Investigation on Energy Transfer and Luminescent Properties of K3Gd(PO4)2:RE3+ (RE = Eu,Tb) Under UV and VUV Excitation

K₃Gd(PO₄)₂:RE³⁺ (RE = Eu, Tb) are prepared by solid‐state reaction and their photoluminescence (PL) properties are investigated under UV and VUV excitation, respectively. The obtained experimental data show that no energy transfer happens among the activator ions Tb³⁺ or Eu³⁺ under UV excitation. Under 147‐nm excitation, the strongest emission intensity of K₃Gd(PO₄)₂:RE³⁺ (RE = Eu, Tb) is obtained when the activator ions Tb³⁺ or Eu³⁺ concentration is 0.8 mol, the integrate emission intensity of K₃Gd_0.2(PO₄)₂:0.8Tb³⁺ is about 204% of commercial phosphor Zn_1.96SiO₄:0.04Mn²⁺ with chromaticity coordinates of (0.340, 0.561) and the decay time of about 5.09 ms under 147‐nm excitation. We analyze the experimental data and propose a possible energy‐transfer mechanism under 147‐nm excitation.     

Luminescence Properties and Energy Transfer of Ce3+,Tb3+‐Coactivatedβ‐SiAlON Phosphors

Using the solid‐state reaction method, Ce³⁺,Tb³⁺‐coactivated Si₅AlON₇ (Si_6?zAl_zO_zN_8?z, z = 1) phosphors were successfully synthesized. The obtained phosphors exhibit high absorption and strong excitation bands in the wavelength range of 240–440 nm, matching well with the light emitting‐diode (LED) chip. The ET from Ce³⁺ to Tb³⁺ ions in Si₅AlON₇:Ce³⁺,Tb³⁺ has been studied and demonstrated by the luminescence spectra and decay curves. Moreover, the phosphors show tunable emissions from blue to green by tuning the relative ratio of the Ce³⁺ to Tb³⁺ ions. Thermal quenching properties of Si₅AlON₇:Ce³⁺,Tb³⁺ had also been investigated and the quenching temperature is ~190°C. These results show that Si₅AlON₇:Ce³⁺,Tb³⁺ could be a promising candidate for a single‐phased color‐tunable phosphor applied in UV‐chip pumped LEDs.     

Composition-dependent intrinsic defect structures in pyroclore RE2B2O7 (RE = La,Nd, Gd; B = Sn,Hf, Zr)

Point defects are closely correlated with various properties of pyrochlore oxides and therefore play a key role on their engineering applications. Here, the native point defect complexes in RE₂B₂O₇ (RE = La, Nd, Gd; B = Sn, Hf, Zr) under stoichiometric and nonstoichiometric compositions are studied by first-principles calculations. The O Frenkel defect complex is predicted to be the predominant defect structure in stoichiometric zirconates and hafnates, whereas the cation antisite defect complex is the predominant one in stannates. In the case of BO₂ excess, the formation of the B-RE antisite defect together with the RE vacancy and the oxygen interstitial is energetically favorable, whereas the RE-B antisite defect together with the oxygen vacancy and the RE interstitial is preferable under the RE₂O₃ excess environments. Additionally, the formation energies of the native defect complexes are greatly affected by the B-site and/or RE-site cations. The strategy on tailoring the intrinsic defect structures of these pyrochlore oxides is proposed. It is expected to guide the experiments on the defect-related property optimization through stoichiometric and nonstoichiometric compositions, so as to meet the specific engineering requirements and promote their commercial applications.     

Photostimulated and Long Persistent Luminescence Properties from Different Crystallographic Sites of β‐Sr2SiO4: Eu2+, R3+ (R = Tm,Gd)

Sintered ceramics of β‐Sr₂SiO₄: Eu²⁺, R³⁺(R=Tm, Gd) were prepared and their spectroscopic properties were evaluated. A large enhancement of green photostimulated luminescence (PSL) was observed from β‐Sr₂SiO₄:Eu²⁺ codoping with Tm³⁺ at a recognizable intensity level, and the most efficient PSL was obtained when the codoping concentration of Tm³⁺ was 0.002. It was proved that the introduction of Tm³⁺ created a large number of oxygen vacancies which serve as traps for electrons excited by UV irradiation. In addition, a distinguishable difference between the photoluminescence (PL) and PSL spectra of β‐Sr₂SiO₄: Eu²⁺, Tm³⁺ was observed, namely the PSL spectrum exhibits only a symmetric emission band peaked at about 540 nm while both 470 and 540 nm peaks were detected in the PL spectrum. It is safe to say that PSL only derives from one emission center of Eu2 in the crystallographic Sr2 sites, which could be ascribed to the different distribution of trap centers for two crystallographic Sr sites .     

Rare earth ion (RE = Tb/Eu/Dy) doped nanocrystalline oxyfluoride glass-ceramic 5BaF2–95SiO2

A series of 5BaF₂-95SiO₂: RE³⁺ (rare earth, RE = Tb/Eu/Dy) glass-ceramics samples, containing BaF₂ nanocrystals with a size of about 5 nm, are successfully synthesized by a sol-gel method under different atmospheric conditions. The structural characteristics, the optical properties, and the thermal stability of the target materials were carried out in this work. According to the X-ray diffraction results, it was observed that the initial Ba(NO₃)₂ crystals are transformed into BaF₂ crystals in SiO₂ glasses during the heat treatment at 650°C. After the calcination, the emission peak intensity related to rare earth ions is significantly higher than that in the xerogel. Meanwhile, the addition of Dy³⁺ can enhance the emission intensity of Tb³⁺ in the co-doped materials. The internal quantum efficiency of the 0.3%Tb³⁺-0.3%Dy³⁺ co-doped product reaches up to ∼50.8%. In addition, the color coordinates of the International Commission (CIE) indicate that the Dy-0.3%Eu co-doped 5BaF₂–95SiO₂ sample could provide red, orange, or blue color emission depending on the Dy³⁺ doping concentration. Moreover, the thermal stability of all the 5BaF₂–95SiO₂:RE³⁺(RE = Tb/Eu/Dy) glass-ceramic shows well, especially 5BaF₂–95SiO₂:0.3%Eu³⁺-0.1%Dy³⁺, whose emission intensity would still maintain more than 90% of the initial strength as rising in temperature. Therefore, by designing the Dy³⁺ doping concentration, the 5BaF₂-95SiO₂:0.3%Eu³⁺-0.1%Dy³⁺ glass-ceramic has potential practical values in high-performance white light emitting diode.     

Photoluminescence Properties of Color‐Tunable Ca3La6(SiO4)6: Ce3+, Tb3+ Phosphors

A series of newly developed color‐tunable Ca₃La₆(SiO₄)₆: Ce³⁺, Tb³⁺ phosphors were successfully prepared in this study. The crystal structures of the prepared phosphors were revealed to be hexagonal with space group P6₃/m, and the lattice parameters were evaluated via utilizing the Rietveld refinement method. Upon excitation at 288 nm, the emission spectra of Ce³⁺and Tb³⁺ ions co‐doped Ca₃La₆(SiO₄)₆ phosphors included a blue emission band and several emission lines. The blue emission band with a peak at 420 nm originated in the f–d transitions of Ce³⁺ ions, and the emission lines in the range of 450–650 nm were assigned to the ⁵D₄ → ⁷F_J (J = 6, 5, 4, 3) transitions of Tb³⁺ ions. Increasing the doping content of Tb³⁺ ions considerably strengthened Tb³⁺ emission and reduced Ce³⁺ emission owing to the energy transfer from Ce³⁺ to Tb³⁺ ions. The mechanism of the energy transfer was confirmed to be a dipole–dipole interaction. The effective energy transfer from Ce³⁺ to Tb³⁺ ions caused a color shift from purplish‐blue to yellowish‐green. Color‐tunable Ca₃La₆(SiO₄)₆: Ce³⁺, Tb³⁺ phosphors have the potential to be utilized in light‐emitting diodes with proper modulation of the amount of Tb³⁺ ions.     

Structure and Luminescence of New Red‐Emitting Materials‐Eu3+‐Doped Triple Orthovanadates NaALa(VO4)2 (A = Ca,Sr, Ba)

The new red‐emitting phosphors of Eu³⁺‐doped triple orthovanadates NaALa(VO₄)₂ (A = Ca, Sr, Ba) were prepared by the high‐temperature solid‐state reaction. The formation of single phase compound with isostructural structure of Ba₃(VO₄)₂ was verified through X‐ray diffraction (XRD) studies. The photoluminescence excitation and emission spectra, the fluorescence decay curves and the dependence of luminescence intensity on doping level were investigated. The phosphor can be efficiently excited by near UV and blue light to realize an intense red luminescence (613 nm) corresponding to the electric dipole transition ⁵D₀→⁷F₂ of Eu³⁺ ions. Their potential applications as red‐emitting phosphors for solid‐state lighting were evaluated in comparison with the Eu³⁺‐doped lanthanum orthovanadate LaVO₄ and other reported references. The luminescence was discussed in detail on the base of the crystal structures. The luminescence thermal stability on temperature was investigated and the thermal activated energy was calculated. The phosphors can be suggested to be a potential red‐emitting phosphor for the application on white LEDs under irradiation of near‐UV or blue chips.     

Synthesis of Red‐Emitting AgGd0.9Eu0.1(MoO4)2 Phosphors by Precipitation at Room Temperature

A series of Eu³⁺‐doped AgGd(MoO₄)₂ red phosphors with well‐defined shape and size were prepared via a precipitation method at room temperature. The samples were characterized by X‐ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and photoluminescence (PL) spectroscopy. The crystallinity, particle size, morphology, and luminescent properties of the as‐prepared products were tuned by controlling the reaction conditions such as the precipitation reagents used and the pH of the initial solution. XRD results showed that all of the synthesized samples adopted a pure tetragonal structure. The formation mechanism of AgGdMo₂O₈ was investigated in detail, and two intermediates were found to be essential. Photoluminescence properties of the as‐prepared AgGd_0.9Eu_0.1(MoO₄)₂ phosphors under diverse experimental conditions were also studied systematically, and their emission spectra showed emission characteristic of Eu³⁺.     

Enhanced Luminescence of Ca14Mg2Si8O28+δN4−δ:Eu2+Phosphors by Codoping Ce3+, Mn2+ for White LEDs and Their Energy‐Transfer Mechanism

The Eu²⁺, M‐codoped(M = Ce³⁺, Mn²⁺) phosphor powders were prepared by a solid‐state reaction. The addition of Ce³⁺ in the Eu²⁺ sites in partially nitridated bredigite‐structure phosphor(CMSN) remarkably enhances the luminescent intensity by ~180% through sensitized luminescence. Dual band emission was observed for Eu, Mn‐codoped CMSN through energy transfer from Eu²⁺ to Mn²⁺. Ce³⁺–Eu²⁺ and Eu²⁺–Mn²⁺ energy‐transfer mechanism was investigated through decay profile analysis using Inokuti–Hirayama model and energy‐transfer parameters are determined. Interaction mechanism was identified as dipole–dipole interaction. In addition, phosphor in glass plates was prepared using the phosphor and its feasibility in white LED application was studied and is presented.     

Synthesis of γ‐Fluoro‐α, β‐unsaturated Carboxylic Esters from Saturated α‐Fluoro Aldehydes

γ‐Fluoro‐α, β‐unsaturated carboxylic esters 7a, 7b and 7d and 4‐fluoro‐4‐phenylbut‐3‐enoic ester ( 8 ) are obtained by two alternative pathways from 2‐fluoro aldehydes 5a—d , either by Horner—Wadsworth—Emmons reaction or by Wittig reaction. The aldehydes 5a—d are prepared by Swern oxidation of the corresponding fluorohydrins 4a—d . These are available from α‐olefins by bromofluorination, bromineby‐acetate replacement and subsequent hydrolysis.     

Uniform colloidal spheres for RE3BO6 (RE = Eu-Yb,Y) and excitation-dependent luminescence of Y3BO6:Eu3+ red phosphor

Phosphor particles of spherical shape and uniform size are desired for high-definition displays to improve the resolution and the overall luminescent performance. However, the synthesis of RE₃BO₆ spherical particles is a considerable challenge in materials science. Here, uniform spheres of RE₃BO₆ (RE = Eu–Yb, Y) have been converted from their colloidal precursor spheres synthesized via homogeneous precipitation. The amorphous precursor spheres are solid particles with decreased boron going from the surfaces to the cores. Smaller particles were observed at decreased ionic radius from Eu³⁺ to Ho³⁺ (including Y³⁺), but particles with nearly unvaried sizes were observed by further decreasing the ionic radius from Ho³⁺ to Yb³⁺. They crystallized in monoclinic RE₃BO₆ at 900°C, with maintaining the spherical shape of precursors. However, the crystal growth and the densification toward the particle surfaces resulted in the formation of hollow spheres for smaller particles and core-shell structured spheres for larger particles. The parameters, a, b, and c, increase nearly monotonically with increasing the radius of rare earth ions. The uniform spheres of Y₃BO₆:Eu³⁺ exhibited a typical red emission at ~613 nm (⁵D₀ → ⁷F₂ electric dipole transition of Eu³⁺), with an intensity ratio I(⁵D₀ → ⁷F₂)/I(⁵D₀ → ⁷F₁) of ~3.5. The luminescence behavior of Y₃BO₆:Eu³⁺ phosphor is dependent on the excitation wavelength, which is closely related to the Eu³⁺ ions at different coordination sites. Driven by a 460-nm blue-LED chip, the Y₃BO₆:Eu³⁺ spheres exhibited a red emission with the CIE coordinates of (~0.65, ~0.35), indicating that they are an excellent red-emitting phosphor candidate for application in white-LEDs.     

Synthesis of α‐Arylphosphonates using Copper‐Catalyzed α‐Arylation and Deacylative α‐Arylation of β‐Ketophosphonates

Efficient methods for the direct arylation and deacylative arylation of β‐ketophosphonates with iodoarenes in presence of a copper(I) or a copper(II) salt as the catalysts have been developed. The corresponding α‐arylphosphonates were obtained in high yields. A tentative mechanism for the deacylative arylation reaction was proposed on the basis of the experimental data.     

Organocatalytic Highly Enantioselective Synthesis of β‐Formyl‐α‐hydroxyphosphonates

The cross‐aldol reaction between enolizable aldehydes and α‐ketophosphonates was achieved for the first time by using 9‐amino‐9‐deoxy‐epi‐quinine as the catalyst. β‐Formyl‐α‐hydroxyphosphonates were obtained in high to excellent enantioselectivities. The reaction works especially well with acetaldehyde, which is a tough substrate for organocatalyzed cross‐aldol reactions. The products were demonstrated to have anticancer activities.     

Efficient Synthesis of β,γ‐Alkynyl α‐Amino Acid Derivatives by Ag(I)‐Catalyzed Alkynylation of α‐Imino Esters

The first catalytic synthesis of β,γ‐alkynyl α‐amino acid derivatives was achieved by direct addition of terminal alkynes to α‐imino esters in the presence of an Ag(I) salt under mild reaction conditions.     

Polyol Synthesis and Investigation of Ce1−xRExO2−x/2 (RE = Sm,Gd, Nd,La, 0 ≤ x ≤ 0.25) Electrolytes for IT‐SOFCs

In this study, we aimed to examine the effect of dopant type and concentration on the ionic conductivity of ceria‐based electrolytes. Ceria electrolytes doped with samarium (SDC), gadolinium (GDC), neodymium (NDC), and lanthanum (LDC) for solid oxide fuel cells were prepared through the polyol process. Acetate compounds of cerium and dopants were used as starting materials, and triethylene glycol was used as a solvent. Prepared powders and pellets were characterized by TG/DTA, XRD, FTIR, SEM, EIS, and EDS techniques. The results of the TG/DTA and XRD indicated that a single‐phase fluorite structure formed at the relatively low calcination temperature of 500°C. The relative densities of the pellets were higher than 90% and these finding were supported by the SEM images. The lattice parameters of the samples increased with the dopant concentration. According to the electrochemical analysis results, the samples with maximum conductivity values were SDC‐20, GDC‐15, NDC‐15, and LDC‐15. The results of the impedance spectroscopy revealed that the SDC‐20 sample exhibited the highest ionic conductivity with a value of 4.29 × 10^?2 S/cm at 800°C in air.     

Synthesis and Pharmacological Evaluation of α4β2 Nicotinic Ligands with a 3‐Fluoropyrrolidine Nucleus

Nicotinic acetylcholine receptors (nAChRs) play an important role in many central nervous system disorders such as Alzheimer’s and Parkinson’s diseases, schizophrenia, and mood disorders. The α₄β₂ subtype has emerged as an important target for the early diagnosis and amelioration of Alzheimer’s disease symptoms. Herein we report a new class of α₄β₂ receptor ligands characterized by a basic pyrrolidine nucleus, the basicity of which was properly decreased through the insertion of a fluorine atom at the 3‐position, and a pyridine ring carrying at the 3‐position substituents known to positively affect affinity and selectivity toward the α₄β₂ subtype. Derivatives 3‐(((2S,4R)‐4‐fluoropyrrolidin‐2‐yl)methoxy)‐5‐(phenylethynyl)pyridine ( 11 ) and 3‐((4‐fluorophenyl)ethynyl)‐5‐(((2S,4R)‐4‐fluoropyrrolidin‐2‐yl)methoxy)pyridine ( 12 ) were found to be the most promising ligands identified in this study, showing good affinity and selectivity for the α₄β₂ subtype and physicochemical properties predictive of a relevant central nervous system penetration.     

Oxygen‐Involved Oxidative Deacetylation of α‐Substituted β‐Acetyl Amides – Synthesis of α‐Keto Amides

α‐Substituted β‐acetyl amides could undergo C C bond cleavage to form α‐keto amides when treated with copper(II) chloride (CuCl₂) and boron trifluoride diethyl etherate (BF₃⋅OEt₂) under an oxygen atmosphere. The yield can be increased by the addition of tert‐butyl hydroperoxide which alone can also effect the reaction. The reaction provides a new protocol for the synthesis of α‐keto amides.

     

Homogeneous Precipitation Synthesis and Low‐Voltage Cathodoluminescence of SnO2:Eu3+ Phosphors for Field Emission Displays

A reddish‐orange‐emitting SnO₂:Eu³⁺ phosphor for field emission displays (FEDs) was successfully synthesized via a homogeneous precipitation route using urea as a precipitant. The influences of the dopant concentration of Eu³⁺ and calcination temperature on optical properties were investigated. The low‐voltage field emission properties of the FED device prepared using the synthesized SnO₂:Eu³⁺ phosphors were reported. Under the UV light, SnO₂:Eu³⁺ phosphors display the strong orange–red emission peaked at 587, 591, and 597 nm due to the ⁵D₀→⁷F₁ magnetic dipole transition of Eu³⁺. The phosphor doped with 1.0 mol% Eu³⁺ possesses the highest photoluminescent (PL) intensity. Under the low‐voltage excitation of 300 V, the fabricated FED device exhibits the bright orange–red emission, high‐voltage brightness saturation, and high color purity, which has a potential application in low‐voltage full color FEDs.     

Multi‐Enzymatic Synthesis of Optically Pure β‐Hydroxy α‐Amino Acids

A novel enzymatic production system of optically pure β‐hydroxy α‐amino acids was developed. Two enzymes were used for the system: an N‐succinyl L ‐amino acid β‐hydroxylase (SadA) belonging to the iron(II)/α‐ketoglutarate‐dependent dioxygenase superfamily and an N‐succinyl L ‐amino acid desuccinylase (LasA). The genes encoding the two enzymes are part of a gene set responsible for the biosynthesis of peptidyl compounds found in the Burkholderia ambifaria AMMD genome. SadA stereoselectively hydroxylated several N‐succinyl aliphatic L ‐amino acids and produced N‐succinyl β‐hydroxy L ‐amino acids, such as N‐succinyl‐L ‐β‐hydroxyvaline, N‐succinyl‐L ‐threonine, (2S,3R)‐N‐succinyl‐L ‐β‐hydroxyisoleucine, and N‐succinyl‐L ‐threo‐β‐hydroxyleucine. LasA catalyzed the desuccinylation of various N‐succinyl‐L ‐amino acids. Surprisingly, LasA is the first amide bond‐forming enzyme belonging to the amidohydrolase superfamily, and has succinylation activity towards the amino group of L ‐leucine. By combining SadA and LasA in a preparative scale production using N‐succinyl‐L ‐leucine as substrate, 2.3 mmol of L ‐threo‐β‐hydroxyleucine were successfully produced with 93% conversion and over 99% of diastereomeric excess. Consequently, the new production system described in this study has advantages in optical purity and reaction efficiency for application in the mass production of several β‐hydroxy α‐amino acids.