Active Species for Ce(IV)-Induced Hydrolysis of Phosphodiester Linkage in cAMP AND DNA

The hydrolysis of cyclic adenosine 3′,5′-monophosphate and 2′-deoxythymidylyl(3′-5′)2′-deoxythymidine by Ce(NH₄)₂(NO₃)₆ was kinetically studied. The rate of hydrolysis was fairly proportional to the concentration of [Ce ^IV ₂ (OH)₄]⁴⁺, showing that this is the catalytically active species. According to quantum-chemical calculation, the two Ce(IV) ions in this [Ce^IV ₂(OH)₄]⁴⁺ cluster are bridged by two OH residues. Upon the complex formation with H₂ PO₄ ^? (a model compound for the phosphodiesters), these two Ce(IV) ions bind the two oxygen atoms of the substrate and enhance the electrophilicity of the phosphorus atom. The catalytic mechanism of Ce(IV)-induced hydrolysis of phosphodiesters has been proposed on the basis these results.     

Slow relaxation of the magnetization in high-nuclearity Ln-complexes

By the surface modification strategy, a novel high-nuclearity lanthanide complex with a discrete structure, Er₂₆I(μ₃-OH)₂₀(μ₃-O)₆(NO₃)₉(IN)₃₃(OH)₃(H₂O)₃₃ (noted Er₂₆, HIN = isonicotinic acid), has been prepared under hydrothermal conditions. The magnetic properties of Er₂₆ and two analogue dysprosium assemblies Dy₃₀I(μ₃-OH)₂₄(μ₃-O)₆(NO₃)₉(IN)₄₁(OH)₃(H₂O)₃₈ (noted Dy₂₆-I) and Dy₂₆I(μ₃-OH)₂₀(μ₃-O)₆(NO₃)₉(IN)_31.25(OH)_4.75(H₂O)_41.75 (noted Dy₂₆-II) have been studied. The results show that the slow relaxation of the magnetization is newly found in Dy₂₆-I constructed from {Dy₂₆} and {Dy₄} cluster units. The {Dy₄} units in Dy₂₆-I, the relative orientation of the complex or the inter-molecular interactions between {Dy₂₆} cores might play an important role in the origin of this magnetic behavior.     

Enhancement of the luminescence properties of Sr3(PO4)2:Dy3+,Li+ white‐light‐emitting phosphors by charge compensator Li+ co‐doping

Sr₃(PO₄)₂:Dy³⁺,Li⁺ phosphors were prepared using a simple high temperature solid method for luminescence enhancement. The structures of the as‐prepared samples agreed well with the standard phase of Sr₃(PO₄)₂, even when Dy³⁺ and Li⁺ were introduced. Under ultraviolet excitation at 350 nm, the Sr₃(PO₄)₂:Dy³⁺ sample exhibited two emission peaks at 483 nm and 580 nm, which were due to the ⁴F_9/2 → ⁶H_15/2 and ⁴F_9/2 → ⁶H_13/2 transitions of Dy³⁺ ions, respectively. A white light was fabricated using these two emissions from the Sr₃(PO₄)₂:Dy³⁺ phosphors. The luminescence properties of Sr₃(PO₄)₂:Dy³⁺,Li⁺ phosphors, including emission intensity and decay time, were improved remarkably with the addition of Li⁺ as the charge compensator, which would promote their application in near‐ultraviolet excited white‐light‐emitting diodes.     

Dy(3+) and Mn(2+) emission in fluoride- and chloride-based Na(3) (SO(4) )X (X = F or Cl) phosphors

In the present study, Na₃(SO₄)X (X = F or Cl) halosulphate phosphors have been synthesized by the solid‐state diffusion method. The phase formation of the compounds Na₃(SO₄)F and Na₃(SO₄)Cl were confirmed by X‐ray powder diffraction (XRD) measurement. Photoluminescence (PL) excitation spectrum measurement of Na₃(SO₄)F:Ce³⁺ and Na₃(SO₄)Cl:Ce³⁺ shows this phosphor can be efficiently excited by near‐ultraviolet (UV) light and presents a dominant luminescence band centred at 341 nm for Ce³⁺, which is responsible for energy transfer to Dy³⁺and Mn²⁺ ions. The efficient Ce³⁺ → Dy³⁺ energy transfer in Na₃(SO₄)F and Na₃(SO₄)Cl under UV wavelength was observed due to ⁴ F_9/2 to ⁶H_15/2 and ⁶H_13/2 level, while Ce³⁺ → Mn²⁺ was observed due to ⁴ T₁ state to ⁶A₁. The purpose of the present study is to develop and understanding the photoluminescence properties of Ce³⁺‐, Dy³⁺‐ and Mn²⁺‐doped fluoride and chloride Na₃(SO₄)X (X = F or Cl) luminescent material, which can be the efficient phosphors in many applications, such as scintillation applications, TL dosimetry and the lamp industry, etc. Copyright © 2012 John Wiley & Sons, Ltd.     

Luminescence and spectroscopic studies of halosulfate phosphors: a review

This review discusses the photoluminescence (PL) characteristics of halosulfate phosphors developed by us. Halosulfate phosphors KCaSO₄Cl:X,Y (X = Eu or Ce; Y = Dy or Mn) and Na₆(SO₄)₂FCl (doped with Dy, Ce or Eu) were prepared using a solid‐state diffusion method. The mechanism of energy transfer from Eu²⁺→Dy³⁺, Ce³⁺→Dy³⁺ and Ce³⁺→Mn²⁺ has also been studied. Dy³⁺ emission in the host at 475 and 570 nm is observed due to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transition, whereas the PL emission spectra of Na₆(SO₄)₂FCl:Ce phosphor shows Ce³⁺ emission at 322 nm due to 5d→4f transition of the Ce³⁺ ion. The main property of KCaSO₄Cl is its very high sensitivity, particularly when doped by Dy, Mn or Pb activators. This review also discusses the PL characteristics of some new phosphors such as LiMgSO₄F, Na₆Pb₄(SO₄)₆Cl₂, Na₂₁Mg(SO₄)₁₀Cl₃ and Na₁₅(SO₄)₅F₄Cl. Copyright © 2014 John Wiley & Sons, Ltd.     

Formation and phosphodiesterolytic activity of lanthanide(III) N,N-bis(2-hydroxyethyl)glycine hydroxo complexes

Potentiometric titrations of N,N-bis(2-hydroxyethyl)glycine (bicine) in the presence of Ln(III) cations (Ln=La, Pr, Nd and Eu) in the pH range extended to ca. 9.5 reveal formation of two types of binuclear hydroxo complexes Ln₂(bic)₂(OH)₄ and Ln₂(bic)(OH)₄ ⁺ (bicH=bicine) in addition to previously reported mononuclear mono- and bis-complexes Ln(bic)²⁺ and Ln(bic)₂ ⁺, which predominate at pH below 8. ¹H NMR titrations of La(III)-bicine mixtures in D₂O show that the complex formation with bicine is slow in the NMR time scale and confirm formation of hydroxide rather than alkoxide complexes in basic solutions. Formation of a different type of hydroxide species under conditions of an excess of metal over ligand is confirmed by studying the absorption spectra of the Nd(III)-bicine system in the hypersensitive region. The binuclear hydroxide complexes are predominant species at pH above 9 and their stabilities increase in the order La < Pr ≈ Nd < Eu. They show fairly high catalytic activity in the hydrolysis of bis(4-nitrophenyl) phosphate (BNPP) at room temperature. Comparison of concentration and pH-dependences of the reaction rates with the species distribution diagrams shows that the catalytic hydrolysis of BNPP proceeds via a Michaelis-Menten type mechanism, which involves the Ln₂(bic)(OH)₄ ⁺ complex as the reactive species. The values of the catalytic rate constants and the Michaelis constants are in the range 0.002-0.004 s⁻¹ and 0.35-1.5 mM, respectively, for all lanthanides studied. The half-life for the hydrolysis of BNPP is reduced from 2000 years to ca. 10 min at 25 °C and pH 9.2 in the presence of 5 mM La(III) and 2.5 mM bicine.     

Synthesis and characterization of KCe(PO3)4 doped with some lanthanide activators

KCe(PO₃)₄ doped with Dy³⁺,Tb³⁺,Yb³⁺and Nd³⁺ phosphors were synthesized by a solid state diffusion method. The prepared samples were characterized by X‐ray diffraction and photoluminescence. KCe(PO₃)₄ exhibits emission in ultraviolet (UV) region which indicates weak Ce³⁺–Ce³⁺ interaction. The Ce³⁺–Ce³⁺energy transfer is not efficient. In light of this, energy transfer from Ce³⁺ to other lanthanides like Dy³⁺, Tb³⁺,Yb³⁺ and Nd³⁺ is rather surprising.     

Copper-Ligand Interactions and Physiological free Radical Processes. Part 2. Influence of Cu2+ Ions on Cu+-Driven Oh Generation and Comparison with Their Effects on Fe2+-Driven Oh Production

In our search to establish a reference ·OH production system with respect to which the reactivity of copper(II) complexes could then be tested, the influence of free Cu²⁺ ions on the Cu⁺/H₂O₂ reaction has been investigated.

This influence depends on the C_Cu²⁺/C_Cu⁺ ratio. At low Cu²⁺ concentrations, ·OH damage to various detector molecules decreases with increasing Cu²⁺ concentrations until C_Cu²⁺/C_Cu⁺ reaches unity. Above this value, ·OH damage increases sharply until C_Cu²⁺/C_Cu⁺ becomes equal to 5 with salicylate and 2 with deoxyribose, ratios for which the protective effect of Cu²⁺ cancels. Finally, at higher concentrations, Cu²⁺ ions logically add their own ·OH production to that normally expected from Cu⁺ ions. The possible origin of this unprecedented alternate effect has been discussed. The possible influence of Cu⁺ ions on the generation of ·OH radicals by water gamma radiolysis has also been tested and, as already established for Cu²⁺ in a previous work, shown to be nonexistent. This definitely confirms that either form of ionised copper cannot scavenge ·OH radicals in the absence of a Iigand.     

Optical and thermal properties of rare earth–doped K4Ca(PO4)2 phosphor

The luminescent properties and energy transfer (ET) mechanism in the Ln³⁺ pair of the RE³⁺ (RE = Eu³⁺, Ce³⁺, Dy³⁺ and Sm³⁺) doped K₄Ca(PO₄)₂ phosphor were successfully investigated using a conventional high-temperature solid-state reaction. In the near infrared (NIR) range, Ce³⁺-doped K₄Ca(PO₄)₂ phosphor exhibited a UV–Vis. emission band, whereas K₄Ca(PO₄)₂:Dy³⁺ exhibited characteristic emission bands centred at 481 and 576 nm in the near-ultraviolet excitation range. The possibility of ET from Ce³⁺ to Dy³⁺ in K₄Ca(PO₄)₂ phosphor was confirmed by a significant increase in the photoluminescence intensity of the Dy³⁺ ion based on the spectral overlap of acceptor and donor ions. X-ray diffraction, Fourier-transform infrared and thermogravimetric analysis/differential thermal analysis TGA/DTA were carried out to study phase purity, presence of functional groups and amount of weight loss under different temperature regimes. Therefore, the RE³⁺-doped K₄Ca(PO₄)₂ phosphor may be a stable phosphor host for light-emitting diode applications.     

Uranyl mixed-ligand complex formation in artificial seawater

Abstract

The stability constants of the mixed uranyl-hydroxo-peroxo-carbonato species have been calculated. By incorporating those and including stability constants and corresponding equilibria into the developed model of seawater species distribution enables the dependence of uranyl species on pH to be evaluated. The calculations show that at seawater conditions (pH = 8), 88.3% of total uranyl-ion is in the form UO₂(CO₃)^4-, 11% is in the form UO₂(CO₃)₂(OH)^3-, and 0.5% in the UO₂(CO₃)(OH)₂^2- mixed-ligand complex form, while in the photic layer, 81.2% of uranyl-ion is in the tricarbonate complex, 10.1% in the form UO₂(CO₃)₂(OH₂)^3-, 7% as UO₂(CO₃)₂(OH)^3-, 0.5% as UO₂(CO₃)(OH)₂^4- and 0.5% as UO₂(O₂)₂^2- species.     

Lanthanide ions promote the hydrolysis of 2,3-Bisphosphoglycerate

The ³¹P NMR studies showed that lanthanide ions promote the site-specific hydrolysis of 2,3-Bisphosphoglycerate (BPG) at pH 7.4 by cleaving the 2 phosphomonoester bond. The effect of fourteen trivalent lanthanide ions and Sc³⁺, and Y³⁺ were compared by the percentage of hydrolysis obtained by determining the inorganic phosphate produced. All the trivalent lanthanide ions promote the hydrolysis, but Sc³⁺ not. Among them, Ce³⁺ affects the reaction mostly. This was mainly attributed to the autooxidation of Ce³⁺ to Ce⁴⁺, since the promoting effect of Ce³⁺ is related to the increasing Ce⁴⁺ amount in the solution and depressed by adding sulphite. Ce⁴⁺ promotes the hydrolysis more efficiently than Ce³⁺ do. The pseudo first-order rate constant for the hydrolysis of BPG by Ce(SO₄)₂ (18.7 mM) at pH 1 and pH 2, 37 °C is 3.1 h^–1 and 0.65 h^–1 respectively. A mechanism with a hydroxo species as reactive intermediate was proposed for the trivalent lanthanide ions. The site-specificity was explainable by this mechanism.     

Effect of Dy3+ or Eu2+ co‐activator on a BaCa(SO4)2:Ce3+ mixed alkaline earth sulfate phosphor

The individual emission and energy transfer between Ce³⁺ and Eu²⁺ or Dy³⁺ in BaCa(SO₄)₂ mixed alkaline earth sulfate phosphor prepared using a co‐precipitation method is described. The phosphor was characterized by X‐ray diffraction (XRD) and photoluminescence (PL) studies and doped by Ce;Eu and Dy rare earths. All phosphors showed excellent blue–orange emission on excitation with UV light. PL measurements reveal that the emission intensity of Eu²⁺ or Dy³⁺ dopants is greater than when they are co‐doped with Ce³⁺. An efficient Ce³⁺ → Eu²⁺ [²T_2g(4f⁶5d) → ⁸S_7/2(4f₇)] and Ce³⁺ → Dy³⁺ (⁴ F_9/2 → ⁶H_15/2 and ⁴ F_9/2 → ⁶H_13/2) energy transfer takes place in the BaCa(SO₄)₂ host. A strong blue emission peak was observed at 462 nm for Eu²⁺ ions and an orange emission peak at 574 nm for Dy³⁺ ions. Hence, this phosphor may be used as a lamp phosphor. Copyright © 2015 John Wiley & Sons, Ltd.     

Identity of the rhizotoxic aluminium species

The aluminium (III) released from soil minerals to the soil solution under acid conditions may appear as hexaaquaaluminium (Al(H₂O)₆ ³⁺, or Al³⁺ for convenience) or may react with available ligands to form additional chemical species. That one or more of these species is rhizotoxic (inhibitory to root elongation) has been known for many decades, but the identity of the toxic species remains problematical for the following reasons. 1. Several Al species coexist in solution so individual species cannot be investigated in isolation, even in artificial culture media. 2. The activities of individual species must be calculated from equilibrium data that may be uncertain. 3. The unexpected or undetected appearance of the extremely toxic triskaidekaaluminium (AlO₄Al₁₂(OH)₂₄(H₂O)₁₂ ⁷⁺ or Al₁₃) may cause misatribution of toxicity to other species, especially to mononuclear hydroxy-Al. 4. If H⁺ ameliorates Al³⁺ toxicity, or vice versa, then mononuclear hydroxy-Al may appear to be toxic when it is not. 5. The identity and activities of the Al species contacting the cell surfaces are uncertain because of the H⁺ currents through the root surface and because of surface charges. This article considers the implications of these problems for good experimental designs and critically evaluates current information regarding the relative toxicities of selected Al species. It is concluded that polycationic Al (charge >2) is rhizotoxic as are other polyvalent cations.     

Bioinspired FeIIICdII and FeIIIHgII complexes: synthesis, characterization and promiscuous catalytic activity evaluation

In this work we report on the synthesis, crystal structure, and physicochemical characterization of the novel dinuclear [Fe^IIICd^II(L)(μ-OAc)₂]ClO₄·0.5H₂O (1) complex containing the unsymmetrical ligand H₂L = 2-bis[{(2-pyridyl-methyl)-aminomethyl}-6-{(2-hydroxy-benzyl)-(2-pyridyl-methyl)}-aminomethyl]-4-methylphenol. Also, with this ligand, the tetranuclear [Fe₂^IIIHg₂^II(L)₂(OH)₂](ClO₄)₂·2CH₃OH (2) and [Fe^IIIHg^II(L)(μ-CO₃)Fe^IIIHg^II(L)](ClO₄)₂·H₂O (3) complexes were synthesized and fully characterized. It is demonstrated that the precursor [Fe^III₂Hg^II₂(L)₂(OH)₂](ClO₄)₂·2CH₃OH (2) can be converted to (3) by the fixation of atmospheric CO₂ since the crystal structure of the tetranuclear organometallic complex [Fe^IIIHg^II(L)(μ-CO₃)Fe^IIIHg^II(L)](ClO₄)₂·H₂O (3) with an unprecedented {Fe^III(μ-O_phenoxo)₂(μ-CO₃)Fe^III} core was obtained through X-ray crystallography. In the reaction 2 → 3 a nucleophilic attack of a Fe^III-bound hydroxo group on the CO₂ molecule is proposed. In addition, it is also demonstrated that complex (3) can regenerate complex (2) in aqueous/MeOH/NaOH solution. Magnetochemical studies reveal that the Fe^III centers in 3 are antiferromagnetically coupled (J = − 7.2 cm^− 1) and that the Fe^III-OR-Fe^III angle has no noticeable influence in the exchange coupling. Phosphatase-like activity studies in the hydrolysis of the model substrate bis(2,4-dinitrophenyl) phosphate (2,4-bdnpp) by 1 and 2 show Michaelis-Menten behavior with 1 being ~ 2.5 times more active than 2. In combination with k_H/k_D isotope effects, the kinetic studies suggest a mechanism in which a terminal Fe^III-bound hydroxide is the hydrolysis-initiating nucleophilic catalyst for 1 and 2. Based on the crystal structures of 1 and 3, it is assumed that the relatively long Fe^III…Hg^II distance could be responsible for the lower catalytic effectiveness of 2.     

Enhanced luminescence and white light emission from Eu3+‐co‐doped K3Ca2(SO4)3Cl:Dy3+ phosphor with near visible ultraviolet excitation for white LEDs

The luminescent properties of europium (Eu)‐ and dysprosium (Dy)‐co‐doped K₃Ca₂(SO₄)₃Cl halosulfate phosphors were analyzed. This paper reports the photoluminescence (PL) properties of K₃Ca₂(SO₄)₃Cl microphosphor doped with Eu and Dy and synthesized using a cost‐effective wet chemical method. The phosphors were characterized by X‐ray diffraction and scanning electron microscopy. The CIE coordinates were calculated to display the color of the phosphor. PL emission of the prepared samples show peaks at 484 nm (blue), 575 nm (yellow), 594 nm (orange) and 617 nm (red). The emission color of the Eu,Dy‐co‐doped K₃Ca₂(SO₄)₃Cl halophosphor depends on the doping concentration and excitation wavelength. The addition of Eu in K₃Ca₂(SO₄)₃Cl:Dy greatly enhances the intensity of the blue and yellow peaks, which corresponds to the ⁴ F_9/2 → ⁶H_15/2 and ⁴ F_9/2 → ⁶H_13/2 transitions of Dy³⁺ ions (under 351 nm excitation). The Eu³⁺/Dy³⁺ co‐doping also produces white light emission for 1 mol% of Eu³⁺, 1 mol% of Dy³⁺ in the K₃Ca₂(SO₄)₃Cl lattice under 396 nm excitation, for which the calculated chromaticity coordinates are (0.35, 0.31). Thus, K₃Ca₂(SO₄)₃Cl co‐doped with Eu/Dy is a suitable candidate for NUV based white light‐emitting phosphors technology. Copyright © 2014 John Wiley & Sons, Ltd.     

Solid‐state synthesis and luminescent properties of yellow‐emitting phosphor NaY(MoO4)2:Dy3+ for white light‐emitting diodes

A yellow‐emitting phosphor NaY(MoO₄)₂:Dy³⁺ was synthesized using a solid‐state reaction at 550 °C for 4 h, and its luminescent properties were investigated. Its phase formation was studied using X‐ray powder diffraction analysis, and there were no crystalline phases other than NaY(MoO₄)₂. NaY(MoO₄)₂:Dy³⁺ produced yellow emission under 386 or 453 nm excitation, and the prominent luminescence was yellow (575 nm) due to the ⁴ F_9/2→⁶H_13/2 transition of Dy³⁺. For the 575 nm emission, the excitation spectrum had one broad band and some narrow peaks; the peaks were located at 290, 351, 365, 386, 426, 453 and 474 nm. Emission intensities were influenced by the Dy³⁺ doping content and a concentration quenching effect was observed; the phenomenon was also proved by the decay curves. Moreover, the Commission International de I'Eclairage chromaticity coordinates of NaY(MoO₄)₂:Dy³⁺ showed similar values at different Dy³⁺ concentrations, and were located in the yellow region. Copyright © 2015 John Wiley & Sons, Ltd.     

Photoluminescence properties and energy transfer in Ce3+/Dy3+ co‐doped Sr3MgSi2O8 phosphors for potential application in ultraviolet white light‐emitting diodes

Sr₃MgSi₂O₈:Ce³⁺, Dy³⁺ phosphors were prepared by a solid‐state reaction technique and the photoluminescence properties were investigated. The emission spectra show not only a band due to Ce³⁺ ions (403 nm) but also as a band due to Dy³⁺ ions (480, 575 nm) (UV light excitation). The photoluminescence properties reveal that effective energy transfer occurs in Ce³⁺/Dy³⁺ co‐doped Sr₃MgSi₂O₈ phosphors, and the co‐doping of Ce³⁺ could enhance the emission intensity of Dy³⁺ to a certain extent by transferring its energy to Dy³⁺. The Ce³⁺/Dy³⁺ energy transfer was investigated by emission/excitation spectra, and photoluminescence decay behaviors. In Sr_2.94MgSi₂O₈:0.01Ce³⁺, 0.05Dy³⁺ phosphors, the fluorescence lifetime of Dy³⁺ (from 3.35 to 27.59 ns) is increased whereas that of Ce³⁺ is greatly decreased (from 43.59 to 13.55 ns), and this provides indirect evidence of the Ce³⁺ to Dy³⁺ energy transfer. The varied emitted color of Sr₃MgSi₂O₈:Ce³⁺, Dy³⁺ phosphors from blue to white were achieved by altering the concentration ratio of Ce³⁺ and Dy³⁺. These results indicate Sr₃MgSi₂O₈:Ce³⁺, Dy³⁺ may be as a candidate phosphor for white light‐emitting diodes. Copyright © 2012 John Wiley & Sons, Ltd.     

Photoluminescence and thermoluminescence properties of pure and rare-earth-doped ZrO2 prepared by Pechini-type sol–gel

In this article, photoluminescence (PL) and thermoluminescence (TL) properties of ZrO₂, ZrO₂:Dy³⁺, ZrO₂:Dy³⁺–Gd³⁺, ZrO₂:Dy³⁺–Yb³⁺, ZrO₂:Dy³⁺–Er³⁺, and ZrO₂:Dy³⁺–Sm³⁺ phosphors synthesized by the Pechini method were investigated. The crystal structure, thermal properties, morphology, PL and TL properties were investigated using X-ray powder diffraction (XRD), differential thermal analysis/thermogravimetric analysis (DTA/TGA), scanning electron microscopy (SEM), PL and TL, respectively. The room temperature emission bands corresponding to ⁴F_9/2 → ⁶H_J (J = 9/2, 11/2, 13/2 and 15/2) transitions of Dy³⁺ ions were measured. The phosphors were analysed using T_m–T_STOP, variable dose, and computerized glow curve fitting methods. Reusability, dose–response, and fading characteristics were investigated. The phosphors have a natural TL emission that vanished by heating treatment. Moreover, new peaks with similar properties to the natural emissions were observed after high-dose irradiation and long-term fading experiments. The glow curves of the phosphors have 13 individual peaks and many low- and high-temperature satellite peaks. The origin of the peaks is ZrO₂ host material and doping with rare-earth ions (Gd³⁺, Dy³⁺, Yb³⁺, Er³⁺ and Sm³⁺) does not lead to a new glow peak. The dopants cause drastic changes in individual peak intensities of ZrO₂.The initial fading rates of all the phosphors are relatively fast, but they slow down as time goes on.     

A Study and Optimization of Complexation of Cobalt Ions with Dihydroquercetin in Aqueous Solutions

This work continues a series of studies devoted to complex formation of ions of biogenic metals with the flavonoid dihydroquercetin (DHQ). The interaction of Со²⁺ ions with DHQ in aqueous solutions has been investigated. It has been found that, at different pH of a solution, complex compounds (CC) with different stoichiometry are formed; a variation of the pH value of a solution from 6.0 to 7.0 results in the formation of compounds (1)–(3) with the metal : flavonoid ligand ratio (Met : L) from 1 : 2 at рН 6.0 (1), through 2 : 3 at pH 6.4–6.7 (2), to 1 : 1 at рН 6.8–7.0 (3). By using the thermogravimetric method and the data of the elemental analysis, the most probable composition of the compounds with the determination of the amount of bound water has been proposed: [CoL₂(H₂O)₄] for (1), [Co₂L₃(ОН)(H₂O)₄] for (2), and [CoL(ОН)(H₂O)₂] for (3). Conditions for the optimization of product yield in the complexation reaction of Со²⁺ ions with DHQ in an aqueous solution have been determined for compound (2): the рН value of solution 6.7; the reaction time 15 min; the temperature of the reaction solution 90°С; the molar ratio of the initial reagents DHQ : Со²⁺ 1 : 1.5; the initial concentration of DHQ 0.020 mol/L and that of Со²⁺ 0.030 mol/L; and the use of CoSO₄ ? 7H₂O as a source of cobalt ions. The yield of the product is 81.8%.

     

Characterization of the 1,25-dihydroxycholecalciferol-stimulated calcium influx pathway in CaCo-2 cells

The present studies were conducted to investigate the mechanisms underlying the 1,25-dihydroxycholecalciferol (1,25(OH)₂D₃)-induced increase in intracellular Ca²⁺ ([Ca²⁺] _i ) in individual CaCo-2 cells. In the presence of 2mm Ca²⁺, 1,25(OH)₂D₃-induced a rapid transient rise in [Ca²⁺] _i in Fura-2-loaded cells in a concentration-dependent manner, which decreased, but did not return to baseline levels. In Ca²⁺-free buffer, this hormone still induced a transient rise in [Ca²⁺] _i , although of lower magnitude, but [Ca²⁺] _i then subsequently fell to baseline. In addition, 1,25(OH)₂D₃ also rapidly induced⁴⁵Ca uptake by these cells, indicating that the sustained rise in [Ca²⁺] _i was due to Ca²⁺ entry. In Mn²⁺-containing solutions, 1,25(OH)₂D₃ increased the rate of Mn²⁺ influx which was temporally preceded by an increase in [Ca²⁺] _i . The sustained rise in [Ca²⁺] _i was inhibited in the presence of external La³⁺ (0.5mm). 1,25(OH)₂D₃ did not increase Ba²⁺ entry into the cells. Moreover, neither high external K⁺ (75mm), nor the addition of Bay K 8644 (1 μm), an L-type, voltage-dependent Ca²⁺ channel agonist, alone or in combination, were found to increase [Ca²⁺] _i , 1,25(OH)₂D₃ did, however, increase intracellular Na⁺ in the absence, but not in the presence of 2mm Ca²⁺, as assessed by the sodium-sensitive dye, sodium-binding benzofuran isophthalate. These data, therefore, indicate that CaCo-2 cells do not express L-type, voltage-dependent Ca²⁺ channels. 1,25(OH)₂D₃ does appear to activate a La³⁺-inhibitable, cation influx pathway in CaCo-2 cells.