites, while the synthesized probe material still maintains its intact framework structure. The unique structure of COFs provides excellent support and protection for Eu3+. Therefore, COF-Eu can rapidly bind with Flu which can transfer the absorbed energy to Eu3+ through an "antenna effect", resulting in red fluorescence. Moreover, there is a good linear relationship between Flu concentration in the range of 0-30 µM, with a detection limit of 41 nM. Simultaneously, the material maintains remarkable reproducibility, with its performance remaining almost unchanged after five cycles of use. Remarkably, the probe demonstrates excellent Flu recovery rates in real samples. This study provides a viable approach for the recognition of flumequine in the environment through a customized fluorescence detection method.

Dual-emission Tb-based coordination polymer as a ratiometric fluorescence probe for the detection of phosphate.

A simple, sensitive dual-emission probe was developed for the detection of phosphate (Pi). The probe Tb-BTB/DPA was synthesized by mixing dual-ligand, 1,3,5-tri(4-carboxyphenyl) benzene (H3BTB) and dipicolinic acid (DPA), with metal ions Tb3+ in ethanol-water solution at 40℃ for 2 h. Tb-BTB/DPA exhibits two emission peaks, the emission at 362 nm is attributed to H3BTB, an energy transfer between Tb3+ nodes, and DPA further enhances the fluorescence of Tb3+ at 544 nm. Pi competes with ligand H3BTB to coordinate Tb3+, resulting in partial collapse of the Tb-BTB/DPA structure and interrupting the electron transfer between H3BTB and Tb3+. Therefore, the emission at 362 nm is enhanced, while the emission at 544 nm is unchanged, and a ratiometric fluorescence method is developed to detect Pi. Tb-BTB/DPA exhibits good linearity within the Pi concentration range (0.1-50 µmol/L), and the detection limit was 25.8 nmol/L. This study provides a new way to prepare probes with dual emission sensing properties.

Polarity-Mediated Antisolvent Control Enables Efficient Lanthanide-Based near-Infrared Perovskite LEDs.

Alloying lanthanide ions (Yb3+) into perovskite quantum dots (Yb3+:CsPb(Cl1-xBrx)3) is an effective method to achieve efficient near-infrared (NIR) luminescence (>950 nm). Increasing the Yb3+ alloying ratio in the perovskite matrix enhances the luminescence intensity of Yb3+ emission at 990 nm. However, high Yb3+ alloying (>15%) results in vacancy-induced inferior material stability. In this work, we developed a polarity-mediated antisolvent manipulation strategy to resolve the incompatibility between a high Yb3+ alloying ratio and inferior stability of Yb3+:CsPb(Cl1-xBrx)3. Precise control of solution polarity enables increased uniformity of the perovskite matrix with fewer trap densities. Employing this strategy, we obtain Yb3+:CsPb(Cl1-xBrx)3 with the highest Yb3+ alloying ratio of 30.2% and a 2-fold higher electroluminescence intensity at 990 nm. We lever the engineered Yb3+:CsPb(Cl1-xBrx)3 to fabricate NIR-LEDs, achieving a peak external quantum efficiency (EQE) of 8.5% at 990 nm: this represents the highest among perovskite NIR-LEDs with an emission wavelength above 950 nm.

Ultrasensitive Colorimetric Luminescence Thermometry by Progressive Phase Transition.

Luminescent materials that display quick spectral responses to thermal stimuli have attracted pervasive attention in sensing technologies. Herein, a programmable luminescence color switching in lanthanide-doped LiYO2 under thermal stimuli, based on deliberate control of the monoclinic (ß) to tetragonal (α) phase transition in the crystal lattice, is reported. Specifically, a lanthanide-doping (Ln3+ ) approach to fine-tune the phase-transition temperature in a wide range from 294 to 359 K is developed. Accordingly, an array of Ln3+ -doped LiYO2 crystals that exhibit progressive phase transition, and thus sequential color switching at gradually increasing temperatures, is constructed. The tunable optical response to thermal stimuli is harnessed for colorimetric temperature indication and quantitative detection, demonstrating superior sensitivity and temperature resolution (Sr = 26.1% K-1 , δT = 0.008 K). The advances in controlling the phase-transition behavior of luminescent materials also offer exciting opportunities for high-performance personalized health monitoring.

A Series of Novel 3D Coordination Polymers Based on the Quinoline-2,4-dicarboxylate Building Block and Lanthanide(III) Ions-Temperature Dependence Investigations.

A series of novel 3D coordination polymers [Ln2(Qdca)3(H2O)x]·yH2O (x = 3 or 4, y = 0-4) assembled from selected lanthanide ions (Ln(III) = Nd, Eu, Tb, and Er) and a non-explored quinoline-2,4-dicarboxylate building block (Qdca2- = C11H5NO42-) were prepared under hydrothermal conditions at temperatures of 100, 120, and 150 °C. Generally, an increase in synthesis temperature resulted in structural transformations and the formation of more hydrated compounds. The metal complexes were characterized by elemental analysis, single-crystal and powder X-ray diffraction methods, thermal analysis (TG-DSC), ATR/FTIR, UV/Vis, and luminescence spectroscopy. The structural variety of three-dimensional coordination polymers can be ascribed to the temperature effect, which enforces the diversity of quinoline-2,4-dicarboxylate ligand denticity and conformation. The Qdca2- ligand only behaves as a bridging or bridging-chelating building block binding two to five metal centers with seven different coordination modes arising mainly from different carboxylate group coordination types. The presence of water molecules in the structures of complexes is crucial for their stability. The removal of both coordinated and non-coordinated water molecules leads to the disintegration and combustion of metal-organic frameworks to the appropriate lanthanide oxides. The luminescence features of complexes, quantum yield, and luminescent lifetimes were measured and analyzed. Only the Eu complexes show emission in the VIS region, whereas Nd and Er complexes emit in the NIR range. The luminescence properties of complexes were correlated with the crystal structures of the investigated complexes.

Novel Aspects about "Lifetime" in Upconversion Luminescence.

Recent progress on the temporal response (TR) of lanthanide-doped upconversion luminescence (UCL) has enriched the means of UCL regulation, promoted advanced designs for customized applications such as biological diagnosis, high-capacity optical coding, and dynamic optical anti-counterfeiting, and pushed us to reacquaint the dynamic responses of sensitizer/activator ions in UCL systems. In particular, the lifetime of UCL should be revisited after discovery of novel experimental phenomena and luminescence mechanisms, i. e., it should be understood as the collective TR (in the decay edge) of all the involved ions rather than the reciprocal of the radiative rate of an individual ion. In this Concept, we retraced the latest understanding of the dynamics in UCL with special attention to the relationship between excitation and emission, means of TR regulation, and discussed existing challenges. It is expected to provide some fundamental insights to deepened understanding, further regulation, and frontier applications of TR features of UCL.

Luminescent Papers with Asymmetric Complexes of Eu(III) and Tb(III) in Polymeric Matrices and Suggested Combinations for Color Tuning.

Complexes of lanthanide ions, such as Eu(III) (red light emission) and Tb(III) (green light emission), with proper ligands can be highly luminescent and color-tunable, also attaining yellow and orange emission under UV radiation. The ligands employed in this work were poly(sodium acrylate), working as polymeric matrix, and 1,10-phenanthroline, taking advantage of its antenna effect. Possibilities of color display were further enhanced by incorporating a cationic polyfluorene with blue emission. This strategy allowed for obtaining cyan and magenta, besides the aforementioned colors. Uncoated cellulose paper was impregnated with the resulting luminescent inks, observing a strong hypsochromic shift in excitation wavelength upon drying. Hence, while a cheap UV-A lamp sufficed to reveal the polyfluorene's blue emission, shorter wavelengths were necessary to visualize the emission due to lanthanide ions as well. The capacity to reveal, with UV-C radiation, a full-color image that remains invisible under natural light is undoubtedly useful for anti-counterfeiting applications. Furthermore, both lanthanide ion complexes and polyfluorenes were shown to have their luminescence quenched by Cu(II) ions and nitroarenes, respectively.

Exploring Ln(III)-Ion-Based Luminescent Species as Down-Shifters for Photovoltaic Solar Cells.

In this work, we have compiled our research on lanthanide-based luminescent materials for use as down-shifter layers in photovoltaic (PV) mini-modules. The complexes we have prepared (C1-17), with formulas [Eu2(phen)2(bz)6] (C1), [Eu2(bphen)2(bz)6] (C2), [Eu(tta)3bphen] (C3), [Eu(bta)3pyz-phen] (C4), [Eu(tta)3pyz-phen] (C5), [Eu(bta)3me-phen] (C6), [Er(bta)3me-phen] (C7), [Yb(bta)3me-phen] (C8), [Gd(bta)3me-phen] (C9), [Yb(bta)3pyz-phen] (C10), [Er(tta)3pyz-phen] (C11), [Eu2(bz)4(tta)2(phen)2] (C12), [Gd2(bz)4(tta)2(phen)2] (C13), [EuTb(bz)4(tta)2(phen)2] (C14), [EuGd(bz)4(tta)2(phen)2] (C15), [Eu1.2Gd0.8(bz)4(tta)2(phen)2] (C16), and [Eu1.6Gd0.4(bz)4(tta)2(phen)2] (C17), can be grouped into three families based on their composition: Complexes C1-6 were synthesized using Eu3+ ions and phenanthroline derivatives as the neutral ligands and fluorinated ß-diketonates as the anionic ligands. Complexes C7-11 were prepared with ligands similar to those of complexes C1-6 but were synthesized with Er3+, Yb3+, or Gd3+ ions. Complexes C12-17 have the general formula [M1M2(bz)4(tta)2(phen)2], where M1 and M2 can be Eu3+, Gd3+, or Tb3+ ions, and the ligands were benzoate (bz-), 2-thenoyltrifluoroacetone (tta-), and 1,10-phenanthroline (phen). Most of the complexes were characterized using X-ray techniques, and their photoluminescent properties were studied. We then assessed the impact of complexes in the C1-6 and C12-17 series on the EQE of PV mini-modules and examined the durability of one of the complexes (C6) in a climate chamber when embedded in PMMA and EVA films. This study emphasizes the methodology employed and the key findings, including enhanced mini-module efficiency. Additionally, we present promising results on the application of complex C6 in a bifacial solar cell.

Sub-micron microparticles with tunable fluorescence emission obtained via co-self-assembly of amidoximed polymeric ligands and lanthanide ions.

Lanthanide coordinating polymeric microparticles have witnessed increasing research interests during the past decades due to their versatile morphology and tunable fluorescent properties. Herein, we have synthesized an amidoximed block copolymer containing aromatic backbone and pendent amidoxime as well as carboxyl groups, which has been employed as the ligand to sensitize the intrinsic fluorescence emission of lanthanide ions of Tb3+ and Eu3+. Furthermore, the lanthanide coordinating polymeric microparticles showing tunable green and red emission fluorescence have been prepared via the emulsion confinement co-self-assembly of amidoximed polymeric ligands with Tb3+ and Eu3+. It is found that both the fluorescence emission and sizes of obtained fluorescent microparticles can be easily modulated in a wide range by tuning concentration of polymers and lanthanide ions, as well as emulsion evaporation temperature. Thanks to their tunable sizes (250-900 nm), fluorescence emission as well as presence of surface active functional groups, the present fluorescent microparticles would find potential applications in in-vitro detection, optical encoding and devices.

Hydrothermal deposition synthesis of dual-mode luminescent material GdVO4 :Eu3+ /carbon dots with optimal luminescence and its application in anti-counterfeiting.

To obtain optimal luminescence, 0.12 g of GdVO4 :3%Eu3+ nanocrystals (NCs) and different volumes of nitrogen-doped carbon dots (N-CDs) crude solution were used as precursors, and the composite synthesized using the hydrothermal deposition method showed optimal luminescence when 11 ml (2.45 mmol) crude solution was used. In addition, similar composites with the same molar ratio as GVE/cCDs(11) were also prepared with the hydrothermal and physical mixing processes. Based on the test results of XRD, XPS, and PL spectra, for the composite GVE/cCDs(11), the highest (lowest) peak intensity of the C-C/C=C (C=O/C=N) bond, which was 1.18 (0.75) times that of GVE/cCDs-m, indicated most N-CDs deposition and led to their highest emission intensity under 365 nm excitation, although nitrogen atoms in the composite were shed slightly during the deposition process. Finally, as can be seen from the patterns designed for security applications that the optimally luminescent composite is one of the most promising candidates in the anti-counterfeiting field.

Photoionic Effect Imposed by Photoresponsive Local Field in a Tellurate Glass with Lanthanide Ions and Ag Nanoparticles.

Understanding the photoionic mechanism in optoelectronic materials offers significant potential for various applications in the fields of laser, data/energy storage, signal processing, and ionic batteries. However, the research on such light-matter interaction using photons of sub-bandgap energy is scarce, especially for those transparent materials with photoactive centers that would generate a local field upon photoillumination. This research investigates the photoionic effect in Yb3+/Er3+ doped tellurate glass with Ag nanoparticles (NPs) embedded. It is found that the photogenerated electric dipole of Yb3+/Er3+ ions and local field of Ag NPs could block the Ag+ migration in an external electric field. The blocking phenomenon of Ag NPs is the so-called Coulomb blocking effect (ascribed to its quantum confinement effect), which would be further enhanced by the additional photoinduced localized surface plasmon resonance (LSPR) effect. Interestingly, the photoresponsive electric dipole of lanthanide ions could cause plasmon oscillation of Ag NPs, resulting in a partial release of the blockade of lanthanide ions and enhanced blockade via quantum confinement of Ag NPs. A model device is proposed according to the photoresistive behavior. The research gives another perspective on the photoionic effect via the photoresponsive local field generated by photoactive centers in optofunctional materials.

Energy transfer mechanism of carboxymethyl chitosan-Eu3+/Tb3+ complex materials and application in multicolor LED.

Biological macromolecules had been studied as ligands in recent years, which not only give the complexes excellent polymer properties, but also have many advantages such as biodegradability. Carboxymethyl chitosan (CMCh) is excellent biological macromolecular ligand because of its abundant active amino and carboxyl groups, and it can smoothly transfer energy to Ln3+ after coordinating. To further study the energy transfer mechanism of CMCh-Ln3+ complexes, CMCh-Eu3+/Tb3+ complexes with different Eu3+/Tb3+ ratios were prepared by using CMCh as a ligand. The morphology, structure, and properties of CMCh-Eu3+/Tb3+ were characterized and analyzed by infrared spectroscopy, XPS, TG and Judd-Ofelt theory, thus the chemical structure of CMCh-Eu3+/Tb3+ was determined. The mechanism of energy transfer was explained in detail, also the Förster resonance transfer model is confirmed, and the hypothesis of energy transfer back was verified by the characterization and calculation methods of fluorescence spectra, UV spectra, phosphorescence spectra and fluorescence lifetime. Finally, CMCh-Eu3+/Tb3+ with different molar ratios were used to prepare a series of multicolor LED lamps, and it extends the application range of biological macromolecules as ligands.

Tunable and Efficient Photoluminescence of Lanthanide-Doped Cs2NaScCl6 Double Perovskite Single Crystals toward Multifunctional Light-Emitting Diode Applications.

Lead-free halide double perovskite, as one of the promising candidates for lead halide perovskite materials, shows great potential in light-emitting diodes (LEDs), benefiting from its environmental friendliness and high chemical stability. However, the poor regulation of the emission spectra severely limits its application range. Herein, various lanthanide ions were successfully doped in Cs2NaScCl6 double perovskite single crystals (DPSCs) to yield effective and stable emissions spanning from visible to near-infrared (NIR) regions. Notably, efficient energy transfer from the host to the dopants enables tunable emissions with good chromaticity, which is rarely reported in the field of lead-free double perovskite. Moreover, density functional theory calculations reveal that the high local electron density around the [LnCl6]3- octahedron in DPSCs plays a key role in the improvement of photoluminescence quantum yields (PLQYs). The optimal PLQYs are up to 84%, which increases around 3 times over that of the undoped sample. Finally, multicolor and NIR LEDs based on Ln3+-doped Cs2NaScCl6 DPSCs were fabricated and had different application functions. Specifically, the single-composite white LED shows adjustable coordinates and correlated color temperatures, while the NIR LED shows good night vision imaging. This work provides new inspiration for the application of efficient multifunctional LEDs based on lead-free double perovskite materials.

Plasmon-Controlled Selective Emission Enhancement of Eu3+ with (Au Core)@(Y(V,P)O4:Eu) Nanostructures.

Plasmonic nanostructures have a capability to control the photoluminescence (PL) emission properties of optical species and thus can dramatically enhance the performances of diverse optical systems and devices. Lanthanide ions typically exhibit multiple PL emission lines. Systematic studies on the plasmon-enabled selective enhancement for the different emission lines of lanthanide ions are still highly desired in order to achieve the fine manipulation on the spectral profile and luminescence intensity ratio (LIR). Herein we report on the synthesis and PL emission properties of monodisperse spherical (Au core)@(Y(V,P)O4:Eu) nanostructures, which integrate the plasmonic and luminescent units into an individual core@shell structure. The localized surface plasmon resonance adjusted through control of the size of the Au nanosphere core enables the systematic modulation of the selective emission enhancement of Eu3+. As revealed by single-particle scattering and PL measurements, the five luminescence emission lines of Eu3+ originating from the 5D0,1 excitation states are affected by the localized plasmon resonance to different extents, which are dependent on both the dipole transition nature and the intrinsic quantum yield of the emission line. Based on the plasmon-enabled tunable LIR, high-level anticounterfeiting and optical temperature measurements for photothermal conversion are further demonstrated. Our architecture design and PL emission tuning results offer many possibilities for constructing multifunctional optical materials by integrating plasmonic and luminescent building blocks into hybrid nanostructures with different configurations.

Time-resolved Fluorescence DNA-based Sensors for Reducing Background Fluorescence of Environment.

The fluorescence assay is one of the popular methods that is applied for detection of different targets. However, this method may show low sensitivity and high background in biological samples due to the natural fluorescence of different compounds in complicated samples. In addition, it inevitably affects the detection results accuracy. A fundamental solution to this problem is the use of the time-resolved fluorescence technique (TRF). The main component of this technique is the use of long fluorescence lifetime reagents. In this review, various time-resolved fluorescent reagents such as complexes of lanthanide ions, lanthanide-doped inorganic nanoparticles; Mn-doped ZnS quantum dots (QDs) and pyrene excimer are introduced. Moreover, TRF sensors, especially TRF aptasensors (DNA-based sensors) are discussed. This review will give new ideas for researchers to develop novel high-sensitive TRF sensors that can remove or decrease background fluorescence and use them for the detection of various targets in complicated samples without treatment.