General strategy for embedding high quality Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> quantum dots and ZnS:Mn<Superscript>2+</Superscript> quantum dots in a silica matrix

In this paper, ZnS:Mn²⁺ quantum dots (QDs) Fe₃O₄ quantum dots (QDs)/SiO₂ nanocomposites were successfully synthesized by reverse microemulsion method. The average diameter of ZnS:Mn²⁺ QDs, Fe₃O₄ QDs and ZnS:Mn²⁺ QDs Fe₃O₄ QDs/SiO₂ nanocomposites was about 5.8, 9 and 29 nm, respectively. As the mass ratio of ZnS:Mn²⁺ to Fe₃O₄ QDs increased from 2.5:4 to 7.5:4, the intensity of the yellow–orange emission coming from Mn²⁺ ions was increased. The superparamagnetic property of ZnS:Mn²⁺ QDs Fe₃O₄ QDs/SiO₂ nanocomposites was observed at room temperature, and the saturation magnetization was decreased as the amount of ZnS:Mn²⁺ QDs increased.     

Chitosan-encapsulated ZnS : M (M: Fe<Superscript>3+</Superscript> or Mn<Superscript>2+</Superscript>) quantum dots for fluorescent labelling of sulphate-reducing bacteria

Chitosan-encapsulated Mn²⁺ and Fe³⁺-doped ZnS colloidal quantum dots (QDs) were synthesized using chemical precipitation method. Though there are many reports on bio-imaging applications of ZnS QDs, the present study focussed on the new type of microbial-induced corrosive bacteria known as sulphate-reducing bacteria, Thiobacillus novellus. Sulphate-reducing bacteria can obtain energy by oxidizing organic compounds while reducing sulphates to hydrogen sulphide. This can create a problem in engineering industries. When metals are exposed to sulphate containing water, water and metal interacts and creates a layer of molecular hydrogen on the metal surface. Sulphate-reducing bacteria then oxidize the hydrogen while creating hydrogen sulphide, which contributes to corrosion for instance, in pipelines of oil and gas industries. In this study, detection and labelling of sulphate-reducing bacteria is demonstrated using fluorescent QDs. Chitosan capped ZnS QDs were synthesized using dopants at different doping concentrations. UV–Vis spectroscopy, XRD and FTIR characterizations were done to identify the optical band gap energy, crystal planes and determine the presence of capping agent, respectively. The morphology and the average particle size of 3.5 ± 0.2 nm were analysed using TEM which substantiated UV–Vis and XRD results. Photoluminescence spectroscopy detected the bacteria attachment to the QDs by showing significant blue shift in bacteria conjugated ZnS QDs. Fluorescence microscopy confirmed the fluorescent labelling of QDs to Thiobacillus novellus bacteria cells making them ideal for bio-labelling applications.     

Fabrication of Fe3O4 Dots Embedded in 3D Honeycomb‐Like Carbon Based on Metallo–Organic Molecule with Superior Lithium Storage Performance

A novel metallo–organic molecule, ferrocene, is selected as building block to construct Fe₃O₄ dots embedded in 3D honeycomb‐like carbon (Fe₃O₄ dots/3DHC) by using SiO₂ nanospheres as template. Unlike previously used inorganic Fe₃O₄ sources, ferrocene simultaneously contains organic cyclopentadienyl groups and inorganic Fe atoms, which can be converted to carbon and Fe₃O₄, respectively. Atomic‐scale Fe distribution in started building block leads to the formation of ultrasmall Fe₃O₄ dots (≈3 nm). In addition, by well controlling the feed amount of ferrocene, Fe₃O₄ dots/3DHC with well‐defined honeycomb‐like meso/macropore structure and ultrathin carbon wall can be obtained. Owing to unique structural features, Fe₃O₄ dots/3DHC presents impressive lithium storage performance. The initial discharge and reversible capacities can reach 2047 and 1280 mAh g^?1 at 0.05 A g^?1. With increasing the current density to 1 and 3 A g^?1, remarkable capacities of 963 and 731 mAh g^?1 remain. Moreover, Fe₃O₄ dots/3DHC also has superior cycling stability, after a long‐term charge/discharge for 200 times, a high capacity of 1082 mAh g^?1 can be maintained (80% against the capacity of the 2nd cycle).     

Effect of combined doping (y<Superscript>3 +</Superscript> + fe<Superscript>3 +</Superscript>) on structural features of nanodispersed zirconium oxide

Fully stabilized zirconium dioxide is widely used. One of the basic requirements to this material is the thermal stability of the structure. The most effective stabilizer for zirconium oxide is yttrium oxide. However, the structure of Y-ZrO₂ degraded at low temperature. Partial substitution of Fe^{3 +} for Y³⁺ decreases both the crystallization and sintering temperature of zirconia ceramic. The aim of present work is the investigation of structural peculiarities of zirconium oxide stabilized by combined dopant depending on chemical composition, synthesis conditions and heat treatment. The polymorphic composition of a ZrO₂-based materials has been determined in series of samples that correspond to the formula [1−(x+y)]ZrO₂⋅xY₂O₃⋅yFe₂O₃ in the temperature range 620–1570 K. It has been found that at the same molar ratio ZrO₂ : doping oxides, the degree of ZrO₂ stabilization increases, and the low-temperature degradation process is retarded by the partial substitution of Fe^{3 +} for Y³⁺. Nonequivalent sites of Fe^{3 +} ions have been identified: two with octahedral coordination for CPH and three with octa-, penta- and tetrahedral coordination for SPH. The possibility of cluster distribution of Fe³⁺ ions and the dependence of the number of vacancies on synthesis conditions have been shown.     

Influence of isovalent and heterovalent substitution for Bi<Superscript>3+</Superscript> and Fe<Superscript>3+</Superscript> on the properties of Bi<Subscript>2</Subscript>Fe<Subscript>4</Subscript>O<Subscript>9</Subscript>-based solid solutions

Bi_2–хLa_хFe₄O₉ and Bi₂Fe_4–2xTi_xCo_xO₉ ferrites have been prepared by solid-state reactions at a temperature of 1073 K. X-ray diffraction data indicate that, in the Bi_2–хLa_хFe₄O₉ system, the limiting degree of La³⁺ substitution for Bi³⁺ ions in Bi₂Fe₄O₉ does not exceed 0.05 and that the limiting degree of substitution in the Bi₂Fe_4–2xTi_xCo_xO₉ system lies in the range 0.05 < x < 0.1. The specific magnetization and specific magnetic susceptibility of the samples have been measured at temperatures from 5 to 300 K in a magnetic field of 0.86 T. The field dependences of magnetization obtained for the Bi_2–хLa_хFe₄O₉ and Bi₂Fe_4–2xTi_xCo_xO₉ ferrites at temperatures of 300 and 5 K demonstrate that partial isovalent substitution of La³⁺ for Bi³⁺ ions in Bi₂Fe₄O₉ and heterovalent substitution of Ti⁴⁺ and Co²⁺ ions for two Fe³⁺ ions leads to partial breakdown of the antiferromagnetic state and nucleation of a ferromagnetic state.     

Design of magnetic and fluorescent Mg-Al layered double hydroxides by introducing Fe3O4 nanoparticles and Eu ions for intercalation of glycine

We describe a novel route for the preparation of magnetic and fluorescent magnesium-aluminum layered double hydroxides by introducing Fe₃O₄ nanoparticles and Eu³⁺ ions. From the powder X-ray diffraction results, it was found that the Fe₃O₄ nanoparticles were highly dispersed in the inner void of octahedral lattice, and the Eu³⁺ ions substituted for the Al³⁺ ions and entered into hydrotalcite lattice through isomorphous replacement. Moderate introduction of Fe₃O₄ nanoparticles and Eu³⁺ ions did not change the lamellar structure of magnesium-aluminum layered double hydroxides. Glycine can also be intercalated into this magnetic and fluorescent layered double hydroxides by ion-exchange method. After intercalation of glycine, the basal spacing of magnetic and fluorescent layered double hydroxides increased from 7.6 to 8.8 Å, indicating that glycine was successfully intercalated into the interlayer space of layered double hydroxides. Magnetic measurements reveal that these novel layered double hydroxides possess paramagnetic property at room temperature, and the emission and excitation spectra indicate the layered double hydroxides exhibit fluorescent property.     

Influence of Mn<Superscript>2+</Superscript> on the up-conversion emission performance of Mn<Superscript>2+</Superscript>, Yb<Superscript>3+</Superscript>, Er<Superscript>3+</Superscript>: ZnWO<Subscript>4</Subscript> green phosphors

The Mn²⁺, Yb³⁺, Er³⁺: ZnWO₄ green phosphors are synthesized successfully through the high temperature solid state reaction method. The micro-structure and morphology have been investigated by means of XRD and EDS. The doped concentrations of Mn²⁺, Yb³⁺, Er³⁺ are measured by ICP. The absorption spectra and emission spectra with different doped concentrations of Mn²⁺ are presented to reveal the influence of Mn²⁺ on the green up-conversion performance. Excited with 970 nm LED, the up-conversion emission peak at 547 nm is obtained and the CIE spectra as well as the green light photo are also presented. The results indicate that the Mn²⁺ ions play the role of the luminescence adjustment in the up-conversion process, which can improve the up-conversion green emission intensity effectively. The luminescence adjustment mechanism of Mn²⁺ ions in Mn²⁺, Yb³⁺, Er³⁺: ZnWO₄ green phosphors has been discussed. The crystal parameters of Dq, B and C are calculated to evaluate the energy level split effect.     

Color tunable luminescence from LaAlO<Subscript>3</Subscript>:Bi<Superscript>3+</Superscript>, Ho<Superscript>3+</Superscript> doped phosphors for field emission displays

Bi³⁺-activated LaAlO₃:Ho³⁺ Phosphor, was prepared by Polyol method, and its photoluminescent properties were investigated under (UV) light excitation. Luminescence studies indicated that optimum concentration of Bi³⁺ and Ho³⁺ in LaAlO₃ was found to be 1 and 1.5 at.%. The luminescent intensity of Ho³⁺ emission lines was remarkably enhanced on exciting with 272 nm, which suggested that efficient energy transfer from Bi³⁺ ions to Ho³⁺ ions takes place. There is significant energy overlap between the emission band of Bi³⁺ ions and the excitation band of Ho³⁺ ions.The ET efficiency has been calculated and found to be 69%. The critical ET distance has been calculated by the concentration–quenching method. The enhanced intensity and tuned luminous color of LaAlO₃: Bi³⁺/Ho³⁺ phosphors from blue to cyan provides a promising material for field emission display devices.     

Easy access to selective binding and recyclable separation of histidine-tagged proteins using Ni<Superscript>2+</Superscript>-decorated superparamagnetic nanoparticles

The development of simple techniques for the separation and purification of recombinant proteins plays an important role in many of the advancements made in biotechnology and nanotechnology. Herein, we report an easy method for the efficient purification of polyhistidine affinity-tagged (His-tagged) proteins by using Ni²⁺-decorated superparamagnetic particles. Monodisperse Ni_0.3Fe_0.7Fe₂O₄ nanoparticles were prepared via a facile and economical one-pot hydrothermal process. Owing to the characteristic molecular recognition ability between nickel(II) ions and the polyhistidine affinity tag, the nanoparticles could be successfully employed to selectively bind and separate His-tagged cyan fluorescent protein (CFP) from an E. coli cell lysate in a recyclable process. Moreover, by changing the divalent metal precursors, various other metal-decorated magnetic nanoparticles can be obtained. This approach offers the possibility of constructing metal-decorated nanoparticles through a simple method and will be highly beneficial in further applications of nanoparticle-based technologies.      

Facile synthesis of water-soluble and superparamagnetic Fe3O4 dots through a polyol-hydrolysis route

Monodisperse Fe₃O₄ dots with a mean size of about 2.3 nm were successfully synthesized via a polyol-hydrolysis route without adding any dispersant. Inorganic iron nitrate was used as the metal source and triethylene glycol (TEG) was used as the polyol solvent. The Fe₃O₄ dots were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), selective area electron diffraction (SAED), Fourier transform infrared (FTIR) spectroscopy, N₂ adsorption–desorption, and magnetization measurements. The as-synthesized Fe₃O₄ dots can not only be coagulated from the polyol by ethanol and acetone, but also easily redispersed in water by ultrasonication, resulting in a clear Tyndall effect. The obtained Fe₃O₄ dots exhibited superparamagnetism at room temperature and the saturation magnetization is much lower than those reported in previous works. The formation mechanism of the Fe₃O₄ dots was proposed to be the hydrolysis of iron nitrates and subsequent dehydration and partial reduction of Fe³⁺ to Fe²⁺ at elevated temperatures in TEG.     

Color-tunable luminescence properties of Sm<Superscript>3+</Superscript>/Dy<Superscript>3+</Superscript> co-doped NaLa(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> phosphors and their energy transfer mechanism

The Sm³⁺, Dy³⁺ doped and Sm³⁺/Dy³⁺ co-doped NaLa(MoO₄)₂ spherical phosphors were hydrothermally synthesized by the EDTA-2Na mediated method. Under the excitation of 297 nm, the quenching concentration of Sm³⁺ in NaLa(MoO₄)₂ host was determined to be 13%, and the concentration quenching mechanism was discussed to be the electric quadrupole–quadrupole interaction. After Sm³⁺ and Dy³⁺ ions were co-doped into the NaLa(MoO₄)₂ host, the energy transfer behaviors resulted from Dy³⁺ to Sm³⁺ ions were investigated by the help of the luminescent spectra of the obtained phosphors. By varying co-doping concentrations of Sm³⁺/Dy³⁺ ions, the emission color of NaLa(MoO₄)₂:Sm³⁺/Dy³⁺ can be tuned from reddish-orange, pink and white to bluish-green. The CIE chromaticity coordinate, the correlated color temperature and the quantum efficiency of NaLa_0.87(MoO₄)₂:1%Sm³⁺, 12%Dy³⁺ were calculated to be (0.356, 0.320), 4353 K and 20%, respectively. Furthermore, in the temperature-dependent analysis, it presented good thermal stability, which can become a promising single-phased white-emitting phosphor for white LEDs devices. Based on these results, the possible energy transfer mechanism between Dy³⁺ and Sm³⁺ in NaLa(MoO₄)₂:Sm³⁺/Dy³⁺ was also proposed.     

Effect of phosphorus ion implantation on the optical properties of thin films of germanium dioxide doped with Er<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript> ions

It is shown that the ion implantation of phosphorus into thin amorphous films of germanium dioxide doped with Er³⁺ and Yb³⁺ ions can be used for enhancing luminescence from Er³⁺ ions at ∼1.53 μm.     

Eu<Superscript>2+</Superscript> and Gd<Superscript>3+</Superscript> Distributions in Fluorohafnate Glasses Studied by Electron Paramagnetic Resonance

We have studied electron paramagnetic resonance spectra of europium- and gadolinium-activated ZBLAN-type fluorohafnate glasses, using the composition 58HfF₄ · 20BaF₂ · 2LaF₃ · 3AlF₃ · 17NaF as an example. The ratio of the concentration of free Eu²⁺ and Gd³⁺ ions to that of ions in clusters has been quantitatively evaluated for the first time. The percentage of free ions has been shown to increase significantly with decreasing activator concentration. At activator concentrations of 1.25 mol % EuF₂ and 1 mol % GdF₃, the activator ions predominantly form clusters and only a small fraction of Eu²⁺ and Gd³⁺ are present as individual ions, whereas at 0.1 mol % EuF₂ the concentration of free ions is comparable to that of ions in the clusters.     

Landau–Zener spin transitions in Fe2+–Fe2+ quantum dots controlling dislocation mobility in NaCl:Fe crystals

Magnetic field induces transition in the distorted Fe²⁺–Fe²⁺ pairs (quantum dots) from the initial bonding singlet state to the high spin antibonding state providing decay of the pairs for two separated Fe²⁺ ions. Dislocations moving under internal stresses easily overcome separated Fe²⁺ ions in comparison with Fe²⁺–Fe²⁺ pairs lying close to the glide plane. Non-monotonous field dependence of dislocation displacements under internal stresses governed by short (100 μs) impulse of high magnetic fields up to 31 T was revealed in NaCl:Fe crystals. This non-typical dependence is the fingerprint of the Landau–Zener non-adiabatic spin transition between singlet and high spin states in quantum dots distorted by mechanical stresses of moving dislocations.     

Ce<Superscript>3+</Superscript> and Eu<Superscript>2+</Superscript> luminescence in calcium and strontium aluminates

Compound CaAl₄O₇ (CA4), SrAl₄O₇ (SA4), CaAl₁₂O₁₉ (CA12) and SrAl₁₂O₁₉ (SA12) have been synthesized by using single step combustion method. The phosphors have been characterized by XRD, SEM and PL techniques. Both CA4 and SA4 possess monoclinic crystal structure whereas CA12 and SA12 possess hexagonal structure. Effects of crystal symmetry on the emission spectrum have been studied by doping the samples with Ce³⁺ and Eu²⁺ ions. The luminescence properties of Ce³⁺ and Eu²⁺ in these hosts is discussed on the basis of their covalent character and the crystal field splitting of the d-orbital of dopant ions. The spectroscopic properties, crystal field splitting, centroid shift, red shift and stokes shift have been studied. Spectroscopic properties of Eu²⁺ ions have been accurately predicted from those of Ce³⁺ ions in the same host. Most importantly experimental results were matched excellently with the calculated results. The preferential substitution of Ce³⁺ and Eu²⁺ at different Ca²⁺, Sr²⁺ crystallographic sites have been discussed. The dependence of emission wavelengths of Ce³⁺ and Eu²⁺ on the local symmetry of different crystallographic sites was also studied by using Van Uitert’s empirical relation. Differences in the emission spectrum of these samples have been observed despite their similar crystal structures and space group. Possible reasons have been discussed.     

Roles of doping ions in persistent luminescence of SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript>:Eu<Superscript>2+</Superscript>, RE<Superscript>3+</Superscript> phosphors

The polycrystalline Eu²⁺ and RE³⁺ co-doped strontium aluminates SrAl₂O₄:Eu²⁺, RE³⁺ were prepared by solid state reactions. The UV-excited photoluminescence, persistent luminescence and thermo-luminescence of the SrAl₂O₄:Eu²⁺, RE³⁺ phosphors with different composition and doping ions were studied and compared. The results showed that the doped Eu²⁺ ion in SrAl₂O₄:Eu²⁺, Dy³⁺ phosphors works as not only the UV-excited luminescent center but also the persistent luminescent center. The doped Dy³⁺ ion can hardly yield any luminescence under UV-excitation, but can form a electron trap with appropriate depth and greatly enhance the persistent luminescence and thermo-luminescence of SrAl₂O₄:Eu²⁺. Different co-doping RE³⁺ ions showed different effects on persistent luminescence. Only the RE³⁺ ion (e.g. Dy³⁺, Nd³⁺), which has a suitable optical electro-negativity, can form the appropriate electron trap and greatly improve the persistent luminescence of SrAl₂O₄:Eu²⁺. Based on above observations, a persistent luminescence mechanism, electron transfer model, was proposed and illustrated.     

Local crystal structure of multiferroic BiMnO<Subscript>3</Subscript> studied by <Superscript>57</Superscript>Fe probe Mössbauer spectroscopy

This paper presents a ⁵⁷Fe probe Mössbauer spectroscopy study of a BiMn_0.96⁵⁷Fe_0.04O₃ manganite synthesized at high pressure (6 GPa). The BiMnO₃ manganite possesses multiferroic properties and exhibits cooperative orbital ordering due to Jahn–Teller active Mn³⁺ ions. ⁵⁷Fe Mössbauer spectra have been measured and analyzed in a wide temperature range, which includes the orbital ordering temperature of BiMnO₃.     

Comparative investigation on the effect of alkaline earth oxides on the intensity of absorption bands due to Cu<Superscript>2+</Superscript>, Mn<Superscript>3+</Superscript> and Cr<Superscript>3+</Superscript> ions in ternary silicate glasses

Absorption characteristics of Cu²⁺, Mn³⁺ and Cr³⁺ ions in ternary silicate (20Na₂O·10RO·70SiO₂, where R=Ca, Sr, Ba) glasses were investigated. The intensities of absorption bands due to Cu²⁺ ion was found to increase with increasing ionic radii of the alkaline earth ions whereas it was found to decrease in case of Mn³⁺ and Cr³⁺ ions with increasing ionic radii of the alkaline earth ions. The results were discussed in the light of relation between linear extinction coefficients of these ions and coulombic force of alkaline earth ions. The change in intensities of Cu²⁺, Mn³⁺ and Cr³⁺ ion is attributed due to change in silicate glass compositions.     

Luminescence of BaSiO<Subscript>3</Subscript> crystals doped with Er<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript>

The Stokes and anti-Stokes luminescence of undoped and rare-earth-doped (Er³⁺ and Yb³⁺) BaSiO₃ has been studied in the temperature range 78–450 K under excitation at 10–1000 mV. The results indicate that the emission mechanism in BaSiO₃ crystals is hole recombination and that the anti-Stokes luminescence is due to consecutive sensitization; that is, the Yb³⁺ ions in the BaSiO₃ compound act as luminescence sensitizers, and the Er³⁺ ions, as activators.