Tunable white-light emission of lanthanide(III) hybrid material based on hectorite

Lanthanide(III) luminescent hybrid materials based on the layered hectorite have been successfully prepared, showing tunable emission colors as well as white light by varying the molar ratio between Eu³⁺ and Tb³⁺.     

Nano Au enhanced upconversion in dichroic Nd3+:Au–antimony glass nanocomposites

Dichroic Nd³⁺:Au–antimony glass (K₂O–B₂O₃–Sb₂O₃) nanocomposites (NCs) have been synthesized by single-step melt-quench thermochemical reduction process. The UV–Vis–NIR spectra show surface plasmon resonance (SPR) band of Au⁰ nanoparticles (NPs) and absorption peaks of Nd³⁺ ions. XRD and SAED results indicate growth of Au⁰ NPs along (200) plane. TEM image reveals elliptical Au⁰ NPs having sizes 12–21 nm (aspect ratio ～1.2) responsible for the dichroic behavior. Photoluminescent upconversion under excitation at 805 nm exhibit two emission bands of Nd³⁺ ions at 540 (green) and 650 (red) nm due to ⁴G_7/2 → ⁴I_9/2 and ⁴G_7/2 → ⁴I_13/2 transitions respectively. Both bands undergo maximum 8 and 11 fold intensity enhancements respectively at 0.03 wt% Au⁰ (4.1 × 10¹⁸ atoms/cm³). Local field enhancement (LFE) induced by Au⁰ SPR and energy transfer (ET) from Au⁰ → Nd³⁺ is found to be responsible for enhancement while ET from Nd³⁺ → Au⁰ and optical re-absorption due to Au⁰ SPR for quenching.     

Synthesis,characterization and properties of microporous lanthanide silicates: K8Ln3Si12O32NO3·H2O (Ln = Eu,Tb, Gd,Sm)

A family of microporous lanthanide silicates, K₈Ln₃Si₁₂O₃₂NO₃·H₂O (denoted LnSiO-CJ3, Ln = Eu, Tb, Gd, Sm), was synthesized under mild hydrothermal conditions at 503 K. The X-ray powder diffraction patterns of these compounds reveal that they are isostructural. The structure of EuSiO-CJ3 was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic space group P-1 (No. 2) with a = 11.599(2) Å, b = 12.225(2) Å, c = 13.829(3) Å, α = 112.99(3)°, β = 92.05(3)°, γ = 90.57(3)°. The structure is based on [Si₃O₈]_n^4n? layers with 6-, 8-, 12-rings that are connected by EuO₆ octahedra to form a 3-D framework with 8-ring channels along the [001] direction. Charge neutrality is achieved by the K⁺ and NO₃^? ions located in the channels. The framework of EuSiO-CJ3 shows good thermal stability, which can be stable up to 1273 K. Ion-exchange capacity of EuSiO-CJ3 was investigated by the exchange of NO₃^? ions with halide ions (F^?, Cl^?, Br^?). The peaks in the emission spectra of LnSiO-CJ3 (Ln = Eu, Tb) belong to the characteristic transitions of Ln³⁺ (Ln = Eu, Tb) respectively. The lifetime measurements of LnSiO-CJ3 (Ln = Eu, Tb) suggest the presence of three Ln³⁺ (Ln = Eu, Tb) environments, which are consistent with the crystallographic results.     

Improved luminescent behavior of YVO4:Eu3+ ceramic phosphors by Li contents

Crystalline phase and surface morphology of phosphors are important factors to determine luminescent characteristics. Li-doped YVO₄:Eu³⁺ ceramic samples were prepared by a solid state reaction method. The Li⁺ concentration was varied from 1 to 3 wt% to improve crystallinity and surface morphology of ceramics. Influence of Li doping on luminescent properties of YVO₄:Eu³⁺ ceramics has been investigated. Photoluminescence spectra have been measured at room temperature using a luminescence spectrometer and excitation by a broadband incoherent ultraviolet light source with an excitation wavelength of 325 nm. The emitted radiation was dominated by a red emission peak at 620 nm radiated from the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions. As Li⁺ ion content increases from 0 to 2 wt%, the photoluminescence (PL) brightness improved. The brightness of 2 wt% Li-doped YVO₄:Eu³⁺ ceramic was increased by a factor of 1.43 in comparison with that of YVO₄:Eu³⁺ ceramic. The enhanced luminescence resulted not only from the improved crystallinity but also from the enhanced surface roughness. The luminescent intensity and surface roughness exhibited similar behavior as a function of Li⁺ ion concentration.     

Enhanced frequency upconversion of Sm3+ ions by elliptical Au nanoparticles in dichroic Sm3+: Au-antimony glass nanocomposites

Dichroic Sm³⁺: Au-antimony glass nanocomposites are synthesized in a new reducing glass (dielectric) matrix (mol%) K₂O–B₂O₃–Sb₂O₃ (KBS) by a single-step melt-quench technique involving selective thermochemical reduction. X-ray diffraction (XRD) and selected area electron diffraction (SAED) results indicate that Au⁰ nanoparticles are grown along the (2 0 0) plane direction. The transmission electron microscopic (TEM) image reveals the elliptical Au⁰ nanoparticles having major axis range 12–17 nm. Dichroic behavior is due to elliptical shape of Au⁰ nanoparticles of aspect ratio ～1.2. Au⁰ NPs of concentration of 0.03 wt% (4.1 × 10¹⁸ atoms/cm³) drastically enhances the intensity (～7-folds) of electric dipole ⁴G_5/2 → ⁶H_9/2 red transition (636 nm) of Sm³⁺ ions and then attenuates with further increase in Au⁰ concentration. The magnetic dipole ⁴G_5/2 → ⁶H_5/2 green (566 nm) and ⁴G_5/2 → ⁶H_7/2 orange (602 nm) transitions remain almost unaffected by presence of nano Au⁰. Local field enhancement (LFE) induced by Au⁰ SPR and energy transfer (ET) from fluorescent Au⁰ → Sm³⁺ ions are found to be responsible for the enhancement while reverse ET from Sm³⁺ → Au⁰ and optical re-absorption due to Au⁰ SPR for attenuation.     

Characterization,EPR and photoluminescence studies of LiAl5O8:Cr phosphors

Red emitting Cr³⁺ doped LiAl₅O₈ powder phosphor was prepared by combustion route using corresponding metal nitrates and urea in a single step. The prepared powder was characterized by X-ray diffraction and surface area measurements were carried out by Brunauer–Emmet–Teller adsorption isotherms. The electron paramagnetic resonance spectrum in the low field regions is typical for isolated Cr³⁺ ions whereas the resonance signal in the high field region with g = 1.95 is due to exchange coupled Cr³⁺–Cr³⁺ pairs. The optical studies show two broad and intense bands characteristic of Cr³⁺ ions in distorted octahedral symmetry. The photoluminescence spectrum gives a narrow red emission at 710 nm corresponding to ²E_g → ⁴A_2g transition upon excitation of 562 nm. The crystal field parameter (Dq), Racah inter-electronic repulsion parameters (B and C) and nephelauxetic parameters have been evaluated and discussed.     

Optical and dielectric properties of isothermally crystallized nano-KNbO3 in Er3+-doped K2O–Nb2O5–SiO2 glasses

Precursor glass of composition 25K₂O–25Nb₂O₅–50SiO₂ (mol%) doped with Er₂O₃ (0.5 wt% in excess) was isothermally crystallized at 800 °C for 0–100 h to obtain transparent KNbO₃ nanostructured glass–ceramics. XRD, FESEM, TEM, FTIRRS, dielectric constant, refractive index, absorption and fluorescence measurements were carried out to analyze the morphology, dielectric, structure and optical properties of the glass–ceramics. The crystallite size of KNbO₃ estimated from XRD and TEM is found to vary in the range 7–23 nm. A steep rise in the dielectric constant of glass–ceramics with heat-treatment time reveals the formation of ferroelectric nanocrystalline KNbO₃ phase. The measured visible photoluminescence spectra have exhibited green emission transitions of ²H_11/2, ⁴S_3/2 → ⁴I_15/2 upon excitation at 377 nm (⁴I_15/2 → ⁴G_11/2) absorption band of Er³⁺ ions. The near infrared (NIR) emission transition ⁴I_13/2 → ⁴I_15/2 is detected around 1550 nm on excitation at 980 nm (⁴I_15/2 → ⁴I_11/2) of absorption bands of Er³⁺ ions. It is observed that photoluminescent intensity at 526 nm (²H_11/2 → ⁴I_15/2), 550 nm (⁴S_3/2 → ⁴I_15/2) and 1550 nm (⁴I_13/2 → ⁴I_15/2) initially decrease and then gradually increase with increase in heat-treatment time. The measured lifetime (τ_f) of the ⁴I_13/2 → ⁴I_15/2 transition also possesses a similar trend. The measured absorption and fluorescence spectra reveal that the Er³⁺ ions gradually enter into the KNbO₃ nanocrystals.     

Cavity ring-down observation of Yb3+ optical absorption in room temperature solution

Cavity ring-down spectroscopy is used to probe the optical absorption of the optical pseudo-two level system [Xe]4f¹³ Yb³⁺ in room temperature solution, a situation where the two-color pump-probe luminescence approach commonly used to study the other [Xe]4fⁿ (2 ≤ n ≤ 12) trivalent lanthanide ions fails. A 1 m optical cavity constructed from two highly reflective mirrors is used to obtain ring-down signals as a function of wavelength from 1 mL samples contained in a quartz cuvette placed in the center of the cavity. Absorption spectra constructed from these signals characteristic of the ⁶H_15/2 → ⁴F_9/2 [Xe]4f⁵ Dy³⁺ and the ⁷F₀ → ⁵D₀ [Xe]4f⁶ Eu³⁺ transitions are presented and compared to the corresponding single pass absorption and two-color pump-probe luminescence spectra to obtain sensitivity estimates. Finally the spectrum for the ²F_5/2 → ²F_7/2 [Xe]4f¹³ Yb³⁺ transition for a model Yb³⁺ complex in room temperature solution is obtained using cavity ring-down spectroscopy for the first time.     

Luminescence properties of yttrium gadolinium orthovanadate nanophosphors and efficient energy transfer from VO43− to Sm3+ via Gd3+ ions

In this paper, luminescence properties of orthovanadates, Y_1−x−yGd_xVO₄:ySm³⁺ (where x = 0.05–0.50, y = 0.01–0.05), and the energy transfer mechanism from VO₄³⁻ to Sm³⁺ via Gd³⁺ ions were investigated in detail. X-ray diffraction (XRD) analysis confirmed the crystalline phase for synthesized nanophosphor in a tetragonal structure with I41/amd space group. The average crystallite size estimated from XRD was ∼28 nm. Field-emission scanning electron microscopy coupled with energy dispersive X-ray analysis revealed oval shaped morphology and composition of the nanophosphor, respectively. From high-resolution transmission electron microscopy observations, the particle sizes were found to be in the range 10–80 nm. The photoluminescence studies of Y_0.77Gd_0.20VO₄:0.03Sm³⁺ nanophosphor under 311 nm excitation exhibits dominant emission peak at 598 nm corresponding to ⁴G_5/2 → ⁶H_7/2 transition. The energy transfer occurs from VO₄³⁻ to Sm³⁺ via Gd³⁺ ions was confirmed by applying Dexter and Reisfeld’s theory and Inokuti-Hirayama model. Moreover, the energy transfer efficiencies and probabilities were calculated from the decay curves. Furthermore, Commission Internationale de l’Eclairage (CIE) color coordinate (0.59, 0.37) has been observed to be in the orange-red (598 nm) region for Y_0.77Gd_0.20VO₄:0.03Sm³⁺ nanophosphor. These results perfectly established the suitability of these nanophosphors in improving the efficiency of silicon solar cells, light emitting diodes, semiconductor photophysics, and nanodevices.     

Dissociative electron attachment to polyatomic molecules: Ion kinetic energy measurements

Dissociative electron attachment to SO₂, NO₂, NF₃ and H₂O₂ is studied in terms of the kinetic energies of the dominant fragment ions. The O^? data from SO₂ show that the two major resonances at 4.6 and 7.2 eV respectively have the same dissociation limit. Similarly, the resonances at 1.8 and 3.5 eV in the O^? channel in NO₂ appear to have same dissociation limit of NO (X ²Π) + O^?, while the resonance at 8.5 eV appears to dissociate to give NO (a ⁴Π_i) along with O^?. We find considerable internal excitation of the neutral fragments in all these cases along with that of NF₃, whereas the negative ion resonance in H₂O₂ appears to fragment almost like a diatomic system with very little internal excitation of the OH and OH^? fragments.     

Synthesis and evaluation of two novel rhodamine-based fluorescence probes for specific recognition of Fec+ ion

Two low cytotoxic fluorescence probes Rb1 and Rb2 detecting Fe³⁺ were synthesized and evaluated. Rb1 and Rb2 exhibited an excellent selectivity to Fe³⁺, which was not disturbed by Ag⁺, Li⁺, K⁺, Na⁺, NH₄⁺, Fe²⁺, Pb²⁺, Ba²⁺, Cd²⁺, Ni²⁺, Co²⁺, Mn²⁺, Zn²⁺, Mg²⁺, Hg²⁺, Ca²⁺, Cu²⁺, Ce³⁺, AcO^?, Br^?, Cl^?, HPO₄^2?, HSO₃^?, I^?, NO₃^?, S₂O₃^2?, SO₃^2? and SO₄^2? ions. The detection limits were 1.87 × 10^?7 M for Rb1 and 5.60 × 10^?7 M for Rb2, respectively. 1:1 stoichiometry and 1:2 stoichiometry were the most likely recognition mode of Rb1 or Rb2 towards Fe³⁺, and the corresponding OFF–ON fluorescence mechanisms of Rb1 and Rb2 were proposed.     

Preparation and spectroscopic properties of nanostructured glass-ceramics containing Yb3+, Er3+ ions and Co2+-doped spinel nanocrystals

Transparent glass-ceramics with Yb³⁺, Er³⁺ ions in glass matrix and tetrahedral Co²⁺-doped MgAl₂O₄ nanocrystals were synthesized. XRD patterns and FESEM micrograph of the glass-ceramics showed that MgAl₂O₄ nanocrystals (sizes of 10–20 nm) are uniformly dispersed in SiO₂ glass matrix. Absorption and emission spectra of the glass-ceramics indicated that Yb³⁺, Er³⁺ remain in SiO₂ glass matrix, while Co²⁺ occupied tetrahedral sites in MgAl₂O₄ nanocrystals, and can function as saturable absorber for Er³⁺. Transparent Co²⁺, Yb³⁺, Er³⁺ co-doped glass-ceramics possesses the spectral requirements and should be a potential laser material used for self-Q-switched microchip laser operating at 1.5–1.6 μm.     

Au@Y2O3:Eu3+ rare earth oxide hollow sub-microspheres with encapsulated gold nanoparticles and their optical properties

A facile method to synthesize novel Au@Y₂O₃:Eu³⁺ hollow sub-microspheres encapsulated with moveable gold nanoparticle core and Y₂O₃:Eu³⁺ as shell via two-step coating processes and a succeeding calcination process has been developed. Silica coating on citrate-stabilized gold nanoparticles with a size of 25 nm can be obtained through a slightly modified Stöber process. Gold particles coated with double shell silica and Eu doped Y(OH)₃ can be obtained by coating on the Au@SiO₂ spheres through simply adding Y(NO₃)₃, Eu(NO₃)₃ and an appropriate quantity of NH₃·H₂O. Au@Y₂O₃:Eu³⁺ hollow sub-microspheres with moveable individual Au nanoparticle as core can be obtained after calcination of Au@Y₂O₃:Eu³⁺ particles at 600 °C for 2 h. These new core–shell structures with encapsulated gold nanoparticles have combined optical properties of both the Au nanoparticles and the Y₂O₃:Eu³⁺ phosphor materials which might have potential applications.     

Comparative study on energetic distortions of SO42− ions matrix-isolated in compounds with kröhnkite-type chains,K2Me(CrO4)2·2H2O and Na2Me(SeO4)2·2H2O (Me = Mg,Co, Ni,Zn, Cd)

Infrared spectra of compounds with kröhnkite-type infinite octahedral–tetrahedral chains, K₂Me(CrO₄)₂·2H₂O and Na₂Me(SeO₄)₂·2H₂O (Me = Mg, Co, Ni, Zn, Cd), as well as infrared spectra of the title double salts containing matrix-isolated SO₄^2? guest ions are presented and discussed in the regions of the X–O stretching modes.The SO₄^2? guest ions matrix-isolated in selenate and chromate matrices exhibit four infrared bands corresponding to the four site-group components of the stretching modes in good agreement with the low site symmetry of the host ions (C₁ site symmetry). The values of Δν₃ (site-group splitting) and Δν_max (the difference between the highest and the lowest wavenumbered components of the stretching modes) are used as an adequate measure for the extent of energetic distortion of the matrix-isolated SO₄^2? guest ions.The influence of different crystal-chemical parameters (Me²⁺–OXO₃ bond strengths, sizes of the Me²⁺ and Me⁺ ions, electronic configurations of the Me²⁺ ions, hydrogen bond strengths, and unit-cell volumes of the host compounds) on the extent of energetic distortion of both the host SeO₄^2? and CrO₄^2? ions, and the SO₄^2? guest ions is analyzed. Correlations between the values of Δν₃ and Δν_max of the guest ions and both the degree of covalency of the respective Me²⁺–OXO₃ bonds and the electronic configurations of the Me²⁺ ions have been found and will be discussed. For example, the energetic distortion of SO₄^2? ions included in the chromate lattices decreases in the order Zn > Cd > Mg as a result of the decreasing covalency of the respective Me²⁺–O bonds in the same order (Δν₃ have values of 73, 58 and 36 cm^?1, respectively). Furthermore, the values of Δν₃ and Δν_max are larger when the metal ions have CFSE ≠ 0 (crystal field stabilization energy, Co²⁺, Ni²⁺). These cations are more resistant to angular deformations of the MeO₆ octahedra (i.e. changes in the O–Me–O bond angles), thus facilitating the extent of distortion of the matrix-isolated SO₄^2? ions as compared to those having CFSE = 0 (Mg²⁺, Zn²⁺ and Cd²⁺). For example, Δν₃ and Δν_max of SO₄^2? ions matrix-isolated in K₂Zn(CrO₄)₂·2H₂O have values of 73 and 163 cm^?1, and 116 and 207 cm^?1 in Na₂Zn(SeO₄)₂·2H₂O, whereas in the respective nickel lattices Δν₃ and Δν_max have values of 88 and 173 cm^?1 (K₂Ni(CrO₄)₂·2H₂O) and 127 and 212 cm^?1 (Na₂Ni(SeO₄)₂·2H₂O).The SO₄^2? guest ions included in selenate matrices, Na₂Me(SeO₄)₂·2H₂O, are remarkably much distorted than in chromate ones, K₂Me(CrO₄)₂·2H₂O, as deduced from the values of Δν₃ and Δν_max owing to a stronger static field caused by the smaller Na⁺ ions as compared to that caused by the larger K⁺ ions. The smaller unit-cell volumes of the selenate host compounds, i.e. the higher repulsion potential at the lattice sites at which the guest ions are situated additionally favor the extent of energetic distortion of the sulfate guest ions in the selenate matrices.     

Anthroneamine based chromofluorogenic probes for Hg2+ detection in aqueous solution

Anthroneamine derivatives 1–3 (H₂O:DMSO; 9:1, HEPES buffer, pH 7.0 ± 0.1) undergo highly selective fluorescence quenching with Hg²⁺. The observed linear fluorescence intensity change allows the quantitative detection of Hg²⁺ between 200 nM/40 ppb—12 μM/2.4 ppm even in the presence of interfering metal ions viz. Na⁺, K⁺, Mg²⁺, Ca²⁺, Ba²⁺, Cr³⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Ag⁺, Cd²⁺, Pb²⁺. Probes 1–3 and their Hg²⁺ complexes also show the broad pH resistance for their practical applicability.     

A family of dodecanuclear Mn11Ln single-molecule magnets

A series of four isostructural dodecanuclear complexes [Mn^III₉Mn^II₂Ln^III(O)₈(OH)(piv)₁₆(NO₃)(CH₃CN)]·xCH₃CN·yC₇H₁₆ (piv = pivalate; x = ½, y = ¾, Ln = Tb (1); x = 2, y = ½, Ln = Dy (2), Ho (3), and Y (4)) has been prepared for which the structural motif described as ‘a lanthanide ion nested in a large manganese shell’ is observed. All compounds show out-of-phase signals in their ac susceptibilities, and their single-molecule magnet behaviour was confirmed by single-crystal micro-SQUID studies of 1-3 which show hysteresis loops of molecular origin at T < 1.0 K. The SMM behaviour observed in compounds 1-3 is more pronounced than that for 4, which contains the diamagnetic Y^III ion. This is principally the result of ferromagnetic coupling between the paramagnetic anisotropic Ln^III ions (Tb^III, Dy^III and Ho^III) and the manganese shell, which enhances the total spin ground state of the complexes.     

Transition metal-chelating surfactant micelle templates for facile synthesis of mesoporous silica nanoparticles

Highly ordered mesoporous silica nanoparticles with tunable morphology and pore-size are prepared by the use of a transition metal-chelating surfactant micelle complex using Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺ ions. These metal ions formed a metal-P123 micelle complex in an aqueous solution, while the metal ions are chelated to the hydrophilic domain such as the poly(ethylene oxide) group of a P123 surfactant. The different complexation abilities of the utilized transition metal ions play an important role in determining the formation of nano-sized ordered MSNs due to the different stabilization constant of the metal-P123 complex. Consequently, from a particle length of 1700 nm in the original mesoporous silica materials, the particle length of ordered MSNs through the metal-chelating P123 micelle templates can be reduced to a range of 180–800 nm. Furthermore, the variation of pore size shows a slight change from 8.8 to 6.6 nm. In particular, the Cu²⁺-chelated MSNs show only decreased particle size to 180 nm. The stability constants for the metal-P123 complex are calculated on the basis of molar conductance measurements in order to elucidate the formation mechanism of MSNs by the metal-chelating P123 complex templates. In addition, solid-state ²⁹Si, ¹³C-NMR and ICP-OES measurements are used for quantitative characterization reveal that the utilized metal ions affect only the formation of a metal-P123 complex in a micelle as a template.     

Vacuum ultraviolet spectroscopic properties of rare earth (RE) (RE = Eu,Tb, Dy,Sm, Tm)-doped K2GdZr(PO4)3 phosphate

The luminescent characteristics of RE (RE³⁺ = Eu, Tb, Dy, Sm and Tm)-doped K₂GdZr(PO₄)₃ have been investigated. The band in the range of 130–157 nm in the VUV excitation spectra of these compounds is attributed to the host lattice or PO₄^3? group absorption and the band from 157 nm to 215 nm with the maximum at 188 nm is due to the O–Zr charge transfer transition. For Eu³⁺-doped sample, the relatively weak band of O^2?–Eu³⁺ charge transfer (CTB) at 222 nm is observed and for Tb³⁺-doped sample, the band at 223 nm is related to the 4f–5d spin-allowed transition of Tb³⁺. For Dy³⁺- and Sm³⁺-doped samples, the O^2?–Dy³⁺ and O^2?–Sm³⁺ CTBs have not been observed, probably due to the 2p electrons of oxygen tightly bound to the zirconium ion in the host lattice. In Tm³⁺-doped sample, the weak O^2?–Tm³⁺ CTB is located at 170 nm. It is observed that there is energy transfer between the host and the luminescent activators (e.g. Eu³⁺, Tb³⁺ and Sm³⁺) except for Tm³⁺.     

A novel approach for determining total titanium from titanium dioxide nanoparticles suspended in water and biosolids by digestion with ammonium persulfate

Titanium dioxide (i.e. TiO₂) in nano-form is a constituent of many nanomaterials that are used in sunscreens, cosmetics, industrial products and in biomedical applications. Quantification of TiO₂ nanoparticles in various matrixes is a topic of great interest for researchers studying the potential health and environmental impacts of nanoparticles. However, analysis of TiO₂ as Ti⁴⁺ is difficult because current digestion techniques require use of strong acids that may be a health and safety risk in the laboratory. To overcome this problem, we developed a new method to digest TiO₂ nanoparticles using ammonium persulfate as a fusing reagent. The digestion technique requires short times to completion and optimally requires only 1 g of fusing reagent. The fusion method showed >95% recovery of Ti⁴⁺ from 6 μg mL^?1 aqueous suspensions prepared from 10 μg mL^?1 suspension of different forms of TiO_2, including anatase, rutile and mixed nanosized crystals, and amorphous particles. These recoveries were greater than open hot-plate digestion with a tri-acid solution and comparable to microwave digestion with a tri-acid solution. Cations and anions commonly found in natural waters showed no significant interferences when added to samples in amounts of 10 ng to 110 mg, which is a much broader range of these ions than expected in environmental samples. Using ICP-MS for analysis, the method detection limit (MDL) was determined to be 0.06 ng mL^?1, and the limit of quantification (LOQ) was 0.20 ng mL^?1. Analysis of samples of untreated and treated wastewater and biosolids collected from wastewater treatment plants yielded concentrations of TiO₂ of 1.8 and 1.6 ng mL^?1 for the wastewater samples, respectively, and 317.4 ng mg^?1 dry weights for the biosolids. The reactions between persulfate ions and TiO₂ were evaluated using stoichiometric methods and FTIR and XRD analysis. A formula for the fusing reaction is proposed that involves the formation of sulfate radicals.     

The mechanism for diamagnetic products formation under the radiolysis of alkali nitrates

Based on optical measurements, the kinetics of peroxynitrite accumulation in alkali nitrate crystals γ-irradiated at 310 K has been investigated. The initial radiation chemical yields were calculated to be 0.60±0.05, 0.14±0.03, 0.35±0.03, 0.65±0.04 (100 eV)⁻¹ for NaNO₃, KNO₃, RbNO₃, and CsNO₃, respectively. The mechanism for the radiolysis of crystalline alkali nitrates is interpreted in terms of formation of the peroxynitrite ions and the nitrite ions from high-energy singlet and triplet excited states of the nitrate ions, respectively. These states can be generating under the radiationless transitions of electrons from the cation conductivity band into the anion conductivity band accompanied by the Auger excitation of the nitrate ions.