Luminescence and energy‐transfer properties of color‐tunable Ca2Mg0.25Al1.5Si1.25O7:Ce3+/Eu2+/Tb3+ phosphors for ultraviolet light‐emitting diodes

A series of Ca₂Mg_0.25Al_1.5Si_1.25O₇:Ce³⁺/Eu²⁺/Tb³⁺ phosphors was been prepared via a conventional high temperature solid‐state reaction and their luminescence properties were studied. The emission spectra of Ca₂Mg_0.25Al_1.5Si_1.25O₇:Ce³⁺,Eu²⁺ and Ca₂Mg_0.25Al_1.5Si_1.25O₇:Ce³⁺,Tb³⁺ phosphors show not only a band due to Ce³⁺ ions (409 nm) but also as a band due to Eu²⁺ (520 nm) and Tb³⁺ (542 nm) ions. More importantly, the effective energy transfer from Ce³⁺ to Eu²⁺ and Tb³⁺ ions was confirmed and investigated by emission/excitation spectra and luminescent decay behaviors. Furthermore, the energy level scheme and energy transfer mechanism were investigated and were demonstrated to be of resonant type via dipole–dipole (Ce³⁺ to Eu²⁺) and dipole–quadrupole (Ce³⁺ to Tb³⁺) reactions, respectively. Under excitation at 350 nm, the emitting color could be changed from blue to green by adjusting the relative doping concentration of Ce³⁺ and Eu²⁺ ions as well as Ce³⁺ and Tb³⁺ ions. The above results indicate that Ca₂Mg_0.25Al_1.5Si_1.25O₇:Ce³⁺,Eu²⁺/Tb³⁺ are promising single‐phase blue‐to‐green phosphors for application in phosphor conversion white‐light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.     

Tunable luminescence properties and energy transfer in LaAl11O18:Eu,Tb phosphor

Eu²⁺ and Tb³⁺ singly doped and co‐doped LaAl₁₁O₁₈ phosphors were prepared by a combustion method using urea as a fuel. The phase structure and photoluminescence (PL) properties of the prepared phosphors were characterized by powder X‐ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence excitation and emission spectra. When the content of Eu²⁺ was fixed at 0.01, the emission chromaticity coordinates could be adjusted from blue to green region by tuning the contents of Tb³⁺ ions from 0.01 to 0.03 through an energy transfer (ET) process. The fluorescence data collected from the samples with different contents of Tb³⁺ into LaAl₁₁O₁₈: Eu, show the enhanced green emission at 545 nm associated with ⁵D₄ –⁷F₅ transitions of Tb³⁺. The enhancement was attributed to ET from Eu²⁺ to Tb³⁺, and therefore Eu²⁺ ion acts as a sensitizer (an energy donor) while Tb³⁺ ion as an activator. The ET from Eu²⁺ to Tb³⁺ is performed through dipole–dipole interaction. The ET efficiency and critical distance were also calculated. The present Eu²⁺–Tb³⁺ co‐doped LaAl₁₁O₁₈ phosphor will have potential application for UV convertible white light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.     

Luminescence properties of barium – gadolinium–titanate ceramics doped with rare‐earth ions (Eu3+ and Tb3+)

Barium‐gadolinium‐titanate (BaGd₂Ti₄O₁₂) powder ceramics doped with rare‐earth ions (Eu³⁺ and Tb³⁺) were synthesized by a solid‐state reaction method. From the X‐ray diffraction spectrum, it was observed that Eu³⁺ and Tb³⁺:BaGd₂Ti₄O₁₂ powder ceramics are crystallized in the form of an orthorhombic structure. Scanning electron microscopy image shows that the particles are agglomerated and the particle size is about 200 nm. Eu³⁺‐ and Tb³⁺‐doped BaGd₂Ti₄O₁₂ powder ceramics were examined by energy dispersive X‐ray analysis, Fourier transform infrared spectroscopy, photoluminescence and thermoluminescence (TL) spectra. Emission spectra of Eu³⁺‐doped BaGd₂Ti₄O₁₂ powder ceramics showed bright red emission at 613 nm (⁵D₀ → ⁷F₂) with an excitation wavelength λ_exci = 408 nm (⁷F₀ → ⁵D₃) and Tb³⁺:BaGd₂Ti₄O₁₂ ceramic powder has shown green emission at 534 nm (⁵D₄ → ⁷F₅) with an excitation wavelength λ_exci = 331 nm ((⁷F₆ → ⁵D₁). TL spectra show that Eu³⁺ and Tb³⁺ ions affect TL sensitivity. Copyright © 2014 John Wiley & Sons, Ltd.     

Interaction of Calf-Thymus DNA With Trivalent La,Eu, and Tb Ions. Metal Ion Binding,DNA Condensation and Structural Features

Abstract

The interaction of calf-thymus DNA with La³⁺, Eu³⁺ and Tb³⁺ has been investigated in aqueous solution at pH 6.5, using metal/DNA(P) molar ratios (r) 1/80, 1/40, 1/20, 1/10, 1/4 and 1/2. Correlations between FTIR spectral changes and DNA structural properties have been established. At low metal/DNA(P) (r) 1/80, the metal ions bind mainly to the PO^? ₂ groups of the backbone, resulting in increased base-stacking interaction and duplex stability. At (r) 1/40 and 1/20, metal ion binding to the PO^? ₂ and the guanine N-7 site (chelation) predominates with minor perturbations of the A-T base pairs. Evidence for this comes from the displacement of the band at 1712 cm^?1 (T,G) towards a lower frequency and the PO^? ₂ antisymmetric band at 1222 cm^?1 towards a higher frequency. At higher metal/DNA(P) ratio, r> 1/20, DNA begins to condensate and drastic structural changes occur, which are accompanied by the shift and intensity changes of several G-C and A-T absorption bands. No major departure from B-DNA conformation was observed before and after DNA condensation eventhough some local structural modifications were observed. A comparison with the Cu-DNA complexes (denaturated DNA) shows some degree of helical destabilizition of the biopolymer in the presence of lanthanide ions.     

Synthesis, crystalline structure and photoluminescence investigations of the new trivalent rare earth complexes (Sm, Eu and Tb) containing 2-thiophenecarboxylate as sensitizer

New complexes with the general formula [RE(TPC)₃ · (H₂O)₂], where RE=Eu³⁺, Sm³⁺, Gd³⁺, Tb³⁺ and TPC=2-thiophenecarboxylate, have been prepared and investigated by photoluminescence spectroscopy. These compounds were characterized by complexometric titration, elemental analyses and infrared spectroscopy. The X-ray crystal structure has been determined for the [Eu(TPC)₃ · (H₂O)₂] compound, indicating that this complex is in dimeric form bridged by two carboxylate ions with monoclinic crystal system and space group P2₁/n. The coordination polyhedron can be described as a distorted square antiprism, where six oxygen atoms belong to the TPC ligand and two oxygen atoms belong to the water molecules, with site symmetry close to C_2v. The theoretical value of the intensity parameter , which is in agreement with the experimental one, indicates that the Eu³⁺ ion is in a highly polarizable chemical environment. Based on the luminescence spectra, the energy transfer from the ligand triplet state (T) of TPC to the excited levels of the Eu³⁺ ion is discussed. The emission quantum efficiency of the ⁵D₀ emitting level of the Eu³⁺ ion was also determined. In the case of the Tb³⁺ ion, the photoluminescence data show the high emission intensity of the characteristic transitions ⁵D₄ → ⁷F_J (J=0-6), indicating that the TPC ligand is a good sensitizer. It is also noticed that the complexes with the Eu³⁺ and Tb³⁺ ions are more luminescent than the complex with the Sm³⁺ ion.     

Utilization of fluorescent lanthanide ions for the study of cation binding to extracellular sites in frog skeletal muscle.

The binding of Tb³⁺ ions to frog muscle has been studied, using fluorescence measurements. Kinetic evidence suggests that Tb³⁺ binds to the muscle at multiple sites. Two major classes can be distinguished: One having relatively fast kinetics and saturating within a few minutes; the second type being either very slow (hours) or consisting of an infinite pool. Binding to the first class of sites is readily reversible and is probably extracellular. It is shown that part of the slow type of binding is also reversible, and is also associated with extracellular binding sites.The binding of terbium is antagonized by other metal ions, their order of effectiveness being: La³⁺, Eu³⁺ > Mn²⁺, Hg²⁺ ? Ca²⁺ > Mg²⁺. A comparison with other studies suggests that part of the binding sites are located at the surface membrane of the muscle. Our experiments raise the possibility that part of the slowly exchanged calcium ions may well be of extracellular origin rather than intracellular one. The limitations and advantages of such studies, as a means to probe ion interactions in complex biological systems are discussed.     

Rare earth activated yttrium aluminate phosphors with modulated luminescence

Yttrium aluminate (Y₃A₅O₁₂) was doped with different rare earth ions (i.e. Gd³⁺, Ce³⁺, Eu³⁺ and/or Tb³⁺) in order to obtain phosphors (YAG:RE) with general formula,Y_3‐x‐aGd_xRE_aAl₅O₁₂ (x = 0; 1.485; 2.97 and a = 0.03). The synthesis of the phosphor samples was done using the simultaneous addition of reagents technique. This study reveals new aspects regarding the influence of different activator ions on the morpho‐structural and luminescent characteristics of garnet type phosphor. All YAG:RE phosphors are well crystallized powders containing a cubic‐Y₃Al₅O₁₂ phase as major component along with monoclinic‐Y₄Al₂O₉ and orthorhombic‐YAlO₃ phases as the impurity. The crystallites dimensions of YAG:RE phosphors vary between 38 nm and 88 nm, while the unit cell slowly increase as the ionic radius of the activator increases. Under UV excitation, YAG:Ce exhibits yellow emission due to electron transition in Ce³⁺ from the 5d level to the ground state levels (²F_5/2, ²F_7/2). The emission intensity of Ce³⁺ is enhanced in the presence of the Tb³⁺ ions and is decreased in the presence of Eu³⁺ ions due to some radiative or non‐radiative processes that take place between activator ions. By varying the rare earth ions, the emission colour can be modulated from green to white and red. Copyright © 2015 John Wiley & Sons, Ltd.     

Terbium(III) fluorescence probe studies on metal ion-binding sites in anticoagulation factor I from Agkistrodon acutus venom

Anticoagulation factor I (ACF I) isolated from the venom of Agkistrodon acutus is an activated coagulation factor X-binding protein with marked anticoagulant activity. Present studies show that holo-ACF I assumes a compactly folded structure in the range of pH 5–6, in which the most interior Trp residues and quenchers are adjacent. Tb³⁺ ions can completely replace both Ca²⁺ ions in holo-ACF I, as determined by equilibrium dialysis. Although the two Tb³⁺ ions in Tb³⁺-ACF I have slightly different luminescence efficiencies, both have similar quenching effects on the intrinsic fluorescence, suggesting that probably there are same numbers of Trp residues close to both Tb³⁺-binding sites. Two Tb³⁺-binding sites with similar apparent Tb³⁺ association constant values, (1.69 ± 0.02) × 10⁷ M^–1 and (1.42 ± 0.01) × 10⁷ M^–1, respectively, were further identified through Tb³⁺ fluorescence titration. In addition, it has been confirmed from the titration of holo-ACF I and Tb³⁺-ACF I with NBS that only interior Trp residues are involved in the energy transfer to Tb³⁺ ions and that all accessible Trp residues located in the surface of holo-ACF I have similar affinity to NBS, while those located in the surface of Tb³⁺-ACF I have two different kinds of affinity to NBS, which strongly suggests a conformational change of holo-ACF I upon substitution of Tb³⁺ for Ca²⁺. The results show that although the Tb³⁺-altered conformation of ACF I cannot support the binding of Tb³⁺-ACF I with FXa, determined by nondenaturing PAGE, Tb³⁺ ions are effective and useful fluorescence probes to analyze the structures and properties of Ca²⁺-binding sites in ACF I.     

Interaction of lanthanide ions with Panulirus interruptus hemocyanin: Evidence for vicinity of some of the cation binding sites

The interaction of a number of lanthanide ions (namely terbium, praseodymium, erbium, lanthanum, gadolinium and europium) with Panulirus interruptus hemocyanin has been studied.Results from O₂-binding experiments indicate that all these ions may substitute for calcium as allosteric effectors of hemocyanin. Addition of the lanthanides to deoxygenated Panulirus hemocyanin saturated with Tb³⁺ results in a quenching of the terbium luminescence. The highly efficient quenching observed in the case of Eu³⁺ may indicate energy-transfer between Tb³⁺ and Eu³⁺. Since energy-transfer between lanthanides is only effective over very short distances, the data suggest that some of the cation binding sites of Panulirus hemocyanin are clustered.     

A simple fluorimetric assay for guanosine nucleotides

It is comparatively easy to assay adenosine 5′-triphosphate either in the presence or absence of other nucleoside triphosphates (1). An assay for UTP has been reported (2) based on its incorporation into RNA using RNA polymerase and a poly(dA-dT) template in the presence of excess [³H]-ATP; this method could be adapted to assay for GTP and CTP. It is known that the fluorescence of Tb³⁺ increases on binding to nucleic acids (3–5), and this enhancement has been attributed both to complex formation between Tb³⁺ and guanine residues in the nucleic acid (3) and also to binding of Tb³⁺ to thiouracil (4).     

Intense visible multicolored luminescence from lanthanide ion‐pair codoped NaGdF4 nanocrystals

Lanthanide ion‐pair (Eu³⁺/Tb³⁺, Dy³⁺/Tb³⁺, Sm³⁺/Tb³⁺ and Eu³⁺/Dy³⁺) codoped NaGdF₄ nanocrystals using Ce³⁺ as the sensitizer were prepared via the polyol method. The nanocrystals with different codoped lanthanide ion‐pairs retain their individual optical properties and the combined spectra can be detected using single‐wavelength excitation at about 251 nm. The combined spectra intensity ratios can be adjusted through control of the doping ions molar ratios. Excited with a UV lamp at 254 nm, the as‐prepared nanocrystals in aqueous solution emit intense visible emissions of different colors. The nanocrystals were coated with SiO₂, to make them biocompatible. Copyright © 2009 John Wiley & Sons, Ltd.     

Divalent metal ions promote the formation of the 5'-splice site recognition complex in a self-splicing group II intron

Group II introns are ribozymes occurring in genes of plants, fungi, lower eukaryotes, and bacteria. These large RNA molecular machines, ranging in length from 400 to 2500 nucleotides, are able to catalyze their own excision from pre-mRNA, as well as to reinsert themselves into RNA or sometimes even DNA. The intronic domain 1 contains two sequences (exon binding sites 1 and 2, EBS1 and EBS2) that pair with their complementary regions at the 3′-end of the 5′-exon (intron binding sites 1 and 2, IBS1 and IBS2) such defining the 5′-splice site. The correct recognition of the 5′-splice site stands at the beginning of the two steps of splicing and is thus crucial for catalysis. It is known that metal ions play an important role in folding and catalysis of ribozymes in general. Here, we characterize the specific metal ion requirements for the formation of the 5′-splice site recognition complex from the mitochondrial yeast group II intron Sc.ai5γ. Circular dichroism studies reveal that the formation of the EBS1 · IBS1 duplex does not necessarily require divalent metal ions, as large amounts of monovalent metal ions also promote the duplex, albeit at a 5000 times higher concentration. Nevertheless, micromolar amounts of divalent metal ions, e.g. Mg²⁺ or Cd²⁺, strongly promote the formation of the 5′-splice site. These observations illustrate that a high charge density independent of the nature of the ion is needed for binding EBS1 to IBS1, but divalent metal ions are presumably the better players.     

Phosphorylation-dependent metal binding by α-synuclein peptide fragments

α-Synuclein (α-syn) is the major protein component of the insoluble fibrils that make up Lewy bodies, the hallmark lesions of Parkinson’s disease. Its C-terminal region contains motifs of charged amino acids that potentially bind metal ions, as well as several identified phosphorylation sites. We have investigated the metal-binding properties of synthetic model peptides and phosphopeptides that correspond to residues 119–132 of the C-terminal, polyacidic stretch of human α-syn, with the sequence Ac-Asp-Pro-Asp-Asn-Glu-Ala-Tyr-Glu-Met-Pro-Ser-Glu-Glu-Gly (α-syn119–132). The peptide pY125 replaces tyrosine with phosphotyrosine, whereas pS129 replaces serine with phosphoserine. By using Tb³⁺ as a luminescent probe of metal binding, we find a marked selectivity of pY125 for Tb³⁺ compared with pS129 and α-syn119–132, a result confirmed by isothermal titration calorimetry. Truncated or alanine-substituted peptides show that the phosphoester group on tyrosine provides a metal-binding anchor that is supplemented by carboxylic acid groups at positions 119, 121, and 126 to establish a multidentate ligand, while two glutamic acid residues at positions 130 and 131 contribute to binding additional Tb³⁺ ions. The interaction of other metal ions was investigated by electrospray ionization mass spectrometry, which confirmed that pY125 is selective for trivalent metal ions over divalent metal ions, and revealed that Fe³⁺ and Al³⁺ induce peptide dimerization through metal ion cross-links. Circular dichroism showed that Fe³⁺ can induce a partially folded structure for pY125, whereas no change was observed for pS129 or the unphosphorylated analog. The results of this study show that the type and location of a phosphorylated amino acid influence a peptide’s metal-binding specificity and affinity as well as its overall conformation. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Interaction of Eu3+ with yeast alcohol dehydrogenase

The activity of yeast alcohol dehydrogenase is markedly enhanced by Eu³⁺ ions. At pH 7.0 two binding constants for Eu³⁺, 1.0 × 10^–2 and 2.0 × 10^–3 M, were obtained using a Scatchard plot. The presence of Zn²⁺ ions restricts the Eu³⁺-induced increase in the activity of yeast alcohol dehydrogenase. Studies on the tryptophan fluorescence of the enzyme in the absence and presence of Eu³⁺ or Zn²⁺ ions showed that Eu³⁺ affects tertiary or quaternary structures, which is consistent with its activation of the enzyme. The presence of Zn²⁺ reverses the conformational changes caused by Eu³⁺. Comparison of the effects of Eu³⁺ with Zn²⁺ for apo-yeast alcohol dehydrogenase indicates that their binding sites on the protein are different.     

Probing the metal ion selectivity in methionine aminopeptidase via changes in the luminescence properties of the enzyme bound europium ion

We report herein, for the first time, that Europium ion (Eu³⁺) binds to the “apo” form of Escherichia coli methionine aminopeptidase (EcMetAP), and such binding results in the activation of the enzyme as well as enhancement in the luminescence intensity of the metal ion. Due to competitive displacement of the enzyme-bound Eu³⁺ by different metal ions, we could determine the binding affinities of both “activating” and “non-activating” metal ions for the enzyme via fluorescence spectroscopy. The experimental data revealed that among all metal ions, Fe²⁺ exhibited the highest binding affinity for the enzyme, supporting the notion that it serves as the physiological metal ion for the enzyme. However, the enzyme-metal binding data did not adhere to the Irving-William series. On accounting for the binding affinity vis a vis the catalytic efficiency of the enzyme for different metal ions, it appears evident that that the “coordination states” and the relative softness” of metal ions are the major determinants in facilitating the EcMetAP catalyzed reaction.     

Red‐ and green‐emitting nano‐clay materials doped with Eu3+ and/or Tb3+

Trivalent europium (Eu³⁺) and terbium (Tb³⁺) ions are important activator centers used in different host lattices to produce red and green emitting materials. The current work shows the design of new clay minerals to act as host lattices for rare earth (RE) ions. Based on the hectorite structure, nano‐chlorohectorites and nano‐fluorohectorites were developed by replacing the OH^? present in the hectorite structure with Cl^? or F^?, thus avoiding the luminescence quenching expected due to the OH^? groups. The produced matrices were characterized through X‐ray powder diffraction (XPD), transmission electron microscopy (TEM), FT‐IR, ²⁹Si MAS (magic angle spinning) NMR, nitrogen sorption, thermogravimetry‐differential scanning calorimetry (TGA‐DSC) and luminescence measurements, indicating all good features expected from a host lattice for RE ions. The nano‐clay materials were successfully doped with Eu³⁺ and/or Tb³⁺ to yield materials preserving the hectorite crystal structure and showing the related luminescence emissions. Thus, the present work shows that efficient RE³⁺ luminescence can be obtained from clays without the use of organic ‘antenna’ molecules.     

Eu3+‐doped polystyrene and polyvinylidene fluoride nanofibers made by electrospinning for photoluminescent fabric designing

Eu³⁺‐doped polystyrene and polyvinylidene fluoride (PVDF/Eu³⁺ and PS/Eu³⁺) nanofibers were made using electrospinning. These fibers were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT‐IR), energy dispersive spectroscopy (EDX) and photoluminescence (PL). Spectral analysis of PVDF/Eu³⁺ and PS/Eu³⁺ nanofibers was based on their emission spectra. A bright red emission was noticed from Eu³⁺ that was assigned to the hypersensitive ⁵D₀ → ⁷F₂ transition. The enhanced intensity ratios of ⁵D₀ → ⁷F₂ to ⁵D₀ → ⁷F₁ transitions in the nanofibers indicated a more polarized chemical environment for the Eu³⁺ ions and greater hypersensitivity for the ⁵D₀ → ⁷F₂ transition, which showed the potential for application in various polymer optoelectronic devices. The Eu³⁺‐doped polymer (PVDF/Eu³⁺ and PS/Eu³⁺) nanofibers are suitable for the photoluminescent white light fabric design of smart textiles. This paper focuses on the potential application of smart fabrics to address challenges in human life.     

155Eu3+ as a probe of metal ion and cationic drug binding sites on native and heat-denatured DNA

A flow-dialysis apparatus suitable for the study of high affinity metal ion binding sites in macromolecules has been utilized to study ¹⁵⁵Eu³⁺ exchange processes, as a function of pH, in both ‘native’ and ‘heat-denatured’ DNA. ‘Free exchange’ of ¹⁵⁵Eu³⁺ was found to occur at a significantly faster rate at pH = 7.0 than at pH = 6.0 for both forms of DNA; while non-radioactive Eu³⁺-induced ‘displacement’ of bound ¹⁵⁵Eu³⁺ occurred at a significantly faster rate at pH = 6.0 than at pH = 7.0 for both species of DNA. These results are consistent with a greater ‘entropic’ driving force for metal ion:DNA complexation at the lower pH value. The effect of ethidium bromide on ¹⁵⁵Eu³⁺ exchange was also examined as a function of pH. The intercalating agent was found to accelerate ¹⁵⁵Eu³⁺ displacement at pH = 6.0 and decelerate displacement at pH = 7.0. All three sets of experiments (i.e., free- exchange of bound ¹⁵⁵Eu³⁺, Eu³⁺-induced displacement of bound ¹⁵⁵Eu³⁺ and ethidium ion-induced displacement of bound ¹⁵⁵Eu³⁺) indicate that the ¹⁵⁵Eu³⁺ ion can serve as a useful probe of metal ion and drug binding sites in nucleic acid polymers, and constitutes a particularly sensitive probe at pH = 6.0.     

Kinetic control of Mg2+-dependent melting of duplex DNA ends by Escherichia coli RecBC

Escherichia coli RecBCD is a highly processive DNA helicase involved in double-strand break repair and recombination that possesses two helicase/translocase subunits with opposite translocation directionality (RecB (3′ to 5′) and RecD (5′ to 3′)). RecBCD has been shown to melt out ∼ 5-6 bp upon binding to a blunt-ended duplex DNA in a Mg²⁺-dependent, but ATP-independent reaction. Here, we examine the binding of E. coli RecBC helicase (minus RecD), also a processive helicase, to duplex DNA ends in the presence and in the absence of Mg²⁺ in order to determine if RecBC can also melt a duplex DNA end in the absence of ATP. Equilibrium binding of RecBC to DNA substrates with ends possessing pre-formed 3′ and/or 5′ single-stranded (ss)-(dT)_n flanking regions (tails) (n ranging from zero to 20 nt) was examined by competition with a fluorescently labeled reference DNA and by isothermal titration calorimetry. The presence of Mg²⁺ enhances the affinity of RecBC for DNA ends possessing 3′ or 5′-(dT)_n ssDNA tails with n < 6 nt, with the relative enhancement decreasing as n increases from zero to six nt. No effect of Mg²⁺ was observed for either the binding constant or the enthalpy of binding (ΔH_obs) for RecBC binding to DNA with ssDNA tail lengths, n ≥ 6 nucleotides. Upon RecBC binding to a blunt duplex DNA end in the presence of Mg²⁺, at least 4 bp at the duplex end become accessible to KMnO₄ attack, consistent with melting of the duplex end. Since Mg²⁺ has no effect on the affinity or binding enthalpy of RecBC for a DNA end that is fully pre-melted, this suggests that the role of Mg²⁺ is to overcome a kinetic barrier to melting of the DNA by RecBC and presumably also by RecBCD. These data also provide an accurate estimate (ΔH_obs = 8 ± 1 kcal/mol) for the average enthalpy change associated with the melting of a DNA base-pair by RecBC.     

Electrospinning preparation and photoluminescence properties of Y3Al5O12:Tb3+ nanostructures

Novel nanostructures of Y₃Al₅O₁₂:Tb³⁺ (denoted as YAG:Tb³⁺ for short) nanobelts and nanofibers were fabricated by calcination of the respective electrospun PVP/[Y(NO₃)₃ + Tb(NO₃)₃ + Al(NO₃)₃] composite nanobelts and nanofibers. YAG:Tb³⁺ nanostructures are cubic in structure with a space group of I_a3d. The thickness and width of the YAG:7%Tb³⁺ nanobelts are respectively ca. 125 nm and 5.9 ± 0.3 µm, and the diameter of YAG:7%Tb³⁺ nanofibers is 166.0 ± 20 nm (95% confidence level). The YAG:Tb³⁺ nanostructures emit predominantly at 544 nm from the energy levels transition of ⁵D₄ → ⁷ F₅ of Tb³⁺ ions under the excitation of 274‐nm ultraviolet light. It was found that the optimum doping molar concentration of Tb³⁺ ions for YAG:Tb³⁺ nanostructures was 7%. Compared with YAG:7%Tb³⁺ nanofibers, YAG:7%Tb³⁺ nanobelts exhibit a stronger photoluminescence (PL) intensity under the same doping concentration. Commission International de l'Eclairage (CIE) analysis demonstrates that the emitting colors of YAG:Tb³⁺ nanostructures are located in the green region and color‐tuned luminescence can be obtained by changing the doping concentration of Tb³⁺ and morphologies of the nanostructures, which could be applied in the field of optical telecommunication and optoelectronic devices. The possible formation mechanisms of YAG:Tb³⁺ nanobelts and nanofibers are also proposed. Copyright © 2014 John Wiley & Sons, Ltd.