Mössbauer effect study of the crystal chemistry of tourmaline

One of the main features of the tourmaline group of minerals is that the six coordinatedY andZ sites, possessing different point group symmetries and sizes, share edges. The ME parameters are, therefore, controlled by the mechanisms by which the tourmaline structure obtains congruency along the common edge between the two octahedra. For example, if the size of theY site in elbaite is increased by replacing Li and Al by Fe²⁺, then, for small values of Fe²⁺, size congruency is maintained by simultaneously replacing Al by Fe²⁺ at theZ site. The ME spectra of Fe-bearing elbaite are therefore characterised by two doublets assigned to Fe²⁺ in theY andZ sites. For higher values of Fe²⁺ at theY site, however, the tourmaline structure reduces the misfit further by oxidation of Fe²⁺ at theY site. The effect of the second mechanism is to increase Fe²⁺-Fe³⁺ interaction centres and thereby promote charge delocalisation. These Fe-Fe charge interactions introduce three more peaks with ME parameters intermediate between Fe²⁺ and Fe³⁺. On the other hand, the replacement of Fe²⁺ by Mg²⁺ reduces the density of Fe²⁺-Fe³⁺ centres, blocks Fe-Fe charge interactions and increases the intensity of Fe³⁺.     

Production of long-lived isomers by 4 MeV endpoint energy bremsstrahlung

Long-lived isomers of ⁸⁷ Sr, ¹⁰³Rh, ¹¹¹Cd, ^{113, 115}In, ¹¹⁷Sn, ¹⁷⁶Lu, ¹⁸⁹Os, ¹⁹³Ir and ¹⁹⁵Pt were produced by means of bremsstrahlung from a 4 MeV end-point energy 25 A intensity electron beam. Isomeric ativities were measured by gamma-spectrometry. Photoex-citation exhibits a steep rise as compared to lower energy excitations of prior experiments by high activity ¹³⁷Cs, ⁶⁰Co, ¹⁴²Pr and ²⁴Na sources. The large variety in the magnitude of the excitation cross section may mostly arise from largely di?ering isomer ratios governed by spin differences between isomeric and ground levels, and likely by di?erences in the multipole character of the upward transitions, too. Isomer excitation seems to exhibit loose correlations with the product of photoabsorption cross section and isomer ratio derived from (n, n′) reactions on the one hand, and with the product of valence proton and neutron numbers and isomer ratio on the other hand.     

Activation cross-sections of titanium isotopes at neutron energies of 13.5–14.8 MeV

The cross-sections for ~(46) Ti(n,2 n)~(45) Ti, ~(46) Ti(n,p)~(46 m+g) Sc+~(47) Ti(n,d*)~(46 m+g) Sc, ~(46)Ti(n,p)~(46 m+g) Sc, ~(47) Ti(n,p)~(47) Sc+~(48) Ti(n,d*)~(47) Sc, ~(47) Ti(n,p)~(47) Sc, ~(48) Ti(n,p)~(48) Sc+~(49) Ti(n,d*)~(48) Sc,~(48) Ti(n,p)~(48) Sc, and ~(50) Ti(n,α)~(47) Ca reactions were investigated around neutron energies of 13.5–14.8 Me V by means of the activation technique. Fast neutrons were produced by the~3 H(d,n)~4 He reaction. Neutron energies from different directions in the measurements were obtained in advance using the method of cross-section ratios for ~(90) Zr(n,2 n)~(89 m+g) Zr and ~(93) Nb(n,2 n)~(92 m) Nb reactions. The results obtained are analyzed and compared with the experimental data provided by the literature and verified nuclear data in the JEFF-3.3,CENDL-3.1, ENDF/B-VIII.0 libraries, as well as results calculated by Talys-1.9 code.     

Production of long-lived isomers by 4 MeV endpoint energy bremsstrahlung

Long-lived isomers of⁸⁷Sr,¹⁰³Rh,¹¹¹Cd,^113,115In,¹¹⁷Sn,¹⁷⁶Lu,¹⁸⁹Os,¹⁹³Ir and¹⁹⁵Pt were produced by means of bremsstrahlung from a 4 MeV endpoint energy 25µA intensity electron beam. Isomeric activities were measured by gamma-spectrometry. Photoexcitation exhibits a steep rise as compared to lower energy excitations of prior experiments by high activity¹³⁷Cs,⁶⁰Co,¹⁴²Pr and²⁴Na sources. The large variety in the magnitude of the excitation cross section may mostly arise from largely differing isomer ratios governed by spin differences between isomeric and ground levels, and likely by differences in the multipole character of the upward transitions, too. Isomer excitation seems to exhibit loose correlations with the product of photoabsorption cross section and isomer ratio derived from (n,n′) reactions on the one hand, and with the product of valence proton and neutron numbers and isomer ratio on the other hand.     

The First in Vivo Observation of C–N Coupling in Mammalian Brain

[5-¹³C,¹⁵N]Glutamine, with ¹J(¹³C–¹⁵N) of 16 Hz, was observed in vivo in the brain of spontaneously breathing rats by ¹³C MRS at 4.7 T. The brain [5-¹³C]glutamine peak consisted of the doublet from [5-¹³C,¹⁵N]glutamine and the center [5-¹³C,¹⁴N]glutamine peak, resulting in an apparent triplet with a separation of 8 Hz. The time course of formation of brain [5-¹³C,¹⁵N]glutamine was monitored in vivo with a time resolution of 20–35 min. This [5-¹³C,¹⁵N]glutamine was formed by glial uptake of released neurotransmitter [5-¹³C]glutamate and its reaction with ¹⁵NH₃ catalyzed by the glia-specific glutamine synthetase. The neurotransmitter glutamate C5 was selectively¹³C-enriched by intravenous [2,5-¹³C]glucose infusion to ¹³C-label whole-brain glutamate C5, followed by [¹²C]glucose infusion to chase ¹³C from the small and rapidly turning-over glial glutamate pool, leaving ¹³C mainly in the neurotransmitter [5-¹³C]glutamate pool, which is sequestered in vesicles until release. Hence, the observed [5-¹³C,¹⁵N]glutamine arises from a coupling between ¹³C of neuronal origin and ¹⁵N of glial origin. Measurement of the rate of brain [5-¹³C,¹⁵N]glutamine formation provides a novel noninvasive method of studying the kinetics of neurotransmitter uptake into glia in vivo, a process that is crucial for protecting the brain from glutamate excitotoxicity.     

Infrared Spectra Interpretations of Clay-Adsorbed Water in Relation to the “Anomalous” Water Controversy

Abstract

The nature of surface adsorbed water has been the subject of countless investigations. Much of the discussion has centered around the degree and strength of H-bonding to surface groups and between adjacent water molecules.^1,2 Water condensed into glass or quartz capillaries sometimes has unusual properties. This unusual water has been referred to as “orthowater,”³ “anomalous water,”^4,5,6 and “polywater”^7,8 and was thought by some to be polymers of water formed by specific surface catalysis.^1–3 Several possible structures of “polywater” have been suggested which require formation of symmetrical or very strong H-bonds between water molecules.^4,6,7 Infrared spectra of polywater have been presented^7,8 and the strongest absorption band which appeared at 1595 cm^?1 was assigned to the symmetric O-H-O bond. However, more recent investigations suggest that the observed polywater bands may actually be SO₄ ^2-, -COOH^?, or HCO₃ ^? bands, impurities collected by surface diffusion,⁹ or bands of a HNO₃ solution formed by corona discharge.¹⁰ Other observers^11,12 suggest that polywater may be a hydrosol formed by surface contaminates.     

N.M.R. Spectra of the Fuchs0Nes: Structure of Naphthofuchsone

Following the initial synthesis of the fuchsones¹I, (α, η -diphenyl-1,4-benzoquinone methides), numerous substituted members of this series have been described by workers interested in triphenylmethane dyes. The fuchsones have been synthesized by the sulfuric acid condensation of benzilic acid and appropriate phenol¹, by dehydration of 4-hydroxytriphenylcarbinol², by oxidation 4-hydroxytri-phenylmethane and by photochemically induced reactions benzophenones with 2,6-dialkylphenols⁴.     

MRCI studies on ground and excited states of CBr

Potential curves and spectroscopic constants for a large number of doublet and quartet states of CBr were obtained by multireference configuration interaction calculations, using valence triple-zeta basis sets with polarization and diffuse functions. Besides the X²Π ground state, 1⁴Σ^?, 1²Δ and 2²Σ⁺ have been found to be stable. Spectroscopic constants calculated for 1²Δ are in excellent agreement with experimental values obtained by Dixon and Kroto in 1963. Their observed predissociation of one component of 1²Δ can be explained by the crossing of the 1²Δ potential near equilibrium by 1²Σ⁺. The 1²Σ⁺ state is calculated to have a shallow long-range minimum at 2.31?Å. The dissociation energy of X²Π is calculated to be 3.43?eV. An observed T _e of 4.97?eV for 2²Σ⁺ agrees with the theoretical value. Several Rydberg states of the 2π→Ryd and 3σ→Ryd series, starting at T _e ?=?5.25?eV, were identified. Photodissociation of CBr by sunlight, important in the ozone cycle, can occur via direct dissociation of the ground state, or by excitation to 1²Δ followed by predissociation. Most dissocative repulsive states lie at higher energies, and are not expected to participate in the photodisscociation of CBr.     

Experimental study for the production cross sections of positron emitters induced from 12C and 16O nuclei by low-energy proton beams

In proton therapy, positron emitters are induced from ¹²C and ¹⁶O nuclei by protons on the beam path in the patient. Many studies for monitoring positron emitters with beam-induced PET technique have been performed by various groups to verify the proton beam range and the dose in the patient for quality assurance (QA). The QA methods proposed by some groups require accurate production cross sections of the positron emitters produced by protons, especially in the low-energy region. The aim of this study was to develop a method for measuring the production cross sections of positron emitters using standard equipment for proton therapy, and to measure the cross sections of positron emitters produced by low-energy protons and verify them in comparison with data of previous experiments. An 80-MeV proton beam was produced by a synchrotron, and the energy was degraded by polyethylene blocks to obtain various beam energies. The number of protons was estimated from the charge induced in a parallel-plate ionization chamber by protons. Low-energy protons of 14–70 MeV were used to bombard ¹²C-rich and ¹⁶O-rich target materials: namely, polyethylene and gelatinous water. The time-activity curve was then measured by a high-sensitivity PET scanner to extract the number of positron emitters produced in the target. The production cross sections for four reaction channels: ¹⁶O(p, pn)¹⁵O, ¹⁶O(p, 3p3n)¹¹C, ¹⁶O(p, 2p2n)¹³N, and ¹²C(p, pn)¹¹C were then measured. The cross sections for the ¹⁶O(p, pn)¹⁵O reaction channel were consistent with data of previous experiments within the uncertainties, while those of ¹²C(p, pn)¹¹C were generally lower than data of previous experiments. These results suggested that further measurements of the production cross sections will be necessary.     

Enhanced radiation hardness of ZnO nanorods versus bulk layers

It is shown that ZnO nanorods grown by MOCVD exhibit enhanced radiation hardness against high energy heavy ion irradiation as compared to bulk layers. The decrease of the luminescence intensity induced by 130 MeV Xe⁺²³ irradiation at a dose of 1.5 × 10¹⁴ cm^–2 in ZnO nanorods is nearly identical to that induced by a dose of 6 × 10¹² cm^–2 in bulk layers. The change in the nature of electronic transitions responsible for luminescence occurs at an irradiation dose around 1 × 10¹⁴ cm^–2 and 5 × 10¹² cm^–2 in nanorods and bulk layers, respectively. High energy heavy ion irradiation followed by thermal annealing is also effective on the quality of ZnO nanorods grown by electrodeposition. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ag离子注入非晶SiO2的光学吸收、拉曼谱和透射电镜研究

能量为200keV的Ag离子，以1×10¹⁶，5×10¹⁶，1×10¹⁷ cm^-2的剂量分别注入到非晶SiO₂玻璃，光学吸收谱显示：注入剂量为1×10¹⁶ cm^-2的样品的光吸收谱为洛伦兹曲线，与Mie理论模拟的曲线形状一致；注入剂量较大的5×10¹⁶，1×10¹⁷ cm^-2的谱线共振吸收增强，峰位红移并出现伴峰. 透射电镜观察分析表明，注入剂量不同的样品中形成的纳米颗粒的大小、形状、分布都不同，注入剂量较大的还会产生明显的表面溅射效应，这些因素都会影响共振吸收的峰形、峰位和峰强. 当注入剂量达到1×10¹⁷ cm^-2时，Ag纳米颗粒内部可能还形成了杂质团簇. 关键词： 离子注入 纳米颗粒 共振吸收 红移     

Spin polarization of β-emitting fragments in high energy heavy ions on Be collisions

The degrees of nuclear spin polarization of ^8,12B, ⁹C, ¹²N, ¹³O, ^20,21F, ²³Mg, ²⁷Si and ³⁹Ca produced in the high energy ^12,13C, ¹⁶O, ²²Ne, ²⁴Mg, ²⁸Si and ⁴⁰Ca ions on Be collisions have been measured systematically, for the technical developments of the nuclear moment studies as well as the hyperfine interaction studies by means of β-NMR technique. The fragment momentum dependences were well reproduced by the simple kinematical model. Incident energy dependence and the mass dependence as well as the reaction angle dependences were qualitatively explained by the mixing of the near and far side collisions. This revised version was published online in August 2006 with corrections to the Cover Date.     

Study of dependence of quasi-particle alignment on proton and neutron numbers in A = 80 region through g-factor measurements

Dependence of quasi-particle alignment on proton and neutron numbers has been studied in A?=?80 mass region through g-factor measurements by using TMF-IMPAD. The experimental results show that for the nuclides ⁸⁴Zr, ⁸⁵Zr and ⁸⁶Zr with Z?=?40 the proton alignment is followed by the neutron alignment in ⁸⁴Zr and ⁸⁵Zr, while the neutron alignment is followed by the proton alignment in ⁸⁶Zr, and for the nuclides ⁸²Sr, ⁸³Y, ⁸⁴Zr and ⁸⁵Nb with N?=?44 the proton aligns only in ⁸²Sr, the proton alignment occurs first that is followed by the neutron alignment in ⁸³Y and ⁸⁴Zr and the neutron alignment is followed by the proton alignment in ⁸⁵Nb. Proton and/or neutron alignments lead to different patterns of the g-factor variation with spin.     

Enhanced luminescent properties of Y3Al5O12:Tb,Ce phosphor prepared by spray pyrolysis

Yttrium aluminum garnet (YAG) particles doped with Tb³⁺ or double doped with Tb³⁺ and Ce³⁺ were prepared by spray pyrolysis and characterized by photo- and cathode-luminescence. It was tried to incorporate a broad band of Ce³⁺ activator into the line peaks of Tb³⁺ in YAG host without the reduction of emission intensity. Ce-codoped YAG:Tb particles showed a broad band emission due to the d-f transition of Ce³⁺ and a reduction in the intensity of emission peaks due to ⁵D₃-⁷F_j (j=3, 4, 5, 6) transition of Tb³⁺ when they were excited by the ultraviolet light of 270 nm. These results supported that an effective energy transfer occurs from Tb³⁺ to Ce³⁺ in YAG host. Codoping Ce³⁺ ions greatly intensified the excitation peak at 270 nm for the emission at 540 nm of Tb³⁺, which means that more lattice defects, involving in the energy absorption and transfer to Tb³⁺, are formed by the Ce³⁺ codoping. The finding gives a promising approach for enhancing the luminescence efficiency.     

Synthesis and Spectral Study of Several Solid M3[Eu(2,6-Pyridinedicarboxylate)3] Salts (M=Li+, Na+, K+, Rb+, Cs+, NH4 +, and Pyridinium+)

Abstract

Salts of the [Eu(2,6-pyridinedicarboxylate)₃]^3- complex anion and various monovalent inorganic and organic counterions (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺, and pyridinium⁺) have been synthesized and studied by emission spectroscopy. The Eu³⁺ ion emission spectra exhibited by these salts have been observed with high resolution (less than 1.0 cm^?1) and at low temperature (77 K). The emission spectra of these compounds indicate that changing the attached counterion does not affect the site symmetry observed by the europium ion beyond slight distortions indicated by small shifts in the energies of the Eu³⁺ electronic levels.     

Competition between exit channels leading to the same residual nucleus in heavy-ion reactions

Competition between pn and d as well as between p2n, dn and t emission in the production of individual residual states has been observed in nuclear reactions induced by ¹⁶O on ¹²C and ¹³C targets. The experimental relative yields for the production of the 417 keV state in ²⁶Al by pn and d emission, measured as a function of bombarding energy in the reaction ¹²C(¹⁶O,pn/d)²⁶Al, are successfully described by Hauser-Feshbach calculations.     

<Superscript>210</Superscript>Pb and <Superscript>210</Superscript>Po determination in environmental samples using liquid scintillation counting and alpha spectrometry

A simple radiochemical procedure has been developed to determine ²¹⁰Pb and ²¹⁰Po in environmental samples from the same matrix. Sediment samples are decomposed by leaching with mineral acids or by microwave digestion, while water samples are pre-concentrated. One part of the resulting solution, spiked with ²⁰⁹Po, is used for ²¹⁰Po determination by spontaneous deposition onto nickel disks (α-spectrometry). The other part is assayed for ²¹⁰Pb, separating the Pb either by anion-exchange (sediment samples), or by solvent extraction (water samples). The ²¹⁰Pb source is finally prepared by precipitation as oxalate and the chemical recovery determined by gravimetry. The ²¹⁰Pb activity concentration is determined by liquid scintillation. A standard sediment sample supplied by IAEA and spiked water samples were analysed to check the procedure. The ²¹⁰Pb and ²¹⁰Po measurements agreed well with the certifications, deviations being less than 10%. The mean recoveries for Pb and Po were (70±12)% and (77±8%) for sediments, and (70±10)% and (81±7)% for waters, respectively.     

Exponential depletion of neutral dangling bonds density (D) by rare-earth doping in amorphous Si films

In this work we study the effect reduction in the density of dangling bond species D⁰ states in rare-earth (RE) doped a-Si films as a function concentration for different RE-specimens. The films a-Si_1−xRE_x, RE=Y³⁺, Gd³⁺, Er³⁺, Lu³⁺) were prepared by co-sputtering and investigated by electron spin resonance (ESR) and Raman scattering experiments. According to our data the RE-doping reduces the ESR signal intensity of the D⁰ states with an exponential dependence on the rare-concentration. Furthermore, the reduction produced by the magnetic rare-earths Gd³⁺ and Er³⁺ is remarkably greater than that caused by Y³⁺ and Lu³⁺, which led us to suggest an exchange-like coupling between the spin of the magnetic REs³⁺ and the spin of silicon neutral dangling bonds.     

White up-conversion emission in Ho/Tm/Yb tri-doped glass ceramics embedding BaF2 nanocrystals

Ho³⁺/Tm³⁺/Yb³⁺ tri-doped glass ceramics with white light emitting have been developed and demonstrated. Pumped by 980 nm laser diode (LD), intensive red, green and blue up-conversions (UC) were obtained. The green emission is assigned to Ho³⁺ ion and the blue emission is assigned to Tm³⁺ ion, whereas the red emission is the combination contribution of the Ho³⁺ and Tm³⁺ ions. The RGB intensities could be adjusted by tuning the rare-earth ion concentration and pump power intensity. Thus, multicolor of the luminescence, including perfect white light with CIE-X=0.329 and CIE-Y=0.342 in the 1931 CIE chromaticity diagram can be obtained in 0.15 Ho³⁺/0.2Tm³⁺/3Yb³⁺ tri-doped glass ceramics embedding BaF₂ nanocrystals pumped by a single infrared laser diode source of 980 nm at 500 mW. The up-conversion luminescence mechanism of Yb³⁺ sensitize Ho³⁺ and Tm³⁺ ions and the energy transfer from Ho³⁺ to Tm³⁺ in oxy-fluoride silicate glass ceramics were analyzed.