Complexation of 3-hydroxy-2,2′-iminodisuccinic acid (HIDS) with Mg2+, Ca2+, Mn2+, Fe3+, Fe2+, Co2+, Ni2+, Cu2+, and Zn2+ ions in aqueous solution

In a search for environmental-friendly metal chelating ligands for industrial applications, the protonation and complex formation equilibria of 3-hydroxy-2,2′-iminodisuccinic acid with Mg²⁺, Ca²⁺, Mn²⁺, Fe³⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺ ions in aqueous 0.1 mol L^?1 NaCl solution were studied at 25°C by potentiometric titration. The model for complexation and the stability constants of the different complexes were determined for each metal ion using the computer program SUPERQUAD. In all cases, complex formation was dominated by stable ML ^{n ?4} complexes.     

钙钛矿结构荧光材料MZrO3:Eu3+,A (M=Ca2+, Ba2+; A=Li+, Na+, K+)的制备及其发光性质

Calcium and barium zirconate powders based upon CaZrO₃:Eu³⁺,A and BaZrO₃:Eu³⁺,A (A=Li⁺, Na⁺, K⁺) were prepared by combustion synthesis method and heating to ~1000℃ to improve crystallinity.The structure and morphology of materials were examined by X-ray diffraction (XRD) and scanningelectron microscopy (SEM). XRD results showed that CaZrO₃:Eu³⁺,A and BaZrO₃:Eu³⁺,A (A=Li⁺, Na⁺, K⁺) perovskites possessed orthorhombic and cubic structures, respectively. The morphologies of all powderswere very similar consisting of small, coagulated, cubical particles with narrow size distributions andsmooth and regular surfaces. The characteristic luminescences of Eu³⁺ ions in CaZrO₃:Eu³⁺,A (A=Li⁺, Na⁺, K⁺) lattices were present with strong emissions at 614 and 625 nm for ⁵D₀→⁷F₂ transitions with other weakeremissions observed at 575, 592, 655, and 701 nm corresponding to ⁵D₀→⁷F_n transitions (where n=0, 1, 3, 4 respectively). In BaZrO₃:Eu³⁺ both the ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transitions at 595 and 613 nm were strong.Photoluminescence intensities of CaZrO₃:Eu³⁺ samples were higher than those of BaZrO₃:Eu³⁺ lattices. Thisremarkable increase of photoluminescence intensity (corresponding to ⁵D₀→⁷F_n transitions) was observedin CaZrO₃:Eu³⁺ and BaZrO₃:Eu³⁺ if co-doped with Li⁺ ions. An additional broad band composed of manypeaks between 440 to 575 nm was observed in BaZrO₃:Eu³⁺,,A samples. The intensity of this band wasgreatest in Li⁺ co-doped samples and lowest for K⁺ doped samples.     

Radioluminescence of Europium(III) in POCl3–SnCl4–235UO2+ 2–Eu3+, and D2O–235UO2+ 2–Eu3+ Solutions

Results of studying the spectral and luminescent properties of Eu³⁺ ions upon homogeneous excitation of POCl₃–SnCl₄–^-UO²⁺ ₂–Eu³⁺ and D₂O–²³⁵UO²⁺ ₂–Eu³⁺ solutions by -particles are presented. It was found that the radioluminescence intensity of Eu³⁺ ions in both solvents increases proportionally to the energy input by -particles. The yield of radioluminescence photons from europium ions in the POCl₃–SnCl₄–UO²⁺ ₂–Eu³⁺ solutions is more than nine times as high as that in D₂O–UO²⁺ ₂–Eu³⁺. The radiation-chemical yields of excited ⁵ D ₀ states of Eu³⁺ ions are 0.74 ± 0.07 and 0.18 ± 0.02 ions/100 eV in POCl₃–SnCl₄–UO²⁺ ₂–Eu³⁺ and D₂O–UO²⁺ ₂–Eu³⁺ solutions, respectively.     

Complexing Power of Vitamin D3 Toward Various Metals. Potentiometric Studies of Vitamin D3 Complexes with Al3+, Cd2+, Gd3+, and Pb2+ Ions in Water–Ethanol Solution

This study reports the stability constants of complexes with vitamin D₃ and Al³⁺, Cd²⁺, Gd³⁺ and Pb²⁺ ions in a water–ethanol medium (30/70% v/v at 25.0°C). The logarithms of the overall stability constants are: ₁ = 12.4 ± 0.5, 7.6 ± 0.3, 9.33 ± 0.07, and 9.1 ± 0.5, respectively, whereas the logarithms of ₂ are 24.4 ± 0.5 (Al³⁺), 14.3 ± 0.3 (Cd²⁺), and 15.4 ± 0.5 (Pb²⁺). Gd³⁺ forms only the 1:1 complex. These values are compared to those reported previously and correlations are established between the stability constants and physical properties, such as the ionization energy.     

Calcul Des Diagrammes De Phases Des Systemes Binaires H2O–MCln (M=Mg2+, Fe2+, Fe3+)

A semi-empirical model consistent with thermodynamical conditions of equilibrium was used and oriented to the calculation of phase diagrams of the binary systems H₂ O-MgCl₂ , H₂ O-FeCl₂ and H₂ O-FeCl₃ . For each solid phase, the exploitation of the experimental and bibliographical data gives a liquidus curve equation comprising a limited number of parameters. A such equation allows to calculate with precision the solubility of the stoichiometric solid phase in a large range of temperature and composition. This revised version was published online in July 2006 with corrections to the Cover Date.     

多孔磁体甲酸盐[M3(HCOO)6](M=Mn2+,Fe2+,Co2+,Ni2+,Fe2+/Zn2+)的研究

综述了近年来我们在多孔磁体甲酸盐系列[M3(HCOO)6](M=Mn2 ,Fe2 ,Co2 ,Ni2 ,Fe2 /Zn2 )获得的研究结果.这些多孔磁体可以在常温下用温和的溶液化学方法制备获得,它们的结构是以MM4四面体为节点的金刚石多孔骨架,呈现了很好的热稳定性、多孔性、广谱的客体包合性能和稳定性.由于客体的包合对多孔磁性骨架的结构参数产生影响以及客体和骨架之间的弱氢键相互作用,这些多孔磁体表现了丰富的和客体调控的磁性质.混合金属的多孔磁体[FexZn3-x(HCOO)6]表现了随着Zn2 的含量增加而发生的由三维磁有序到自旋玻璃、再到超顺磁体、最后到顺磁体的渐次转变.     

Front Cover: Method development for the investigation of Mn2+/3+, Cu2+, Co2+, and Ni2+ with capillary electrophoresis hyphenated to inductively coupled plasma–mass spectrometry

The lifetime of lithium ion batteries (LIBs) decreases under continuous cycling due to various degradation processes, such as dissolution of transition metals (TMs) from the electrodes. Therefore, suitable methods to analyze the oxidation states of TMs are mandatory to better understand the dissolution mechanisms of TMs from positive and negative electrodes (LIBs). To investigate the dissolution of Mn²⁺ and Mn³⁺ in electrolytes of LIBs, a previously implemented capillary electrophoresis (CE) method with UV/Vis spectroscopy detection was further developed with the aim of higher sensitivities and additional detection of other dissolved divalent TMs such as Co²⁺, Ni²⁺, and Cu²⁺. Therefore, inductively coupled plasma–mass spectrometry was applied instead of UV/Vis for detection. This also allows the use of Ga³⁺ instead of the previously used Cu²⁺ as an internal standard, which solves the limitation of this method for cycled LIBs due to copper dissolution from the copper-based current collector. The CE buffer based on sodium diphosphate as complexing agent for the stabilization of Mn³⁺ and cetyltrimethylammonium bromide as dynamic capillary wall modifier was optimized in terms of concentrations and pH. Finally, both manganese species and Co²⁺, Ni²⁺, and Cu²⁺ could be analyzed within 15 min. With this improved method, the dissolution of TMs in LIBs for positive electrode materials such as LiNi_0.5Mn_1.5O₄ (LNMO) or LiNi_xCo_yMn_zO₂ (NCM, x + y + z = 1) can be studied in future in more detail.     

Impact of metal ions (Cr3+, Co2+, Ni2+, Cu2+ and Zn2+) substitution on the structural,magnetic and catalytic properties of substituted Co–Mn ferrites synthesized by sol–gel route

Journal of Sol-Gel Science and Technology - Manganese substituted cobalt ferrites (CoMn x Fe2?x O4, x?=?0.2, 0.4, 0.6, 0.8 and 1.0) synthesized using sol gel autocombustion method...     

稀土离子(La3+, Gd3+, Yb3+, Ce3+)对线粒体的氧化损伤

主要考察了稀土离子对线粒体氧化损伤(膜脂质过氧化、膜蛋白氧化、线粒体DNA氧化)的作用。结果表明,稀土离子(La3 ,Gd3 ,Yb3 ,Ce3 )浓度大于2×10-5mol.L-1时,对线粒体膜脂质过氧化、膜蛋白氧化均有明显的促进作用;在对Fe2 诱导的线粒体氧化过程中,La3 ,Gd3 和Yb3 能明显地增强Fe2 的氧化作用,而Ce3 对Fe2 的作用表现出明显的拮抗作用,此外Ce3 对Fe2 诱导的线粒体DNA氧化损伤表现出明显的拮抗作用,显示了Ce3 的特殊性。     

Study of the state of uranoarsenates MII(AsUO6)2·nH2O(MII = Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Pb2+) in aqueous solutions

State of uranoarsenates M^II(AsUO₆)₂·nH₂O (M^II = Mn, Co, Ni, Cu, Zn, Cd, Pb) in aqueous solutions in a wide range of acidity (pH 0?C14) was studied. Acid-base boundaries of existence of the compounds were estimated, products of conversion were identified, and solubility of M^II(AsUO₆)₂·nH₂O was determined. On the basis of the obtained data the solubility products and Gibbs functions of formation of uranoarsenates, and the solubility curves were calculated, phase diagrams of uranium(VI) and arsenic(V) in solutions and in equilibrium solid phases were constructed with the use of the equilibrium thermodynamics technique.     

A 3-D inorganic–organic hybrid based on saturated Wells–Dawson polyoxoanion and K+, linked by an Ag–Ag bond

A 3-D complex K₂[Ag₂(biim)₂]₂P₂W₁₈O₆₂ (biim?=?biimidazole) (1) has been hydrothermally synthesized and characterized by IR, thermogravimetric, and single-crystal X-ray diffraction. Single-crystal X-ray structural analysis reveals that 1 exhibits a 1-D wavelike chain constructed from µ₃-bridging oxygen atoms of [P₂W₁₈O₆₂]^6? and [Ag₂(biim)₂]²⁺. The K⁺ link to six oxygen atoms of three P₂W₁₈ clusters and 12 equatorial terminal oxygen atoms of P₂W₁₈ clusters link to six K⁺, resulting in a 3-D framework with a relatively short Ag–Ag bond [2.836?Å]. The electrochemical behavior of 1 modified carbon paste electrode (1-CPE) has been studied. The results indicate that 1-CPE has remarkable stability.     

一种含芴聚合物对Pb2+,Cd2+,Cr3+金属离子的检测

利用一种芴类共轭聚合物,通过紫外分光光度计与荧光分光光度计测试其对Pb~(2+),Cd~(2+)和Cr~(3+)三种金属离子的紫外响应性与荧光淬灭性。在聚合物溶液中分别加入Pb~(2+),Cd~(2+)和Cr~(3+)三种金属离子,紫外吸收峰位于298nm和308nm;荧光最大发射峰位于335nm。研究发现,Pb~(2+)对聚合物溶液的紫外响应性有影响,Cd~(2+)和Cr~(3+)对聚合物溶液的紫外响应性无明显影响;Pb~(2+)对聚合物溶液的荧光强度有轻微增强的作用,而加入Cd~(2+)和Cr~(3+)的聚合物溶液荧光强度骤降,发生了明显的淬灭。不同pH值范围下的光谱研究表明,pH值在5.0～6.0区间时,加入Cr~(3+),聚合物溶液荧光强度明显下降;pH值在6.0～7.0区间时,加入Cd~(2+),荧光强度明显下降;pH值在4.5～6.0区间时,加入Pb~(2+),荧光强度明显下降。     

The basis set convergence of the Hartree–Fock energy for H3 +, Li2 and N2

 By using completely optimized basis functions it is shown that the convergence of the Hartree–Fock energy for the H₃ ⁺, Li₂ and N₂ molecules is significantly better described by exponential behavior than by inverse power dependence. This is the case both with respect to the number of basis functions of a given type and with respect to the highest angular momentum function included. The Hartree–Fock limit for H₃ ⁺ is estimated to be −1.300372125 hartree. Received: 14 February 2000 / Accepted: 12 April 2000 / Published online: 18 August 2000     

Étude structurale comparée des chromates: M(I)M(III)(CrO4)2; M(I) = Li+, Na+, K+, Rb+, Cs+, NH4+, Ag+ et Tl+; M(III) = Al3+, Fe3+, Cr3+, Tl3+ et Bi3+

Among compounds of formula type M(I)M(III)(CrO₄)₂, the structures of trivalent bismuth compounds are always different from the others, because the surrounding of bismuth is never well-defined. Besides, nearly all these compounds have two-dimensional structures with the exception of Tl(I)Tl(III)(CrO₄)₂ which is three-dimensional. This structural type can exist only when the ionic radius of the monovalent cation has a value near that of O²⁻ ion (1.40 Å), as for Rb⁺, NH₄⁺ and Tl⁺.     

Performances catalytiques de faujasites Y échangées par des cations de Ce3+, La3+, UO22+, Co2+, Sr2+, Pb2+, Tl+ et NH4+ dans la réaction de dismutation du toluène

The catalytic performance of exchanged Y faujasites by Ce³⁺, La³⁺, UO₂²⁺, Co²⁺, Sr²⁺, Pb²⁺, Tl⁺ and NH₄⁺ ions were studied in a disproportionation reaction in the gaseous phase. It was shown that total acidity generated by exchanged ions is responsible of the catalytic activity. Rare earths (cerium, lanthanum and uranium) catalysts have appreciable performance and allowed one to obtain an important xylenes proportion at 400 to 450 °C. The decrease of xylenes and trimethylbenzenes proportion in studied catalysts shows the implication of xylenes in toluene disproportionation reaction.     

稀土离子(La3+,Ce3+,Tb3+,Y3+)对炎症及血小板聚集的影响

研究稀土离子(La3 ,Ce3 ,Tb3 ,Y3 )对炎症、血小板聚集及蛋白磷酸化的影响.采用二甲苯使小鼠耳部致炎,腹腔注射稀土离子,观察炎症的变化;利用血小板聚集仪观察稀土离子对血小板聚集的影响;用放射标记法测量稀土对血小板蛋白磷酸化程度的影响.结果表明,稀土离子在2.5×10-4mol·L-1·kg-1的注射剂量下,能显著加强炎症反应;1×10-3mol·L-1的轻稀土(La3 ,Ce3 )对由ADP诱导的血小板聚集有明显的抑制作用,而重稀土(Tb3 ,Y3 )有明显的促进作用;浓度在1×10-6～1×10-4mol·L-1时,轻、重稀土均可促进血小板蛋白磷酸化.稀土离子对炎症、血小板聚集及蛋白磷酸化的影响与稀土的种类和剂量有关.     

碱土金属离子(Mg2+,Ca2+,Ba2+)掺杂对长余辉荧光粉SrAl2O4:Eu2+,Dy3+发光性能的影响

采用高温固相法制备了碱土金属离子(Mg2 ,Ca2 ,Ba2 )掺杂的SrAl2O4:Eu2 ,Dy3 长余辉荧光粉.XRD谱分析表明,随着基质中掺人的碱土金属离子(Mg2 ,Ca2 ,Ba2 )浓度增加,基质晶格常数也随之发生变化.Mg2 ,Ca2 和Ba2 3种碱土离子在SrAl2O4中的固溶范围分别为40%,15%和30%.光谱分析则表明在固溶范围内随着掺杂Mg3 ,Ca2 和Ba2 浓度的增大,样品的发射峰值会在480～530 nm范围出现规律性移动.适当浓度的Mg2 ,Ba2 掺杂会不同程度地提高样品的发光强度,而Ca2 的掺杂则会降低发光强度.但是碱土金属离子(Mg2 ,Ca2 ,Ba2 )的掺杂并不能延长SrAl2O4:Eu2 ,Dy3 荧光粉的余辉时间.     

The pK 2 * for the dissociation of H2SO3 in NaCl solutions with added Ni2+, Co2+, Mn2+, and Cd2+ at 25°C

The pK ₂ ^* for the dissociation of sulfurous acid from I=0.5 to 6.0 molal at 25°C has been determined from emf measurements in NaCl solutions with added concentrations of NiCl₂, CoCl₂, McCl₂ and CdCl₂ (m=0.1). These experimental results have been treated using both the ion pairing and Pitzer's specific ion-interaction models. The Pitzer parameters for the interaction of M²⁺ with SO ₃ ^2? yielded $$\begin{gathered} \beta _{NiSO_3 }^{(0)} = - 5.5, \beta _{NiSO_3 }^{(1)} = 5.8, and \beta _{NiSO_3 }^{(2)} = - 138 \hfill \\ \beta _{CoSO_3 }^{(0)} = - 12.3, \beta _{CoSO_3 }^{(1)} = 31.6, and \beta _{CoSO_3 }^{(2)} = - 562 \hfill \\ \beta _{MnSO_3 }^{(0)} = - 8.9, \beta _{MnSO_3 }^{(1)} = 18.7, and \beta _{MnSO_3 }^{(2)} = - 353 \hfill \\ \beta _{CdSO_3 }^{(0)} = - 7.2, \beta _{CdSO_3 }^{(1)} = 13.8, and \beta _{CdSO_3 }^{(2)} = - 489 \hfill \\ \end{gathered} $$ The calculated values of pK ₂ ^* using Pitzer's equations reproduce the measured values to within ±0.01 pK units. The ion pairing model yielded $$\begin{gathered} logK_{NiSO_3 } = 2.88 and log\gamma _{NiSO_3 } = 0.111 \hfill \\ logK_{CoSO_3 } = 3.08 and log\gamma _{CoSO_3 } = 0.051 \hfill \\ logK_{MnSO_3 } = 3.00 and log\gamma _{MnSO_3 } = 0.041 \hfill \\ logK_{CdSO_3 } = 3.29 and log\gamma _{CdSO_3 } = 0.171 \hfill \\ \end{gathered} $$ for the formation of the complex MSO₃. The stability constants for the formation of MSO₃ complexes were found to correlate with the literature values for the formation of MSO₄ complexes.     

A novel magnetic biosorbent prepared using an oak shell waste material as an efficient adsorbent for consecutive removal of Pb2+, Ag+, Ba2+, Sr2+, and CrO42− from aqueous solutions

In this research, the performance of a new biosorbent prepared using low-cost oak shell waste materials for consecutive removal of particular cations and chromate anions from aqueous solutions was studied. The adsorbent impregnated with Pb²⁺, Ag⁺, Ba²⁺, and Sr²⁺ was used to remove chromate anions by the formation of an appropriate insoluble precipitate. The biosorbent was characterized by FTIR, XRD, SEM, TG-DTG, and VSM techniques. The adsorption capacities of 133.84, 53.12, 50.12, and 40.39 mg g^?1 were obtained for chromate for the samples containing Pb²⁺, Ag⁺, Ba²⁺, and Sr²⁺ cations, respectively. The chromate uptake was inversely proportional to the k_sp of the chromate precipitate and increased with the cation content of the adsorbent. The adsorption process was kinetically fast and the equilibrium was established within 10 min. The experimental data were analyzed by the Langmuir, Freundlich, Sips, and Redlich-Peterson isotherm models. The data were fitted to the Langmuir isotherm, indicating that chromate was adsorbed homogeneously on the adsorbent surface.     

Luminescent core–shell Fe3O4@Gd2O3:Er3+, Li+ composite particles with enhanced optical properties

Bifunctional magneto-optical nanocomposites with Fe₃O₄ nanoparticles as a core and erbium and lithium codoped gadolinium (Gd₂O₃:Er³⁺, Li⁺) as the shell were synthesized successfully using a simple urea homogeneous precipitation method. The fabricated Fe₃O₄@Gd₂O₃:Er³⁺, Li⁺ particles were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, photoluminescence spectroscopy and quantum design vibrating sample magnetometry. The upconversion emission intensity was enhanced significantly comparing to that without Li⁺ ions. These bifunctional composites are expected to be potentially applied for drug delivery, cell separation and bioimaging.