Spatiotemporal dynamics of Ca2+ signaling and its physiological roles

Changes in the intracellular Ca²⁺ concentration regulate numerous cell functions and display diverse spatiotemporal dynamics, which underlie the versatility of Ca²⁺ in cell signaling. In many cell types, an increase in the intracellular Ca²⁺ concentration starts locally, propagates within the cell (Ca²⁺ wave) and makes oscillatory changes (Ca²⁺ oscillation). Studies of the intracellular Ca²⁺ release mechanism from the endoplasmic reticulum (ER) showed that the Ca²⁺ release mechanism has inherent regenerative properties, which is essential for the generation of Ca²⁺ waves and oscillations. Ca²⁺ may shuttle between the ER and mitochondria, and this appears to be important for pacemaking of Ca²⁺ oscillations. Importantly, Ca²⁺ oscillations are an efficient mechanism in regulating cell functions, having effects supra-proportional to the sum of duration of Ca²⁺ increase. Furthermore, Ca²⁺ signaling mechanism studies have led to the development of a method for specific inhibition of Ca²⁺ signaling, which has been used to identify hitherto unrecognized functions of Ca²⁺ signals.     

EPR spectra of Mn2+ ions in precipitated divalent impurity phases in monocrystalline NaCl

The EPR spectra of Mn²⁺ ions embedded into precipitated phases of Mg²⁺, Cd²⁺, Fe²⁺ and Ca²⁺ in NaCl single crystals have been investigated. The spectrum from samples whose major impurity is Mg, Cd or Fe corresponds to Mn²⁺ substituting some divalent cation inside the Suzuki phase (6NaCl.MCl₂). The existence of such a phase has been ascertained by means of Raman spectroscopy. On the other hand, the EPR spectrum of Ca²⁺ doped samples has been attributed to Mn²⁺ inside various CaCl₂ precipitates.     

Simultaneous registration of Ca2+ transients and volume changes in rat mesangial cells: Evaluation of the effects of protein kinase C down-regulation

The intracellular free Ca²⁺ concentration ([Ca²⁺]_i) could be correlated with the contractile response in rat mesangial cells using an apparatus which measured both biochemical processes simultaneously. Long-term pretreatment of mesangial cells with 12-O-tetradecanoly-phorbol 13-acetate (24 h, 500 nM) increased the (20 nM) angiotensin II-induced mobilization of Ca²⁺ and led to an enhanced and sustained contraction of the cells. The contractile response was delayed by approximately 3.5 s with respect to the intracellular increase in Ca²⁺ concentration. The simultaneous registration of Ca²⁺ transients and cell contractions confirms that [Ca²⁺]_i is the major determinant of the angiotensin II-mediated mesangial cell contraction.Dedicated to Professor Horst H. A. Linde on the occasion of his 60th birthday.     

Protection of cortical cells by equine estrogens against glutamate-induced excitotoxicity is mediated through a calcium independent mechanism

Background  

High concentrations of glutamate can accumulate in the brain and may be involved in the pathogenesis of neurodegenerative disorders such as Alzheimer's disease. This form of neurotoxicity involves changes in the regulation of cellular calcium (Ca²⁺) and generation of free radicals such as peroxynitrite (ONOO^-). Estrogen may protect against glutamate-induced cell death by reducing the excitotoxic Ca²⁺ influx associated with glutamate excitotoxicity. In this study, the inhibition of N-methyl-D-aspartate (NMDA) receptor and nitric oxide synthase (NOS) along with the effect of 17β-estradiol (17β-E₂) and a more potent antioxidant Δ⁸, 17β-estradiol (Δ⁸, 17β-E₂) on cell viability and intracellular Ca²⁺ ([Ca²⁺]_i), following treatment of rat cortical cells with glutamate, was investigated.     

Eu2+激活的Ca3SiO5绿色荧光粉的制备和发光特性研究

研究了Eu²⁺激活的绿色发光材料Ca₃SiO₅的制备条件和发光性质. Eu²⁺中心形成主峰值为501 nm和次峰值为570 nm的特征宽带，两峰值叠加形成发射峰值为502nm的绿色发射光谱带. 利用这些光谱结果和Van Uitert 经验公式，确认Ca₃SiO₅:Eu²⁺中存在两种性质有差异的Eu²⁺发光中心，它们分别占据基质中八配位的Ca²⁺(Ⅰ)格位和四配位的Ca²⁺(Ⅱ)格位. 其激发光谱分布在250—450 nm的波长范围，峰值位于375 nm处，可以被InGaN管芯产生的350—410 nm辐射有效激发. 关键词： 发光 荧光粉 绿色荧光粉 3SiO₅')" href="#">Ca₃SiO₅ 2+')" href="#">Eu²⁺     

Calcium substituting B-site in relaxor ferroelectrics with perovskite structure probed by chemical ordering

Chemical ordering of Ca²⁺ doped 0.9Pb(Mg_1/3Nb_2/3)O₃-0.1PbTiO₃ ceramics were investigated by dielectric spectra, TEM diffraction and A_1g mode in Raman spectra. It is found degree of relaxor behavior increases first, and then decreases. It conflicts the prediction Ca²⁺ substitutes for A-site ion Pb²⁺ according to crystal chemistry theory. In this letter, a new mechanism that Ca²⁺ substitutes for B-site ions has been proposed, which satisfactorily explained change of chemical ordering. It exhibits strong evidence doped ions with larger ionic radius (Ca²⁺) are quite possibly substitute much smaller ones (Nb⁵⁺ or Ti⁴⁺) in B-site rather than all substitute larger A-site ion in relaxor ferroelectrics.     

Synthesis and color-tunable luminescence properties of novel calcium aluminate silicate chloride phosphors

Eu²⁺ and Mn²⁺ co-doped calcium aluminate silicate chloride phosphors with the chemical composition of Ca₃Al₂Si₂O₈Cl₄:Eu²⁺, Mn²⁺ have been prepared by a solid-state method, and their luminescence properties have been investigated by tuning the En²⁺/Mn²⁺ ions concentration. The phase formation and microstructure of Ca₃Al₂Si₂O₈Cl₄:Eu²⁺, Mn²⁺ phosphors have been illuminated by XRD and SEM analysis. Photoluminescence (PL) spectrum reveals that Ca₃Al₂Si₂O₈Cl₄:Eu²⁺ exhibits a strong blue emission band centered at 431 nm, while Ca₃Al₂Si₂O₈Cl₄:Eu²⁺, Mn²⁺ can emit bluish-white light by adjusting the Mn²⁺ content appropriately. The energy transfer mechanism involving Eu²⁺–Mn²⁺ have also been investigated.     

EPR observation of phase transitions in calcium cadmium acetate hexahydrate: Using Mn2+ and Cu2+ ions as probe

Results of temperature dependence of EPR spectra of Mn²⁺ and Cu²⁺ ions doped calcium cadmium acetate hexahydrate (CaCd(CH₃COO)₄·6H₂O) have been reported. The investigation has been carried out in the temperature range between room temperature (～ 300 K) and liquid nitrogen temperature. A I-order phase transition at 146 ± 0.5 K has been confirmed. In addition a new II-order phase transition at 128 ± 1 K has been detected for the first time. There is evidence of large amplitude hindered rotations of CH₃ groups which become frozen at ～ 128 K. The incorporation of Cu²⁺ and Mn²⁺ probes at Ca²⁺ and Cd²⁺ sites respectively provide evidence that the phase transitions are caused by the molecular rearrangements of the common coordinating acetate groups between Ca²⁺ and Cd²⁺ sites. In contradiction to the previous reports of a change of symmetry from tetragonal to orthorhombic below 140 K, the symmetry of the host is concluded to remain tetragonal in all the three observed phases between room temperature and liquid nitrogen temperature.     

Ca₂BO₃Cl:Ce³⁺,Tb³⁺:A novel tunable emitting phosphor for white light-emitting diode

<正>Ca₂BO₃Cl:Ce³⁺,Ca₂BO₃Cl:Tb³⁺,and Ca₂BO₃Cl:Ce³⁺,Tb³⁺ phosphors are synthesized by a high temperature solid-state reaction.The emission intensity of Ce³⁺ or Tb³⁺ in Ca₂BO₃Cl is influenced by the Ce³⁺ or Tb³⁺ doping content,and the optimum concentrations of Ce³⁺ and Tb³⁺ are 0.03 mol and 0.05 mol,respectively.The concentration quenching effect of Ce³⁺ or Tb³⁺ in Ca₂BO₃Cl occurs,and the concentration quenching mechanism is d-d interaction for either Ce³⁺ or Tb³⁺.The Ca₂BO₃Cl:Ce³⁺,Tb³⁺ can produce colour emission from blue to green by properly tuning the relative ratio between Ce³⁺ and Tb³⁺,and the emission intensity of Tb³⁺ in Ca₂BO₃Cl can be enhanced by the energy transfer from Ce³⁺ to Tb³⁺.The results indicate that Ca₂BO₃Cl:Ce³⁺,Tb³⁺ may be a promising double emission phosphor for UV-based white light emitting diodes.     

Spatiotemporal Aspects of Prolactin-Induced Calcium Signaling

We have examined the spatiotemporal aspects of PRL-induced Ca²⁺ signals using high-speed fluo-3 confocal imaging. We found that PRL stimulated Ca²⁺ entry and intracellular Ca²⁺ mobilization. Ca²⁺ influx was seen as a peripheral increase in [Ca²⁺]_i without amplification in the nucleus region. Intracellular Ca²⁺ mobilization was seen as a propagating intracellular calcium wave with a strong amplification in the nuclear region. The amplitude of PRL-induced Ca²⁺ increases would be sufficient to stimulate cell proliferation. Furthermore, PRL induced an increase in [³H]thymidine incorporation. These data suggest that PRL would be able to induce mitogenesis through a Ca²⁺-dependent pathway.     

Bicarbonate Coordinates to Mn3+ during Photo-Assembly of the Catalytic Mn4Ca Core of Photosynthetic Water Oxidation: EPR Characterization

Assembly of the catalytic cluster, Mn₄CaO _x Cl _y , comprising the water-oxidizing complex (WOC) of photosystem II (PSII), occurs during biogenesis in the presence of the apo-WOC-PSII complex, Mn²⁺, Ca²⁺ and Cl^? cofactors under weak illumination. The in vitro assembly process known as photo-activation involves several intermediates that have been resolved in previous kinetic studies. (Bi)carbonate has been shown to stimulate the rate of formation and yield of the first stable light-induced Mn³⁺ assembly intermediate (IM₁) from Mn²⁺ bound to the high-affinity assembly site in apo-WOC-PSII. ¹³C electron spin echo envelope modulation has previously revealed that (bi)carbonate is a ligand to this Mn²⁺. Herein, we use parallel-mode electron paramagnetic resonance (EPR) spectroscopy to characterize the Mn³⁺ photoproduct, which exists as a ternary complex with carbonate at the high-affinity assembly site (in the absence of Ca²⁺) formulated as [CO₃-Mn³⁺-apo-WOC-PSII]. The EPR-derived spectral parameters of IM₁ (the g value, ⁵⁵Mn hyperfine coupling constant (A _Z) and the ligand-field splitting parameters D/E) are independent of solution pH, in marked contrast to their strong pH dependence in the absence of bicarbonate. (Bi)carbonate coordination “chemically isolates” the IM₁ from external pH changes, much like that caused by Ca²⁺ coordination, revealing similar roles in photo-assembly. The cumulative results reveal that (bi)carbonate and Ca²⁺ coordination control the ligand field strength and symmetry around the initial high-affinity Mn³⁺, consistent with the possible formation of a μ₂-oxide bridge in IM₁, [Mn³⁺(O^2?)Ca²⁺]. These events greatly improve the quantum yield of subsequent steps in photo-assembly.     

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.     

Luminescent properties of Li2 (Ca0.99, Eu0.01) SiO4: B3+ particles as a potential bluish green phosphor for ultraviolet light-emitting diodes

In our study, the 1% mol Eu²⁺ doped Li₂CaSiO₄: B³⁺ phosphors were prepared by the combustion method as fluorescent material for ultraviolet, light-emitting diodes (UV-LEDs) used as a light source. The properties of Li₂ (Ca_0.99, Eu_0.01) SiO₄: B³⁺ phosphors with urea concentration, doping boric acid and a series of initiating combustion temperature were investigated. The crystallization and particle sizes of Li₂ (Ca_0.99, Eu_0.01) SiO₄: B³⁺ has been investigated by using powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). Luminescence measurements showed that the phosphors can be efficiently excited by UV to the visible region, and exhibited bluish green light with a peak of 480 nm. The results showed that the boric acid was effective in improving the luminescence intensity of Li₂ (Ca_0.99, Eu_0.01) SiO₄: B³⁺ and the optimum molar ratio of boric acid to calcium nitrate was about 0.06. The optimized phosphors Li₂ (Ca_0.99, Eu_0.01) SiO₄: B _0.06 ³⁺ showed 180% improved emission intensity compared with that of the Li₂ (Ca_0.99, Eu_0.01) SiO₄ phosphors under ultraviolet (λ_ex =287 nm) excitation.      

UVC emitting phosphors obtained by spray pyrolysis

The broadband inter-configurational (4f¹5d¹→4f²) emission of Pr³⁺ doped in lanthanum orthophosphate (LaPO₄) and in calcium pyrophosphate (Ca₂P₂O₇) has been investigated under plasma excitation. The synthesis by spray pyrolysis at moderate temperature followed by a controlled annealing proves to be a very efficient way to produce good quality UVC emitting phosphor Ca_1.92Pr_0.04Na_0.04P₂O₇ (α phase). The emission of this phosphor in the wavelength range 200-350 nm has been measured with a prototype device, which can be employed for anti-microbial testing.     

Growth and comparison of physicochemical properties of pure,Ca and Sr doped NH4Sb3F10 single crystals for electro optic applications

Single crystals of pure, Ca²⁺ and Sr²⁺ doped NH₄Sb₃F₁₀ are grown by slow evaporation technique. The effect of dopants on the growth and physicochemical properties also have been investigated and reported for the first time. The grown crystals are characterized with the aid of single crystal X-ray diffractometry to confirm the crystal structure. EDAX studies are done to confirm the presence of dopants in the crystal lattice. The vibrational frequencies of various group ligands in the crystals have been derived from the Fourier transform infrared (FT-IR) spectrum. From the optical absorption spectrum the band gap energy was calculated and it was found to be 5.76, 6.29 and 6.35 eV for pure, Ca²⁺ and Sr²⁺ doped NH₄Sb₃F₁₀ crystals respectively. Thermal stability of the sample has been analysed using TG-DTA analysis. The activation energy of pure, Ca²⁺ and Sr²⁺ doped NH₄Sb₃F₁₀ crystals were calculated from the dc conductivity measurements and it is found to be 0.2728, 0.2816 and 0.3622 eV Experimental results shows improved physicochemical properties when the dopant is added to the pure material.     

Synthesis and electrochemical characterization of M2Mn3O8 (M = Ca,Cu) compounds and derivatives

M₂Mn₃O₈ (M = Ca²⁺, Cu²⁺) compounds were synthesized and characterized in lithium cells. The M²⁺ cations, which reside in the van der Waals gaps between adjacent sheets of Mn₃O₈⁴⁻, may be replaced chemically (by ion-exchange) or electrochemically with Li. More than 7 Li⁺/Cu₂Mn₃O₈ may be inserted electrochemically, with concomitant reduction of Cu²⁺ to Cu metal, but less Li can be inserted into Ca₂Mn₃O₈. In the case of Cu²⁺, this process is partially reversible when the cell is charged above 3.5 V vs. Li, but intercalation of Cu⁺ rather than Cu²⁺ and Li⁺/Cu⁺ exchange occurs during the subsequent discharge. If the cell potential is kept below 3.4 V, the Li in excess of 4 Li⁺/Cu₂Mn₃O₈ can be cycled reversibly. The unusual mobility of + 2 cations in a layered structure has important implications both for the design of cathodes for Li batteries and for new systems that could be based on M²⁺ intercalation compounds.     

Controlling intracellular Ca2+ spiral waves by the local agonist in the cell membrane

A modified spatially extended Tang-Othmer Ca2+ model is used to study intracellular Ca2+ spiral waves numerically.It is found that,as a local stimulation,the local agonist-binding on the cell membrane,which enhances the local concentration of the messenger molecule inositol 1,4,5-trisphosphate(IP 3),can influence the dynamics of the spiral waves.1) Strong enough stimuli can change the spiral wave from a meandering to a rigidly rotating one.2) On the other hand,strong enough stimuli can suppress the spiral wave from the system.It provides the theoretical clue for controlling the spiral waves by stimulating the cell membrane.     

Studies on adsorptions of metallic ions in water by zirconium glyphosate (ZrGP): Behaviors and mechanisms

A new adsorbent named zirconium glyphosate [Zr(O₃PCH₂NHCH₂COOH)₂·0.5H₂O, denoted as ZrGP] and its selective adsorptions to Pb²⁺, Cd²⁺, Mg²⁺ and Ca²⁺ ions in water were reported in this paper. Compared to other zirconium adsorbents, such as zirconium phosphate [Zr(HPO₄)₂], ZrGP exhibited highly selective adsorption to Pb²⁺ in solution which contained Pb²⁺, Cd²⁺, Mg²⁺ and Ca²⁺ ions. The loaded ZrGP with metallic ions can be efficaciously regenerated by aqueous solution of HCl (1.0 M) without any noticeable capacity loss, and almost all of it can be reused and recycled. The memory effect on structural regeneration of ZrGP was also found when Mg²⁺ and Ca²⁺ were adsorbed. To be specific, the structure of ZrGP was destroyed due to adsorbing these two ions, but it could be regenerated after the loaded materials were dipped in HCl solution (1.0 M) for several minutes to remove metallic ions.     

Change of membrane fluidity and protein conformation involved in [Ca2+]i overload in neuronal cells induced by ONOO−

Considerable evidence indicates that the formation of peroxynitrite (ONOO⁻) with superoxide anion (O₂^−⊙ot) may be involved in the neuronal toxicity of NO. Here, the effects of ONOO⁻ on intracellular free calcium concentration ([Ca²⁺]_i) in single MN9D cells was studied by the Fura-2 microfluorometric technique. The results showed that [Ca²⁺]_i was increased dose-dependently with the addition of ONOO⁻ (0–40 μmol/l) after 5 s and then decreased rapidly back to the basal level after ONOO⁻ was removed. [Ca²⁺]_i response to ONOO⁻ can be blocked by removing Ca²⁺ from the bath or adding L-type calcium channel antagonist nifedipine (10 μmol/l) to the bath. [Ca²⁺]_i transients by ONOO⁻ were substantially inhibited by dithiothreitol (DTT), which indicated ONOO⁻ may alter the L-type calcium channel on neuronal cell by thiol oxidation. To elucidate the mechanism of ONOO⁻ on [Ca²⁺]_i, the electron spin resonance spin-labeling technique was used to study the effects of ONOO⁻ on the membrane fluidity and the membrane protein conformation on freshly dissociated neurons. The results indicate that ONOO⁻ decreases membrane fluidity both near the surface and deep in the membrane and affects protein conformation. The fact that DTT effectively inhibits the deterioration supports the conclusion that the change of membrane fluidity and protein conformation is involved in [Ca²⁺]_i overload in neuronal cells induced by ONOO⁻.     

Photoluminescence properties and energy transfer of Ca3WO6:Sm3+ co-doped Eu3+

A reddish-orange phosphor, Ca₃WO₆:Sm³⁺, was synthesized by the convenient solid-state reaction method and characterized by X-ray diffraction (XRD). Photoluminescence properties and concentration quenching of Ca₃WO₆:Sm³⁺ phosphor have been discussed in the excitation and emission spectra. Ca₃WO₆:Sm³⁺ phosphor is able to generate a strong excitation peak, which matches the emission wavelength from near-UV LEDs. Energy transfer from Sm³⁺ to Eu³⁺ in Ca₃WO₆ host is observed and investigated in detail. The chromaticity coordinates of Ca₃WO₆:Sm³⁺ can be regulated to approach the NTSC standard values of red phosphor by codoping Eu³⁺ ions. The photoluminescence properties suggest that novel Ca₃WO₆:Sm³⁺, Eu³⁺ phosphor might have a potential application for near-UV LEDs.