Photoluminescence properties of rare‐earth‐doped (Er3+,Yb3+) Y2O3 nanophosphors by a combustion synthesis method

In this work, we report the synthesis of Y₂O₃:Er³⁺, Y₂O₃:Yb³⁺ and Y₂O₃:Er³⁺,Yb³⁺ nanophosphors by the combustion synthesis method using urea as fuel. The doping agents were incorporated in the form of erbium nitrate and ytterbium nitrate. X‐Ray diffraction (XRD) patterns revealed that the synthesized particles have a body‐centered cubic structure with space group Ia‐3. The photoluminescence (PL) properties were investigated after UV and infrared irradiation at room temperature. A strong characteristic emission of Er³⁺ and Yb³⁺ ions was identified, and the influence of doping concentration on the PL properties was systematically studied. Energy transfer from Yb³⁺ to Er³⁺ ions was observed in Y₂O₃ nanophosphors. The obtained result may be useful in potential applications such as bioimaging. Copyright © 2015 John Wiley & Sons, Ltd.     

Interaction of phospholipids (Lysophosphatidylethanolamines) with water and sodium cation

We have performed detailed ab initio SCF calculations on the intermolecular interaction energies for one Na⁺ ion and one water molecule with two molecular fragments, one exemplifying a phospholipid (PL) head (PLHD) and the other, a phospholipid tail (PLTL). A 6-12-1 atom-atom pair potential for the interaction of a Na⁺ ion and water with a lysophosphatidyl-ethanolamine (LPEA) was derived from these results by a fitting procedure. This fitted potential was used to obtain isoenergy maps that provide energy profiles of the Na⁺ ion and the water around the phospholipids. The interaction of the Na⁺ ion with PL, as well as the interaction of water with the PL, can be visualized from these maps, which, as expected, show regions of hydrophilicity and hydrophobicity for the water and indicate a very strong binding site for the Na⁺ ion on the phosphate. It appears to be a stationary site that would limit the Na⁺ ion mobility. This binding site is located near the double-bonded oxygen atom of the phosphate group; its binding energy for Na⁺ is 67 kcal/mol. On the other hand the NH⁺ group of PLHD ahows strong electrostatic repulsion of Na⁺ while interacting with water with a binding energy of 13 kcal/mol. This potential energy well region for water is separated from another of similar depth near the phosphate by a barrier and both regions are expected to act as binding sites for water.     

The structure and luminescence properties of Mn2+/Eu2+/Er3+‐doped MgO‐Ga2O3‐SiO2 glasses and glass‐ceramics

The MgO–Ga₂O₃–SiO₂ glasses and glass‐ceramics samples doped with Eu²⁺/Mn²⁺/Er³⁺ and heated in reductive atmosphere were prepared by the sol–gel method. The structure, morphology and the luminescence properties were studied using X‐ray diffraction, high‐resolution transmission electron microscope, fluorescence spectra, and up‐conversion emission. The luminescence characteristics of doped ions could be influenced by temperature and matrix component. The characteristic emission of Mn²⁺, Eu²⁺ and Er³⁺ were seen and the energy transfer efficiency from Eu²⁺ to Mn²⁺ was enhanced as Mn²⁺ concentration was increased. In addition, the two‐photon process was determined for the Er³⁺‐doped samples.     

Tunable emission,energy transfer and charge compensation in SrMoO4:Sm3+,Tb3+,Na+ phosphor

A series of SrMoO₄:Sm³⁺,Tb³⁺,Na⁺ phosphors was synthesized using a high‐temperature solid‐state reaction method in air. On excitation at 290 nm, SrMoO₄:Sm³⁺,Tb³⁺ phosphor emitted light that varied systematically from green to reddish‐orange on changing the Sm³⁺ and Tb³⁺ ion concentrations. The emission intensities of SrMoO₄:Sm³⁺ and SrMoO₄:Sm³⁺,Tb³⁺ phosphors were increased two to four times due to charge compensation when Na⁺ was added as a charge compensator. The luminescence mechanism and energy transfer could be explained using energy‐level diagrams of the MoO₄^2– group, Sm³⁺ and Tb³⁺ ions. SrMoO₄:Sm³⁺,Tb³⁺,Na⁺ could be used as reddish‐orange phosphor in white light‐emitting diodes (LEDs) based on an ~ 405 nm near‐UV LED chip. This research is helpful in adjusting and improving the luminescence properties of other phosphors. Copyright © 2015 John Wiley & Sons, Ltd.     

Distance measurements between the metal-binding sites in thermolysin using terbium ion as a fluorescent probe.

A single terbium ion has been introduced into thermolysin replacing two of the four calcium ions, and the fluorescence properties of the protein-bound terbium have been studied. The fluorescence of Tb⁺³ is tremendously enhanced (～7 × 10³) upon binding and is significantly quenched when divalent cobalt is substituted for the zinc ion normally found in the enzyme. By use of the Förster equation for energy transfer the distance between the protein-bound Tb⁺³ and Co⁺² in the active site was calculated to be 13.6±0.5 A. This agrees closely with the value of 13.9 A obtained from the crystal structure and suggests that energy transfer between the two metal ions bound to the protein takes place by a dipole-dipole mechanism.     

Luminescent properties of 4‐aminobenzo‐15‐crown‐5 after preferential binding of ferric ions in aqueous solutions

We report a combined approach that introduces the use of 4‐aminobenzo‐15‐crown‐5 (4AB15C5) for the detection of ferric(III) ions by colorimetric, ultraviolet (UV)–visible light absorption, fluorescence, and live‐cell imaging techniques along with density functional theory (DFT) calculations. We have found that 4AB15C5 is sensitive and selective for binding ferric(III) ions in aqueous solutions. DFT calculations using the polarizable continuum model have been used to explain the strong binding of the ferric ion by 4AB15C5 in aqueous solutions. The detection limit in the fluorescence quenching measurements was found to be as low as 50 μM for the ferric ion with a determined Stern–Volmer constant of 1.52 × 10⁴ M^?1. Fluorescence intensity did not change for other ions tested, Fe²⁺, Co²⁺, Mn²⁺, Mg²⁺, Zn²⁺, Ca²⁺, NH₄⁺, Na⁺, and K⁺ ions. Live‐cell fluorescence imaging was also used to check the intracellular variations in ferric ion levels. Our spectroscopic data indicated that 4AB15C5 can bind ferric ions selectively in aqueous solutions.     

Preparation and up‐conversion luminescence properties of LaOBr:Yb3+/Er3+ nanofibers via electrospinning

LaOBr:Yb³⁺/Er³⁺ nanofibers were synthesized for the first time by calcinating electrospun PVP/[La(NO₃)₃ + Er(NO₃)₃ + Yb(NO₃)₃ + NH₄Br] composites. The morphology and properties of the final products were investigated in detail using scanning electron microscopy (SEM), energy dispersion spectroscopy (EDS), X‐ray diffractometry (XRD) and fluorescence spectroscopy. The results indicate that LaOBr:Yb³⁺/Er³⁺ nanofibers are tetragonal in structure with a space group of P4/nmm. The diameter of LaOBr:Yb³⁺/Er³⁺ nanofibers is ~ 147 nm. Under the excitation of a 980‐nm diode laser, LaOBr:Yb³⁺/Er³⁺ nanofibers emit strong green and red up‐conversion emission centering at 519, 541 and 667 nm, ascribed to the ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴ F_9/2 → ⁴I_15/2 energy‐level transitions of Er³⁺ ions, respectively. The up‐conversion luminescent mechanism of LaOBr:Yb³⁺/Er³⁺ nanofibers is advanced. Moreover, near‐infrared emission of LaOBr:Yb³⁺/Er³⁺ nanofibers is obtained under the excitation of a 532‐nm laser. The formation mechanism of LaOBr:Yb³⁺/Er³⁺ nanofibers is proposed. LaOBr:Yb³⁺/Er³⁺ nanofibers could be important up‐conversion luminescent materials. Copyright © 2014 John Wiley & Sons, Ltd.     

Influence of Er3+ concentration on the photoluminescence characteristics and excitation mechanism of Gd2O3:Er3+ phosphor synthesized via a solid‐state reaction method

An Er³⁺‐doped phosphor of Gd₂O₃ (Gd₂O₃:Er³⁺) was prepared using a conventional solid‐state reaction method. The structure and particle size were determined from X‐ray powder diffraction measurements. The average particle size of the phosphor was in between 20 and 50 nm. The particle size and structure of the phosphor were further confirmed by transmission electron microscopy (TEM) analysis. Luminescence spectra were recorded under excitation wavelengths of 275, 380, 515 and 980 nm. The visible upconversion and downconversion luminescence spectra of the Gd₂O₃:Er³⁺ phosphor were investigated as a function of Er³⁺ ion concentration. The upconverted emission at 980 nm excitation shows enhanced red emission with respect to green emission as the dopant concentration increased. Similar results were observed for downconversion emission under 275 and 380 nm excitation wavelengths. The mechanisms responsible for populating the ⁴S_3/2 and ⁴ F_9/2 levels, for green and red emissions, respectively, are different for different excitations and for different concentrations of Er³⁺. Copyright © 2014 John Wiley & Sons, Ltd.     

Dependence of the optical absorption and Na+ binding energies of coumarin-crown ethers on the size and attachment position of ether ring: density functional investigation

The crowned coumarin complexes are well known compounds for their ion recognition abilities. They undergo photophysical changes upon cation binding. On the basis of density functional theory calculations, we examined the sodium cation (Na⁺) binding energies of coumarin-crown ethers based on 15-Crown-5 (15 C5) and 18-Crown-6 (18 C6) as well as the optical absorptions of coumarin-crown ethers based on 12-Crown-4 (12 C4), 15 C5 and 18 C6. We explored why the attachment of crown ether ring to coumarin affects the Na⁺ binding energies of coumarin-crown ethers and also why the optical absorption of coumarin is modified by the crown ethers. Our study reveals that the Na⁺ ion binding energies of coumarin-crown ethers depend strongly on the size of the crown ether ring and also on the attachment position of the ether ring on coumarin. These factors affect the intramolecular charge transfer and overall stability of the complexes. The absorptions of the coumarin and ether ring parts of coumarin-crown ether are red shifted from those of isolated coumarin and crown ether, respectively. The red-shift of the coumarin ester group absorption is much stronger depending on the attachment position of the ether ring to coumarin. The absorption intensity of the coumarin part in coumarin-crown ethers is reduced for the benzene group absorption, but is enhanced for the ester group absorption.

Effect of annealing on down‐conversion properties of monoclinic Gd2O3:Er3+ nanophosphors

Erbium‐doped nano‐sized Gd₂O₃ phosphor was prepared by a solution combustion method in the presence of urea as a fuel. The phosphor was characterized by X‐ray diffractometry (XRD), Fourier transform infra‐red spectroscopy, energy dispersive X‐ray analysis (EDX) and transmission electron microscopy (TEM). The results of the XRD shows that the phosphor has a monoclinic phase, which was further confirmed by the TEM results. Particle size was calculated by the Debye–Scherrer formula. The erbium‐doped Gd₂O₃ nanophosphor was revealed to have good down‐conversion (DC) properties and the intensity of phosphor could be modified by annealing. The effects of annealing at 900°C on the particle size and luminescence properties were studied and compared with freshly prepared Gd₂O₃:Er³⁺ nanoparticles. The average particle sizes were calculated as 8 and 20 nm for the freshly prepared samples and samples annealed at 900°C for 1 h, respectively. The results show that both freshly prepared and annealed Gd₂O₃:Er³⁺ have monoclinic structure. Copyright © 2014 John Wiley & Sons, Ltd.     

Ion Selectivity of the Cytoplasmic Binding Sites of the Na,K-ATPase: I. Sodium Binding is Associated with a Conformational Rearrangement

To investigate Na⁺ binding to the ion-binding sites presented on the cytoplasmic side of the Na,K-ATPase, equilibrium Na⁺-titration experiments were performed using two fluorescent dyes, RH421 and FITC, to detect protein-specific actions. Fluorescence changes upon addition of Na⁺ in the presence of various Mg²⁺ concentrations were similar and could be fitted with a Hill function. The half-saturating concentrations and Hill coefficients determined were almost identical. As RH421 responds to binding of a Na⁺ ion to the third neutral site whereas FITC monitors conformational changes in the ATP-binding site or its environment, this result implies that electrogenic binding of the third Na⁺ ion is the trigger for a structural rearrangement of the ATP-binding moiety. This enables enzyme phosphorylation, which is accompanied by a fast occlusion of the Na⁺ ions and followed by the conformational transition E₁/E₂ of the protein. The coordinated action both at the ion and the nucleotide binding sites allows for the first time a detailed formulation of the mechanism of enzyme phosphorylation that occurs only when three Na⁺ ions are bound. Received: 8 October 1998/Revised: 29 December 1998     

Plasmonic Coupling in Er3+:Au Tellurite Glass

In this paper, we report on luminescence and absorbance effects of Er⁺³:Au-doped tellurite glasses synthesized by a melting-quenching and heat treatment technique. After annealing times of 2.5, 5.0, 7.5, and 10.0 h, at 300 °C, the gold nanoparticles (GNP) effects on the Er⁺³ are verified from luminescence spectra and the corresponding levels lifetime. The localized surface plasmon resonance around 800 nm produced a maximum fluorescence enhancement for the band ranging from 800 to 840 nm, corresponding to the transitions ⁴H_11/2 → ⁴I_13/2 (805 nm) and ⁴S_3/2 → ⁴I_13/2 (840 nm), with annealing time till 7.5 h. The measured lifetime of the levels ⁴H_11/2 and ⁴S_3/2 confirmed the lifetime reduction due to the energy transfer from the GNP to Er⁺³, causing an enhanced photon emission rate in these levels.     

Tunable photoluminescence properties of Sr1‐yCayMoO4:Sm3+ phosphors (0 ≤ y < 1)

A series of Sr_1‐x‐yCa_yMoO₄:xSm³⁺ (0 ≤ x ≤ 7 mol% and 0 ≤ y < 1) phosphors was synthesized by a conventional solid‐state reaction method in air, and their structural and spectroscopic properties were investigated. The optimal doping concentration of Sm³⁺ in SrMoO₄:Sm³⁺ phosphor is 5 mol%. Under excitation with 275 nm, in Sr_1‐x‐yCa_yMoO₄:xSm³⁺ (0 ≤ x ≤ 7 mol% and 0 ≤ y < 1) phosphors, the emission band of the host was found to overlap with the excitation bands peaking at ~500 nm of Sm³⁺ ion, and the energy transfer from MoO₄^2? group to Sm³⁺ ion can also be observed. The International Commission on Illumination (CIE) chromaticity coordinates of Sr_0.95‐yCa_yMoO₄:0.05Sm³⁺ phosphors with excitation 275 nm varied systematically from an orange (0.4961, 0.3761) (y = 0) to a white color (0.33, 0.3442) (y = 0.95) with increasing calcium oxide (CaO) concentration. However, Sr_0.95‐yCa_yMoO₄:0.05Sm³⁺ phosphors with excitation at 404 nm only showed red emission and the energy transfer between MoO₄^2? group to Sm³⁺ ion was not observed. The complex mechanisms of luminescence and energy transfer are discussed by energy level diagrams of MoO₄^2? group and Sm³⁺ ion. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of erbium ion concentration on structural and luminescence properties of lead borosilicate glasses for fiber amplifiers

This investigation reports, the effect of the concentration of erbium and lead ions on the physical, structural and optical properties of lead borosilicate glasses. These glasses were synthesized by the melt quench method. In the synthesis, the concentration of the erbium (Er³⁺) ion was varied in the order of 0.0, 0.1, 0.5, 1.0 and 2.0 mol% and lead (Pb²⁺) ion was varied in the order of 30, 29.9, 29.5, 29 and 28 mol%. The glasses were analyzed using X‐ray diffraction (XRD), Fourier transform infrared (FT‐IR) and UV–vis–NIR spectroscopy. From XRD, the amorphous nature of lead borosilicate glasses was confirmed. The functional groups which were present in the glasses have been identified by analyzing the FT‐IR spectrum. From the absorption spectra, the oscillator strengths as well as the Judd–Ofelt (JO) intensity parameters were determined and compared with other hosts. The JO intensity parameters were further used to calculate certain radiative properties for the excited luminescent levels of Er³⁺ ion. From emission spectra, full width at half maxima (FWHM), stimulated emission cross‐sections (σ_e) and certain lasing parameters were evaluated and compared with reference host glasses. The lifetimes of ⁴I_13/2 excited level of Er³⁺ ion have also been recorded and analyzed. The calculated and experimental lifetimes were compared in terms of quantum efficiencies. From the photoluminescence analysis, the erbium doped lead borosilicate glasses well suited for optical fiber amplifiers are discussed.     

Two‐channel near‐infrared fluorescence Ag+ ion sensing of a new star‐shaped dendrimer

A new near‐infrared fluorescence sensor PDI‐PD for Ag⁺ ions was successfully prepared and its structure characterized by ¹H nuclear magnetic resonance (NMR), ¹³C NMR and high‐resolution mass spectrometry; matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (HRMS MALDI‐TOF). The probe exhibited rapid, sensitive, and selective two‐channel fluorescence responses towards Ag⁺ ions and protons. The probe has a marked high binding affinity and high sensitivity for Ag⁺, with a detection limit of 1.4 × 10^?6 M. An approximately five‐fold enhanced core emission at 784 nm was attributed to fluorescence resonance energy transfer (FRET). The enhanced core emission of the probe with Ag⁺ ions based on photo‐induced electron transfer and FRET is discussed. In addition, the probe presented a visible colour change. All experimental results demonstrated that PDI‐PD is an efficient tool for the selective, sensitive and rapid detection of Ag⁺ ions and protons using two‐channel fluorescence responses.     

Synthesis and characterization of erbium‐doped YAlO3 phosphor

In the yttrium aluminium system, the YAlO₃ phosphor is a prominent host because of the yttrium aluminium ratio (1:1). Phosphor was synthesized by the solid‐state reaction method at variable concentrations of erbium (0.1–2.5 mol%). This method is suitable for large‐scale production and is a less time‐consuming method when compared with the soft synthesis method. The prepared sample was characterized by X‐ray diffraction technique and the crystallite size was calculated by Scherer's formula. Vibrational and bending analysis of prepared phosphor for optimized concentration of erbium ion is described based on the Fourier transform infrared spectroscopic technique. The photoluminescence (PL) emission spectra of prepared phosphor for variable concentrations of erbium ion were recorded and the excitation spectrum was found to be at 291 nm with three shoulder peaks at 305, 270 and 242 nm. For 291 nm excitation, the emission spectrum was found at 546 nm and 552 nm. PL intensity increased with increasing concentrations of erbium and after 2 mol% emission intensity decreased due to concentration quenching. Spectrophotometric determination of YAlO₃:Er³⁺ is described by CIE co‐ordinates and shows an intense emission in the green region such that the prepared phosphor can act as a single host for green light emission. Thermoluminescence glow curve analysis of the YAlO₃:Er³⁺ phosphor was recorded for different ultraviolet (UV) light exposures and gamma exposure. Different gamma doses 0.5–2 kGy show a linear response. Kinetic parameters were calculated by the peak shape method. Copyright © 2015 John Wiley & Sons, Ltd.     

Spectral‐converting study of Ba9–3(m+n)/2ErmYbnY2Si6O24 (m = 0.005 – 0.2, n = 0 – 0.3) orthosilicate phosphors

Optical materials composed of Ba_9–3(m+n)/2Er_mYb_nY₂Si₆O₂₄ (m = 0.005–0.2, n = 0–0.3) were prepared using a solid‐state reaction. The X‐ray diffraction patterns of the obtained phosphors were examined to index the peak positions. The photoluminescence (PL) excitation and emission spectra of the Er³⁺‐activated phosphors and the critical emission quenching as a function of Er³⁺ content in the Ba_9–3m/2Er_mY₂Si₆O₂₄ structure were monitored. The spectral conversion properties of Er³⁺ and Er³⁺–Yb³⁺ ions doped in Ba₉Y₂Si₆O₂₄ phosphors were elucidated under diode‐laser irradiation at 980 nm. Up‐conversion emission spectra and the dependence of the emission intensity on pump power for the Ba_8.55Er_0.1Yb_0.2Y₂Si₆O₂₄ phosphor were investigated. The desired up‐conversion of the emitted light, which passed through the green, yellow, orange and red regions of the spectrum, was achieved through the use of appropriate Er³⁺ and/or Yb³⁺ concentrations in the host structure and 980 nm excitation light. The up‐conversion mechanism in the phosphors is described by an energy‐level schematic. Copyright © 2015 John Wiley & Sons, Ltd.     

A Novel Graphene Oxide Wrapped Na2Fe2(SO4)3/C Cathode Composite for Long Life and High Energy Density Sodium‐Ion Batteries

The cathode materials in the Na‐ion battery system are always the key issue obstructing wider application because of their relatively low specific capacity and low energy density. A graphene oxide (GO) wrapped composite, Na₂Fe₂(SO₄)₃@C@GO, is fabricated via a simple freeze‐drying method. The as‐prepared material can deliver a 3.8 V platform with discharge capacity of 107.9 mAh g^?1 at 0.1 C (1 C = 120 mA g^?1) as well as offering capacity retention above 90% at a discharge rate of 0.2 C after 300 cycles. The well‐constructed carbon network provides fast electron transfer rates, and thus, higher power density also can be achieved (75.1 mAh g^?1 at 10 C). The interface contribution of GO and Na₂Fe₂(SO₄)₃ is recognized and studied via density function theory calculation. The Na storage mechanism is also investigated through in situ synchrotron X‐ray diffraction, and pseudocapacitance contributions are also demonstrated. The diffusion coefficient of Na⁺ ions is around 10^?12–10^?10.8 cm² s^?1 during cycling. The higher working voltage of this composite is mainly ascribed to the larger electronegativity of the element S. The research indicates that this well‐constructed composite would be a competitive candidate as a cathode material for Na‐ion batteries.     

Enhanced green emissions of Er3+/Yb3+ co‐doped Gd2(MoO4)3 by co‐excited up‐conversion processes

Improving the emission from rare earth ions doped materials is of great importance to broaden their application in bio‐imaging, photovoltaics and temperature sensing. The green emissions of Gd₂(MoO₄)₃:Er³⁺/Yb³⁺ powder upon co‐excitation with 980 and 808 nm lasers were investigated in this paper. Distinct enhancement of green emissions was observed compared with single laser excitation. Based on the energy level structure of Er³⁺, the enhancement mechanism was discussed. Moreover, the result of temperature‐dependent enhancement revealed that the enhancement factor reached its maximum (2.5) as the sample heated to 120°C, which is due to the competition of two major thermal effects acting in the co‐excited up‐conversion processes. In addition, the same enhancement of green emissions was also observed in Gd₂(MoO₄)₃:Er³⁺ powder and NaYF₄:Er³⁺/Yb³⁺ powder.