Characterisation of human hair surfaces by means of static ToF-SIMS: A comparison between Ga and C60 primary ions

This study deals with the secondary ion yield improvement induced by using C₆₀⁺ primary ions instead of Ga⁺ ones to characterize human hair surfaces by ToF-SIMS. For that purpose, a bunch of hair fibres has been analysed with both ion sources. A high improvement is observed for the detection of amino acids with C₆₀⁺ primary ions as compared to Ga⁺ ions. As an example, a yield enhancement factor greater than 3000 is found for the CNO⁻ peak. A similar gain is observed for the positive secondary ions characteristic of the amino acids. Most of the atomic ions, such as Ca⁺, O⁻ and S⁻, constitute minor peaks with C₆₀⁺ ions while they often dominate the spectrum in the case of Ga⁺ ions. However, with the C₆₀⁺ source, a series of inorganic combination peaks with the elements Ca, S and O are observed in the positive spectra (i.e. HCaSO₄⁺), while they are marginal with the Ga⁺ source. For the mass range beyond 100 m/z and in both polarities, the hair fingerprints are similar with both sources. In average, for a comparable number of primary ions per spectrum, the C₆₀⁺ ion source gives intensities between two and three orders of magnitude higher than the Ga⁺ one.     

Trapped-hole centers in MgO single crystals

The properties of the majority trapped-hole centers in MgO, such as g-factors, positions of absorption and luminescence bands, and temperatures of thermal destruction, have been analyzed with the emphasis on the observed regular trends and interrelations between the properties of these centers. Particular emphasis has been placed on the positively charged [Be]⁺ and [Ca]⁺ trapped-hole centers, which have a large cross section for recombination with conduction electrons. In these centers, a hole is localized at an oxygen ion near the impurity Be²⁺ or Ca²⁺ ion located at a regular cation site. The generation and transformation of defects due to the recombination of either relaxed conduction electrons with OH⁻-containing hole centers or cold and hot electrons with [Be]⁺ and [Ca]⁺ centers have been considered. Using the interrelation of the characteristics of hole centers and taking into account that the recombination emission band revealed at ∼6.8 eV is due to the Ca²⁺-containing centers that are stable below 50 K, the prospects for the EPR detection of the [Ca]⁺ center at T < 4.2 K have been discussed.     

Isotope-selective trapping of rare calcium ions using high-power incoherent light sources for the second step of photo-ionization

Rare calcium isotope ⁴⁸Ca⁺ (0.187%) has been selectively loaded in a linear Paul trap using two ultraviolet light emitting diodes with the output power of 85 mW for the second excitation in a two-step photo-ionization process. Isotope selectivity has been achieved by utilizing the isotope shifts for the 4s^{2 1} S ₀–4s4p¹ P ₁ transition of neutral calcium atom. Sympathetic cooling of ⁴⁸Ca⁺ ions has been demonstrated using ⁴⁰Ca⁺ ions as refrigerant ions. Purification of rare isotope ⁴²Ca⁺ ions (0.647%) from a mixture of ⁴⁰Ca⁺ (96.9%) and ⁴²Ca⁺ ions has been performed by adjusting the detuning of the cooling laser frequency, which overcomes the imperfect selectivity for some rare isotopes having close resonance frequencies to that of ⁴⁰Ca in the 4s^{2 1} S ₀–4s4p¹ P ₁ transition. The methods can be applied to ⁴³Ca⁺ ion (0.135%) that has been considered as one of the attractive candidates for quantum information processing as well as for an optical frequency standard. PACS 32.80.Fb; 32.80.Pj; 32.80.Rm     

Separation of laser-cooled 42Ca+ and 44Ca+ in a linear Paul trap

Rare calcium isotope ions, ⁴²Ca⁺ and ⁴⁴Ca⁺, were efficiently separated from a laser-cooled ionic cloud in a linear Paul trap which was loaded from an atomic source of a natural isotope mixture of calcium, in spite of their negligibly small abundances (0.647% and 2.086%, respectively) compared with that of ⁴⁰Ca (96.94%). Selective heating and cooling that arise from the isotope shifts were mainly used for the elimination of the isotopes; selective heating and cooling enable flexible separation when combined with other mechanisms such as the inherent mass selectivity of RF traps. Received: 7 July 2000 / Published online: 10 January 2001     

Ion exchange equilibrium between cation exchange membranes and aqueous solutions of K+/Na+, K+/Ca2+, and Na+/Ca2+

Equilibrium between synthetic ion exchangers and solutions of cations has been the subject of this investigation. Competitive ion exchange reactions were studied for two cation exchange membranes (CMX and CRP) involving K⁺, Na⁺, and Ca²⁺ ions. The ionic strength of the equilibrating solutions was maintained constant, but the molar fraction varied; all experiments were conduced with nitrate as nonexchanging anions at 25 °C. Adsorption isotherm for the three binaries systems: K⁺/Na⁺, K⁺/Ca²⁺, and Na⁺/Ca²⁺ were studied. The obtained results show that potassium was the most strongly sorbed and the selectivity order for CMX and CRP membranes is K⁺>Ca²⁺>Na⁺ at 0.1 M, under the experimental conditions. Selectivity coefficients , , and for the three binaries and for the two membranes were determined at an ionic strength of 0.1 M and at a constant temperature of 25 °C. We remark that all the selectivity coefficient values are quite different from the unit. Ternary equilibrium was taken for the Ca²⁺/K⁺/Na⁺ system. It was found that binary selectivity data could be successfully used to predict the ternary ion exchange equilibrium.     

Biological fractionation of stable Ca isotopes in Göttingen minipigs as a physiological model for Ca homeostasis in humans

In order to investigate fractionation of calcium (Ca) isotopes in vertebrates as a diagnostic tool to detect Ca metabolism dysfunction we analyzed the Ca isotopic composition (δ^44/40Ca?=?[(⁴⁴Ca/⁴⁰Ca)_sample/(⁴⁴Ca/⁴⁰Ca)_reference]?1) of diet, faeces, blood, bones and urine from Göttingen minipigs, an animal model for human physiology. Samples of three groups were investigated: 1. control group (Con), 2. group with glucocorticosteroid induced osteoporosis (GIO) and 3. group with Ca and vitamin D deficiency induced osteomalacia (?CaD). In contrast to Con and GIO whose average δ^44/40Ca_faeces values (0.39?±?0.13‰ and 0.28?±?0.08‰, respectively) tend to be lower than their diet (0.47?±?0.02‰), δ^44/40Ca_faeces of ?CaD (?0.27?±?0.21‰) was significantly lower than their δ^44/40Ca_diet (0.37?±?0.03‰), but also lower than δ^44/40Ca_faeces of Con and GIO. We suggest that the low δ^44/40Ca_faeces of ?CaD might be due to the contribution of isotopically light Ca from gastrointestinal fluids during gut passage. Assuming that this endogenous Ca source is a common physiologic feature, a fractionation during Ca absorption is also required for explaining δ^44/40Ca_faeces of Con and GIO. The δ^44/40Ca_urine of all groups are high (>2.0‰) reflecting preferential renal reabsorption of light Ca isotopes. In Göttingen minipigs we found a Ca isotope fractionation between blood and bones (Δ^44/40Ca_blood-bone) of 0.68?±?0.15‰.     

Enhanced UVB emission and analysis of chemical states of Ca5(PO4)3OH:Gd3+,Pr3+ phosphor prepared by co-precipitation

Hydroxyapatite (Ca₅(PO₄)₃OH) is a well-known bioceramic material used in medical applications because of its ability to form direct chemical bonds with living tissues. This mineral is currently used as a host for rare-earth ions (e.g. Gd³⁺, Pr³⁺, Tb³⁺, etc.) to prepare phosphors that can be used in light emitting devices of different types. In this study Ca₅(PO₄)₃OH:Gd³⁺,Pr³⁺ phosphors were prepared by the co-precipitation method and were characterised by x-ray diffraction, x-ray photoelectron spectroscopy, scanning electron microscopy, high resolution transmission electron microscopy, energy dispersive x-ray spectroscopy and photoluminescence spectroscopy. The x-ray diffraction pattern was consistent with the hexagonal phase of Ca₅(PO₄)₃OH referenced in JCPDS card number 73-0293. The x-ray photoelectron spectroscopy data indicated that Ca²⁺ occupied two different lattice sites, referred to as Ca1 and Ca2. The photoluminescence data exhibited a narrowband emission located at 313 nm, which is associated with the ⁶P_7/2→⁸S_7/2 transition of the Gd³⁺ ion. This emission is classified as ultraviolet B and it is suitable for use in phototherapy lamps to treat various skin diseases. The photoluminescence intensity of the 313 nm emission was enhanced considerably by Pr³⁺ co-doping.     

Application of percolation theory to ion-exchanged molecular sieves A

The unit cell of dehydrated zeolite A is cubic and its {100} faces constitute “windows” of a large cavity located at the center. In sodium-form zeolite A, Na⁺ partially blocks the window, through which oxygen but not nitrogen molecules can pass. By ion-exchanging two Na⁺s with one Ca²⁺, an unblocked or “open window” can be introduced. By preparing well defined (Na, Ca)-A zeolites having various compositions, the nitrogen percolation process was quantitatively studied. A curve for the number of percolatable cells vs the open-window concentration was deduced, and compared with Hammersley's theoretical curve. The theoretical curve has a sharp cut-oft at a concentration of one open-window per unit cell. The observed curve was steeper in this transition region than the theoretical one, but has a tail in the region corresponding to lower concentrations of open windows. The first tendency is ascribed to an ordered alignment of open-windows in their spatial distribution. The second is attributed to incompleteness of the blocking action of Na⁺. Substituted Ca²⁺ and vacant cation sites change the Madelung potential at the Na⁺ site, so that the curvature of the potential valley for Na⁺ may become gentle. As a result, Na⁺ can easily be displaced and make way for a visiting nitrogen molecule.     

Swelling of K+, Na+ and Ca2+-montmorillonites and hydration of interlayer cations: a molecular dynamics simulation

This paper performs molecular dynamics simulations to investigate the role of the monovalent cations K, Na and the divalent cation Ca on the stability and swelling of montmorillonite. The recently developed CLAYFF force field is used to predict the basal spacing as a function of the water content in the interlayer. The simulations reproduced the swelling pattern of these montmorillonites, suggesting a mechanism of their hydration different (K+ 相似文献   

Selective loading and laser cooling of rare calcium isotope 43Ca+

We report a method for loading ⁴³Ca⁺ ions selectively in a linear Paul trap using ultraviolet light-emitting-diodes (LEDs) for the second excitation in a two-step photo-ionization process. The difficulty in working with ⁴³Ca⁺ is its low natural abundance (0.135%). In order to load ⁴³Ca⁺ selectively, we utilize the isotope shifts for the 4s^{2 1} S ₀–4s4p¹ P ₁ transition of neutral calcium atoms. We discuss the limitation of the selectivity of the employed photo-ionization scheme and observe spectra from unwanted isotopes as well as that from ⁴³Ca⁺. Purification of ⁴³Ca⁺ is performed by adjusting the detuning of the cooling laser frequency and trapping potential. The method of loading and purification can be used in the application of trapped ⁴³Ca⁺ for an optical frequency standard and for quantum information processing. PACS 32.80.Fb; 32.80.Pj     

Precision spectroscopy with two correlated atoms

We discuss techniques that allow for long coherence times in laser spectroscopy experiments with two trapped ions. We show that for this purpose not only entangled ions prepared in decoherence-free subspaces can be used but also a pair of ions that are not entangled but subject to the same kind of phase noise. We apply this technique to a measurement of the electric quadrupole moment of the 3d²D_5/2 state of ⁴⁰Ca⁺ and to a measurement of the line width of an ultra-stable laser exciting a pair of ⁴⁰Ca⁺ ions. PACS 03.67.-a; 06.30.Ft; 37.10.Ty     

High resolution laser spectroscopy of metallic atoms and molecules: Storage of singly and doubly charged ions transferred from externally generated laser plasmas

A radio-frequency (RF) ion trap has been constructed for high resolution laser spectroscopy of metallic ions. Ions in externally generated laser plasma have been directly introduced into the RF ion trap. An Nd:YAG laser is used to vaporize and ionize sample metals placed behind a ring electrode. Both hyperbolic and cylindrical electrodes are successfully used for confinement of the ions. Trapped ions are detected either with a quadrupole mass spectrometer or with a photomultiplier for the measurement of laser-induced fluorescence. Metallic ions such as Ca⁺, Ba⁺, La⁺, Nd⁺, Tm⁺, Lu⁺, and Ta⁺ have been confined for the time range of several to 20 minutes in the presence of He buffer gas, and a doubly charged ion Ba²⁺ for several seconds. Some ions like Nd⁺, Lu⁺, Hf⁺, and Ta⁺ are found to be highly reactive with background gaseous molecules.     

Die Anregungsfunktion bei Elektronenstoß für den Übergang Ca 41 S nach Ca+ 42 P 3 2/0

The excitation function for population of the Ca⁺ 4² P ₃ ^2/0 -term from the ground state of neutral Ca by electron impact is measured. Cascading effects are taken into account.     

Downregulation of calcium-dependent NMDA receptor desensitization by sodium-calcium exchangers: a role of membrane cholesterol

Background

The plasma membrane Na⁺/Ca²⁺-exchanger (NCX) has recently been shown to regulate Ca²⁺-dependent N-methyl-d-aspartate receptor (NMDAR) desensitization, suggesting a tight interaction of NCXs and NMDARs in lipid nanoclasters or “rafts”. To evaluate possible role of this interaction we studied effects of Li⁺ on NMDA-elicited whole-cell currents and Ca²⁺ responses of rat cortical neurons in vitro before and after cholesterol extraction by methyl-β-cyclodextrin (MβCD).

Results

Substitution Li⁺ for Na⁺ in the external solution caused a concentration-dependent decrease of steady-state NMDAR currents from 440?±?71 pA to 111?±?29 pA in 140 mM Na⁺ and 140 mM Li⁺, respectively. The Li⁺ inhibition of NMDAR currents disappeared in the absence of Ca²⁺ in the external solution (Ca²⁺-free), suggesting that Li⁺ enhanced Ca²⁺-dependent NMDAR desensitization. Whereas the cholesterol extraction with MβCD induced a decrease of NMDAR currents to 136?±?32 pA in 140 mM Na⁺ and 46?±?15 pA in 140 mM Li⁺, the IC₅₀ values for the Li⁺ inhibition were similar (about 44 mM Li⁺) before and after this procedure. In the Ca²⁺-free Na⁺ solution the steady-state NMDAR currents after the cholesterol extraction were 47?±?6% of control values. Apparently this amplitude decrease was not Ca²⁺-dependent. In the Na⁺ solution containing 1 mM Ca²⁺ the Ca²⁺-dependent NMDAR desensitization was greater when cholesterol was extracted. Obviously, this procedure promoted its development. In agreement, Li⁺ and KB-R7943, an inhibitor of NCX, both considerably reduced NMDA-activated Ca²⁺ responses. The cholesterol extraction itself caused a decrease of NMDA-activated Ca²⁺ responses and, in addition, abolished the effects of Li⁺ and KB-R7943. The cholesterol loading into the plasma membrane caused a recovery of the KB-R7943 effects.

Conclusions

Taken together our data suggest that NCXs downregulate the Ca²⁺-dependent NMDAR desensitization. Most likely, this is determined by a tight functional interaction of NCX and NMDAR molecules because of their co-localization in membrane lipid rafts. The destruction of these rafts is accompanied by an enhancement of NMDAR desensitization and a loss of NCX-selective agent effects on NMDARs.

     

Hyperpolarizabilities of alkaline-earth metal ions Be+, Mg+, and Ca+

The knowledge of the hyperpolarizabilities of atoms and ions is helpful for the analysis of the high order effects of the frequency shifts in precision spectroscopy experiments. Liu et al. [Phys. Rev. Lett. 114, 223001(2015)] proposed to establish all-optical trapped ion clocks using laser at the magic wavelength for clock transition. To evaluate the high-order frequency shifts in this new scheme of optical clocks, hyperpolarizabilities are needed, but absent. Using the finite field method based on the B-spline basis set and model potentials, we calculated the electric-field-dependent energy shifts of the ground and low-lying excited states in Be+, Mg+, and Ca+ in the field strength range of 0.0-6×10.5 a.u.. The scalar and tensor polarizabilities(α0, α2) and hyperpolarizabilities(γ0, γ2, γ4) were deduced. The results of the hyperpolarizabilities for Be+ showed good agreement with the values in literature, implying that the present method can be applied for the effective estimation of the atomic hyperpolarizabilities,which are rarely reported but needed in experiments. The feasibility of optical trapping of Ca+ is discussed, and the contributions of hyperpolarizabilities to the transition frequency shift for Ca+ in the optical dipole trap are estimated using quasi-electrostatic approximation.     

In situ 1H NMR Study of Nanoreactor Interaction NH3–H2O in Zeolite Nanopores

The interaction between ammonium NH₃ and H₂O molecules in zeolitic nanopores is studied by in situ ¹H nuclear magnetic resonance (NMR) method. The powder and single crystal samples of natural zeolites, heulandites Ca₄[Al₈Si₂₈O₇₂]·24H₂O and clinoptilolite (Na, K,Ca_1/2)₆[Al₆Si₃₀O₇₂], were used as the model system. It is shown that penetration of NH₃ into the zeolitic nanopores is accompanied by disordering of the hydrogen sublattice of zeolitic water and by the fast proton exchange NH₃ + H₂O ? [NH₄]⁺ + [OH]^? characterized by correlation frequency v _c = ~40 kHz. Another nanoreactor interactions are represented by interaction of [NH₄]⁺ ions with exchangeable Na⁺ and Ca²⁺ ions of the zeolitic structure. The slow ionic exchange [NH₄]⁺ → [Na,Ca_1/2]⁺ and binding of [NH₄]⁺ in cationic sites of the framework were visualized by NMR spectroscopy along with stepwise release of (Na,Ca_1/2)OH from zeolitic pores to the external surface of zeolite grains.     

Calcifications in human osteoarthritic articular cartilage: ex vivo assessment of calcium compounds using XANES spectroscopy

Calcium (Ca²⁺)‐containing crystals (CCs), including basic Ca²⁺ phosphate (BCP) and Ca²⁺ pyrophosphate dihydrate (CPPD) crystals, are associated with severe forms of osteoarthritis (OA). Growing evidence supports a role for abnormal articular cartilage mineralization in the pathogenesis of OA. However, the role of Ca²⁺ compounds in this mineralization process remains poorly understood. Six patients, who underwent total knee joint replacement for primary OA, have been considered in this study. Cartilage from femoral condyles and tibial plateaus in the medial and lateral compartments was collected as 1 mm‐thick slices cut tangentially to the articular surface. First, CCs presence and biochemical composition were assessed using Fourier transform infrared spectroscopy (FT‐IR). Next, Ca²⁺ compound biochemical form was further assessed using X‐ray absorption spectroscopy (XAS) performed at the Ca²⁺K‐absorption edge. Overall, 12 cartilage samples were assessed. Using FT‐IR, BCP and CPPD crystals were detected in four and three out of 12 samples, respectively. Ca²⁺ compound biochemical forms differed between areas with versus without CCs, when compared using XAS. The complete set of data shows that XANES spectroscopy can be used to accurately characterize sparse CCs in human OA cartilage. It is found that Ca²⁺ compounds differ between calcified and non‐calcified cartilage areas. In calcified areas they appear to be mainly involved in calcifications, namely Ca²⁺ crystals.     

Time-resolved response of fluorescent alkali ion indicators and detection of short-lived intermediates upon binding to molecular cavities

Stopped-flow kinetic studies have been performed to determine the kinetic parameters of K⁺ binding to the fluorescent cryptand F222 and of Na⁺binding to F221 at pH 8.O. The results clearly indicate that a comparatively stable intermediate is formed before the rate-limiting binding step occurs with a rate constant around 30 s^–1 under the chosen experimental conditions. The conversion of the intermediate to the final cation complex is assigned to the final penetration of the already bound, but still partially solvated cation into the ligand's cavity. The main fluorescence intensity change found upon cation binding is attributed to the second reaction step, and not to the fast, initial binding reaction. The comparatively slow overall binding reaction is interpreted on the bases of a special solvate substitution mechanism which, in principle, can also account for the 1500 times slower binding of Ca 2⁺ to F221. With regard to time-resolved analytical Na⁺ and K⁺ determinations, the response times under the chosen conditions are around 20 ms. Differentiation between Na⁺ and Ca²⁺, for example, is possible with F221 on the basis of completely different response times.     

Core-excited α-cluster structure in44Ti

With the use of a schematic⁴⁰Ca^*+α model, the low-lying positiveK=O2+ and 2⁺ bands in⁴⁴Ti, which start from the band-head energyE _x =1.90 MeV and 2.88 MeV, respectively, are shown to be well interpreted by an α-cluster structure with an excited⁴⁰Ca core, i.e.,³⁶Ar+α+α structure.     

Ab initio study of spectroscopic properties of the calcium hydride molecular ion

In the present work, all adiabatic potential energy curves, spectroscopic constants and dipole moments of CaH⁺ molecular ion dissociating below the ionic limit Ca²⁺H⁻ are presented. These curves are determined by an ab initio approach involving a non-empirical pseudo-potential for the Ca core, core-valence correlation accounted in operator form with two types of core polarization potentials (CPP) and full valence Configuration Interaction. The molecule is thus treated as a two-electron system. The potential energy curves and the spectroscopic constants are presented. In addition, the permanent and transition dipole moments are calculated for most of the states and reveal the underlying ionic states. A rather good agreement with the available theoretical works in the literature is obtained for the spectroscopic constants of the lowest states of the CaH⁺ molecule.