The status of strontium in biological apatites: an XANES/EXAFS investigation

Osteoporosis represents a major public health problem through its association with fragility fractures. The public health burden of osteoporotic fractures will rise in future generations, due in part to an increase in life expectancy. Strontium‐based drugs have been shown to increase bone mass in postmenopausal osteoporosis patients and to reduce fracture risk but the molecular mechanisms of the action of these Sr‐based drugs are not totally elucidated. The local environment of Sr²⁺ cations in biological apatites present in pathological and physiological calcifications in patients without such Sr‐based drugs has been assessed. In this investigation, X‐ray absorption spectra have been collected for 17 pathological and physiological calcifications. These experimental data have been combined with a set of numerical simulations using the ab initioFEFF9 X‐ray spectroscopy program which takes into account possible distortion and Ca/Sr substitution in the environment of the Sr²⁺ cations. For selected samples, Fourier transforms of the EXAFS modulations have been performed. The complete set of experimental data collected on 17 samples indicates that there is no relationship between the nature of the calcification (physiological and pathological) and the adsorption mode of Sr²⁺ cations (simple adsorption or insertion). Such structural considerations have medical implications. Pathological and physiological calcifications correspond to two very different preparation procedures but are associated with the same localization of Sr²⁺versus apatite crystals. Based on this study, it seems that for supplementation of Sr at low concentration, Sr²⁺ cations will be localized into the apatite network.     

Effecting factors of the emission spectral characteristics of rare-earth strontium aluminate for anti-counterfeiting application

The rare-earth strontium aluminate phosphor with stable physical and luminescent performances is a suitable rare-earth luminescent material for spectrum-fingerprint anti-counterfeiting fiber. In order to promote further the development of variety and the improvement of anti-counterfeiting effects of spectrum-fingerprint fiber, in this research, several kinds of rare-earth strontium aluminates and spectrum-fingerprint anti-counterfeiting fiber were prepared by solid-state reaction and special spinning technique, respectively. The effects upon manufacturing elements of strontium aluminate including calcining temperature, Al/Sr ratios, the addition of H₃BO₃, Eu²⁺ and Dy³⁺ and external environmental factors of applications such as fiber-forming polymer on emission spectral characteristics were investigated systematically in the anti-counterfeiting application. The results showed that with the increase in the calcining temperature, the amounts of H₃BO₃ doping and the concentration of Eu²⁺ and Dy³⁺, the emission intensity of rare-earth strontium aluminate increased and reached to the peak at a certain point at start, and then decreased gradually beyond this point. Al/Sr molar ratios influenced not only the intensity but also the wavelength of emission. Fiber-forming polymer had little effect on the emission wavelength and the shape in the luminescence, but greatly lowered the intensity of emission.     

Nuclear ground state spins of short-lived strontium isotopes

Nuclear ground state spins of the odd-mass strontium isotopes between A=79 and 97 were determined by measurements of the hyperfine structure in the ionic transition 5s²S_1/2?5p²P_3/2. The spins of⁹³Sr and⁹⁷Sr are revised to I=5/2 and I=1/2, respectively, while assignments for the remaining isotopes are confirmed.     

Dispersion and polarization interactions of the strontium atom

Dispersion coefficients involving the 5s ^{2 1} S ^e and 5s5p ^1,3P ^o states of strontium are determined from a large basis configuration interaction calculation. Dispersion coefficients are presented for the strontium dimer and also for strontium interactions with hydrogen and the rare gases. Polarizabilities and oscillator strengths from some low lying states are also given. The ground state polarizability and that of the 5s5p ¹P ^o and 5s4d ¹D ^e states are very similar in size.     

Stark broadening of singly ionized strontium and calcium lines

Profiles of five calcium II and six strontium II lines have been measured in an argon plasma behind the reflected shock wave. The plasma was produced in an electromagnetically drivenT tube and calcium and strontium were present as an impurities. Electron densities were in the range 1.91–3.40·10¹⁷ cm^?3 and the electron temperatures between 10300 and 14200 °K. The half halfwidths of the measured profiles of some Ca II and Sr II multiplets show large discrepancies with theoretical predictions.     

High temperature and pressure thermodynamics of strontium: A macroscopic approach

Close proximity of d-bands (above) to the Fermi level (E _F) makes the heavy alkaline earth metals (Ca, Sr and Ba) fairly sensitive to external influences like temperature and pressure. Softening of some of the phonon modes at high temperatures and/or pressures implies that anharmonic effects can play an important role in determining lattice dynamics and related properties. In the conventional approach, phonon density of states (p-dos) have to be calculated at each volume to compute free energy and thereby the other thermodynamic properties, which is computationally quite demanding. Using an alternative technique, the mean-field potential (MFP) approach was combined with the relatively soft local pseudopotential to obtain the free energy at different temperatures and pressures. The results for phonon frequency shifts at finite temperatures using the MFP approach and those calculated from p-dos within the quasiharmonic approximation are very similar. This validates the use of the MFP approach coupled with the local pseudopotential to estimate vibrational response of the system at high-temperature and high-pressure environments. The present scheme was used to study various thermophysical properties for elemental strontium at elevated temperatures and pressures, including the high-pressure melting curve and temperature along the shock Hugoniot. Computed results are affirmatively compared and analyzed with other reported data. The present scheme completely bypasses traditional cumbersome calculations, and it is computationally convenient yet accurate.     

2-photon ionization for efficient seeding and trapping of strontium ions

We describe an efficient way to photoionize strontium atoms in a linear radio-frequency trap. We use a 2-photon second order process to excite the autoionization resonance (4d²+5p²) ¹D₂ in neutral strontium (Sr). A doubled Ti:sapphire laser system is used at 431 nm to provide 100 fs pulses at 82 MHz. The fabrication of the laser systems for addressing the Sr⁺ transitions necessary for laser cooling and excitation of quantum jumps, vacuum system and ion trap structure are also described. With the current setup a easy and repeatable trapping of linear ion chains is readily achieved at very low Sr vapor pressures.     

Fine-structure splittings of 2F states of singly ionized strontium

We have studied the 4d?nf and 5d?nf (n = 4?8) transitions of singly ionized strontium using high-resolution optical spectroscopy. The ²F fine structure is inverted in all the states observed and decreases from ?1.06cm^?1 in 4f to ?0.26 cm^?1 in 8f.     

Persistent Luminescence of Eu2☎ and Na☎ Doped Alkaline Earth Aluminates

The luminescence and afterglow properties of the Eu^2? and Na^? doped alkaline earth aluminales, stoichiometric and non-stoichiometric (M_x Al₂O₄:Eu^2?, Na^?; M = Ca or Sr, x = 0.97, 1.00 or 1.03, X_Na, = 0.02), were studied. Broad band luminescence and afterglow of the Eu^2? ion were observed in the blue (λ_max = 440nm) and green (λ_max = 520nm) region for the calcium and strontium aluminates, respectively. Both Na^? co-doping and strontium excess quenched the afterglow efficiently. The results supported the mechanism of the persistent luminescence where the cation vacancies act as traps. The results for the calcium aluminates were ambiguous, probably due to the slightly larger ionic radius of the Na^? with respect to that of Ca^2?. The sodium ions may not fit into the calcium sites and thus form (an) independent compound(s).     

Loose‐powder technique for X‐ray fluorescence analysis of ancient pottery using a small (100 mg) powdered sample

A molded‐loose‐powder technique using a small powdered sample (100 mg) was developed for the X‐ray fluorescence analysis of 22 components (Na₂O, MgO, Al₂O₃, SiO₂, P₂O₅, K₂O, CaO, TiO₂, MnO, Fe₂O₃, V, Cr, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, and Pb) in ancient pottery. This loose powder specimen was prepared by pressing the small powdered sample into a sample holder, formed from a stainless steel disk (48‐mm diameter × 0.8‐mm height) with a hole (11‐mm diameter), by hand. Calibration standards were prepared by homogenizing chemical reagents containing these 22 analytes using the concentration ranges of 166 ancient potteries and three clay materials from Japan. The calibration curves of these benchmark mixtures exhibited a good linearity (correlation coefficient, r = 0.990–1.000), accuracy, and reproducibility compared with those of other synthesized specimens and three reference standards. The lower limits of detection were less than tens of mg kg^?1 (e.g., 94 mg kg^?1 for Na₂O, 11 mg kg^?1 for P₂O₅, 1.1 mg kg^?1 for Rb, and 0.9 mg kg^?1 for Y). Using the present method, we determined 22 components in two prehistoric potteries from Japan. The advantage of this method is that only a small amount of sample is required, which can be prepared easily and rapidly and reused for other analyses. Copyright © 2012 John Wiley & Sons, Ltd.     

Analysis of magnetic disaccommodation in La-Co-substituted strontium ferrites

M-type strontium ferrites substituted by La³⁺-Co²⁺(Sr_1−xLa_xFe_12−xCo_xO₁₉) were prepared by ceramic process. Effects of the substituted amount of La³⁺ and Co²⁺ on structure and magnetic properties of Sr_1−xLa_xFe_12−xCo_xO₁₉ compounds have systematically been investigated by X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and magnetic disaccommodation. In the measurement range from 80 to 500 K, the magnetic disaccommodation is represented by means of isochronal curves. It is well known that magnetic disaccommodation cannot be obviously found in the M-type of pure strontium ferrites. However, three peaks were observed in Sr_1−xLa_xFe_12−xCo_xO₁₉, and this behavior is explained in terms of the presence of Fe²⁺ cation and to the site occupation by the magnetic Co²⁺ ionic within the hexagonal structure.     

Fluorescence of Eu-activated alkaline earth halosilicates

Three luminescent materials, each with a distinct and novel crystalline structure have been found in the alkaline earth halosilicate series. Their emission is in the blue/green part of the spectrum, the peaks falling at 500 nm for the Sr/Cl compound, 442 nm for the Ca/Cl compound and 514 nm for the Ca/Br compound. The strontium chlorsilicate, Sr₂Si₃O₈ 2SrCl₂, is of particular interest showing good temperature dependence characteristics (365 nm excitation) and also exhibiting an acicular crystal habit. Other alkaline earth/halide combinations and the binary alkaline earth systems were examined.     

Analysis of n(87Sr)/n(86Sr), δ88Sr/86SrSRM987 and elemental pattern to characterise groundwater and recharge of saline ponds in a clastic aquifer in East Austria

Elemental and isotopic pattern of n(⁸⁷Sr)/n(⁸⁶Sr) and δ⁸⁸Sr/⁸⁶Sr_SRM987 were used to characterise groundwater and recharge of saline ponds in a clastic aquifer in East Austria. Therefore, shallow, artesian and thermal groundwaters of the investigated aquifer along with rainfall and rivers were analysed using (MC) ICP-MS. The n(⁸⁷Sr)/n(⁸⁶Sr) ratio and elemental pattern changed with aquifer depth as a result of progressing bedrock leaching and dissolution with increasing groundwater residence time. The n(⁸⁷Sr)/n(⁸⁶Sr) ratio of shallow groundwater below saline ponds of 0.71019?±?0.00044 was significantly different from thermal groundwater of 0.71205?±?0.00035 (U, k?=?2). In contrast to previous theories, this result suggested no recharge of saline ponds by upwelling paleo-seawater. Isotope pattern deconvolution revealed that rainfall accounted to about 60% of the n(⁸⁷Sr)/n(⁸⁶Sr) ratio of shallow groundwater below saline ponds. The δ⁸⁸Sr/⁸⁶Sr_SRM987 values of groundwater decreased from about 0.25 ‰ in most shallow, to predominantly negative values of about –0.24 ‰ in artesian groundwater. This result indicated leaching and dissolution of weathered minerals. In turn, the δ⁸⁸Sr/⁸⁶Sr_SRM987 of deep thermal groundwater showed positive values of about 0.12 ‰, which suggested removal of ⁸⁶Sr from solution by carbonate precipitation. These results highlight the potential of δ⁸⁸Sr/⁸⁶Sr_SRM987 signature as an additional geochemical tracer.     

Tailoring MoS2 Ultrathin Sheets Anchored on Graphene Flexible Supports for Superstable Lithium‐Ion Battery Anodes

2D MoS₂ has a significant capacity decay due to the stack of layers during the charge/discharge process, which has seriously restricted its practical application in lithium‐ion batteries. Herein, a simple preform‐in situ process to fabricate vertically grown MoS₂ nanosheets with 8–12 layers anchored on reduced graphene oxide (rGO) flexible supports is presented. As an anode in MoS₂/rGO//Li half‐cell, the MoS₂/rGO electrode shows a high initial coulomb efficiency (84.1%) and excellent capacity retention (84.7% after 100 cycles) at a current density of 100 mA g^?1. Moreover, the MoS₂/rGO electrode keeps capacity as high as 786 mAh g^?1 after 1000 cycles with minimum degradation of 54 µAh g^?1 cycle^?1 after being further tested at a high current density of 1000 mA g^?1. When evaluated in a MoS₂/rGO//LiCoO₂ full‐cell, it delivers an initial charge capacity of 153 mAh g^?1 at a current density of 100 mA g^?1 and achieves an energy density of 208 Wh kg^?1 under the power density of 220 W kg^?1.     

Luminescence of europium and ytterbium ions in strontium hexaborate

We have studied the luminescent properties of Eu^2+/3+ and Yb²⁺ ions in strontium hexaborate SrB₆O₁₀ for excitation in the 120–400 nm region. The luminescence spectra of Ln²⁺ ions in SrB₆O₁₀ consist of overlapping bands in the 370–520 nm region, due to 5d → 4f transitions at several nonequivalent centers. In the excitation spectra, besides the bands associated with 4f → 5d transitions in the Ln²⁺ ions, we also observe a band in the 135–160 nm region due to the transitions O(2p) → B(2s,2p) within the borate anions. The luminescence of the Eu³⁺ ions is excited most efficiently in the region of the Eu³⁺ charge transfer band (λ_max = 226 nm). The results obtained are compared with data for Ln in other strontium borates. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 770–774, November–December, 2006.     

Effects of strontium on the characteristics of Pb(Zr1/2Ti1/2)O3--Pb(Zn1/3Nb2/3)O3 ceramics

The dielectric and piezoelectric properties of pyrochlore-free lead zirconate titanate-lead zinc niobate ceramics were investigated systematically as a function of Sr doping. The powders of Pb_{(1? x )}Sr _x [0.7(Zr_{1 / 2}Ti_{1 / 2})–0.3(Zn_{1 / 3}Nb_{2 / 3})]O₃, where x?=?0–0.06 were prepared using the columbite-(wolframite) precursor method. The ceramic materials were characterized using X-ray diffraction, dielectric spectra, hysteresis and electromechanical measurements. The phase-pure perovskite phase of Sr-doped PZN--PZT ceramics was obtained over a wide compositional range. The results showed that the optimized electrical properties were also achieved at composition x?=?0.0, which were K _P?=?0.69, d ₃₃?=?670?pC?N^?1, P _r?=?31.9?µC?cm^?2 and ε_rmax?=?18600. Maximum dielectric constant values of the systems decreased rapidly with increasing Sr concentration. Moreover, with increasing Sr concentration dielectric constant versus temperature curves become gradually broader. The diffuseness parameter increased significantly with Sr doping. Furthermore, Sr doping has been shown to produce a linear reduction in the transition temperature (T _m)?=?294.1–12.7x°C with concentration (x). Sr shifts the transition temperature of this system at a rate of 12.7°C?mol^?1%.     

Simultaneous diffusion of calcium and strontium in KCl single crystals

Concentration dependent diffusion coefficients for ⁴⁵Ca²⁺ and ⁸⁵Sr²⁺ in purified KCl were measured using a sectioning method. KCl was purified by an ion exchange — Cl₂?HCl process and the crystals grown under $\text{1}\text{6}$ atmosphere of HCl. The tracers were purified on small disposable ion exchange columns to remove precessor and daughter impurities prior to use in a diffusion anneal. Isothermal diffusion anneals were made in the temperature range from 451% to 669%C. At temperatures above 580%C (the lowest melting eutectic in this system) diffusion was from a vapor source: below 580%C surface depositied sources were used. The saturation diffusion coefficients. enthalpies and entropies of impurity-vacancy associations were calculated using the common ion model for simultaneous diffusion of divalent ions in alkali halides. In KCl the saturation diffusion coefficients D_S(ca) and D_s(Sr) are given by

$\text{D}{}_{\mathrm{s}}\text{(Ca) = 9.93 × 10}{}^{\mathrm{?5}}\text{exp(?0.592}\text{eV}\text{kT}\text{)}\text{cm}{}^2\text{sec}$

(1) and

$\text{D}{}_{\mathrm{s}}\text{(Sr) = 1.20 × 10}{}^{\mathrm{?3}}\text{exp(?0.871}\text{eV}\text{kT}\text{)}\text{cm}{}^2\text{sec}$

(2) for calcium and strontium, respectively. The Gibbs free energy of association of the impurity vacancy complex in KCl for calcium can be represented by

$\text{Δg(Ca) = ?-0.507 eV + (2.25 × 10}{}^{\mathrm{?4}}\text{eV}\text{\%K}\text{)T}$

(3) and that for strontium by

$\text{Δg(Sr) = ?0.575 eV + (2.90 × 10}{}^{\mathrm{?4}}\text{eV}\text{\%K}\text{)T}$

. (4)     

Two-color three-photon resonant excitation spectrum of strontium in the autoionization region

We report new studies of the odd parity autoionizing Rydberg series of strontium attached to the 4d( ² D _{3/2, 5/2}) ionic limits possessing J = 1-3 based on the two-color three photon resonant excitation technique in conjunction with an atomic beam apparatus. Using the 4d ²³ P ₀ intermediate levels, we have been able to record the autoionizing Rydberg series of J = 1 whereas, from the 4d ²³ P ₂ intermediate level the series of Rydberg levels possessing J = 1, 2 and 3 have been observed. The level assignments and the line shapes simulations of the autoionizing resonances have been made using the multichannel quantum defect theory. Received 21 November 2001 / Received in final form 2 May 2002 Published online 19 July 2002