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.     

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⁺.     

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.     

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。     

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.     

Effect of Na+, Li+, Pb2+, Ba2+, Si2+, and Ca2+ cations on force constants of W-O and Mo-O bonds of WO4 2− and MoO4 2− anions in melts

By a matrix method of successive approximations, using perturbation theory, the complete set of force constants has been calculated for the free anions WO,^2– and MoO₄ ^2– and for systems MEO₄ ^2–(M = Na₂ ⁺, Li₂ ⁺, Pb²⁺,Sr²⁺, Ca²⁺; E = W, Mo) on the basis of known frequencies of IR and Raman spectra of the corresponding individual melts. Analysis of the results indicates an increase in the force constants of E-O bond stretching and the bending force constants for AD- and MoO₄ ^2– with increasing specific charge of the cation in a field of singly or doubly charged cations.Deceased.Poltava Engineering Construction Institute. Institute of General and Inorganic Chemistry, Academy of Sciences of the Ukrainian SSSR, Kiev. Translated from Teoreticheskuya i ÉksperimentaI'naya Khimiya, No. 1, pp. 120–123, January–February, 1991. Original article submitted January 12, 1989.     

不同阳离子(NH4+,Na+,K+,Ca2+)溴化物对商用SCR催化剂化学中毒影响机制研究

燃煤飞灰中的碱金属和碱土金属对 NH3-SCR 催化剂的活性有显著的影响. 近年来, 研究者针对碱金属/碱土金属氧化物对 SCR 催化剂中毒作用开展了大量研究. 另一方面, 研究普遍认为, 含溴化合物对提高 SCR 催化剂汞氧化性能具有明显促进作用. 目前为止, 针对碱金属/碱土金属溴化物对 SCR 催化剂影响的系统研究较少. 我们课题组系统研究了不同阳离子的溴化物 (NH4Br, NaBr, KBr 和 CaBr2) 对商用 V2O5-WO3/TiO2催化剂性能的影响.与未中毒样品相比, KBr 中毒后的催化剂 (记为 L-KBr) 上 NOx转化率明显下降, 而 NaBr 和 CaBr2中毒的催化剂 (分别记为 L-NaBr 和 L-CaBr) 上的 SCR 活性也有一定程度的降低. 另外 L-NaBr, L-KBr 和 L-CaBr 催化剂的 N2选择性较差. XPS 结果显示, KBr 中毒后化学吸附氧 (Oα) 比例减小; 同时, KBr 中毒后还原性和表面酸度降低, 这些可能是导致 L-KBr催化剂的活性和 N2选择性变差的主要原因. 对于 L-CaBr 催化剂, 中毒后化学吸附氧 Oα比例有所增加, 这与 H2-TPR 结果显示可还原性增强一致. O2-TPO 结果显示, L-CaBr 催化剂可氧化性降低, 说明 CaBr2中毒还是影响到催化剂表面的氧化还原循环. 催化剂 CaBr2中毒后表面被覆盖减少了反应活性位数量, 但表面酸性的增强可能会抵消活性位点损失带来的负面影响. NH3氧化结果显示, NH3在 L-CaBr 催化剂表面发生过氧化反应, 特别是高温下生成较多 N2O, 降低 N2选择性, 这可能是高温下 L-CaBr 催化剂 SCR 活性和 N2选择性下降的重要原因. CO2-TPD 结果表明, L-KBr 和 L-CaBr 催化剂表面碱性强度增加, 可能有助于增加 NOx物种的吸附量. 基于以上活性评价和表征分析结果, 我们尝试建立了不同溴化物中毒的催化剂表面酸碱性、氧化还原和催化性能之间的关系.     

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.     

高锰酸钾-鲁米诺反应体系中碱土金属离子Mg2+,Ca2+,Sr2+,Ba2+化学发光行为研究

将被认为没有化学发光活性的第二主族(碱土金属)离子Mg^2 ,Ca^2 ,Sr^2 ,Ba^2 溶液注入到已充分反应的高锰酸钾与鲁米诺混合液中时,又发生了新的化学发光反应,并检测到强的化学发光信号．在对有关反应的动力学性质、化学发光光谱、紫外可见光谱及其它一系列实验研究的基础上,提出了可能的化学发光反应机理．同时,优化了反应条件,评价了这一反应用于Mg^2 ,Ca^2 ,Sr^2 ,Ba^2 分析的可行性．     

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.     

Complexation of 4′-nitrobenzo-15-crown-5 with Li+, Na+, K+, and NH 4 + cations in acetonitrile–methanol binary solutions

The complexation processes between Li⁺, Na⁺, K⁺ and NH ₄ ⁺ cations with macrocyclic ligand, 4′-nitrobenzo-15C5, were studied in acetonitrile–methanol (AN–MeOH) binary mixtures at different temperatures using conductometric method. The conductance data show that the stoichiometry of the complexes formed between the ligand and Li⁺, Na⁺, K⁺ and NH ₄ ⁺ cations is 1:1(M:L). Addition of 4′-nitrobenzo-15C5 to these cations solution, causes a continuous increase in the molar conductivities which indicates that the mobility of the complexed cations is more than the uncomplexed ones. The values of stability constants of the complexes were determined from conductometric data using GENPLOT computer program. The obtained results show that the selectivity order of the ligand for Li⁺, Na⁺, K⁺ and NH ₄ ⁺ cations changes with the nature and composition of the binary mixed solvent. The values of thermodynamic parameters (ΔH°_c, ΔS°_c) for formation of the complexes were obtained from temperature dependence of the stability constants using the van’t Hoff plot. The results show that the complexes are both enthalpy and entropy stabilized. A non-linear behavior was observed between the stability constants (log K _f ) of the complexes and the composition of the AN–MeOH binary solution.     

Li~+,Na~+,K~+,Mg~(2+)/Cl~-,SO_4~(2-)-H_2O体系Pitzer热力学模型

介绍了描述25℃Li+,Na+,K+,Mg2+/Cl-,SO42--H2O体系的热力学Pitzer模型.给出了为获得Pitzer混合参数而测定的Li+/Cl-,SO42--H2O,Li+,K+/Cl--H2O,Li+,Na+/Cl--H2O等三元体系和Li+,Mg2+/Cl-,SO42--H2O四离子体系溶液的渗透系数.详细叙述如何利用热力学数据和溶解度数据,获得Li+,Mg2+/Cl-,SO42--H2O,Li+,K+/Cl-,SO42--H2O,Li+,Na+/Cl-,SO42--H2O体系全部混合参数及7种锂盐Gibbs标准生成自由能.进而通过数据对比,介绍了本模型在含Li+多组分溶液25℃热力学性质计算、含Li+多组分体系25℃溶解相平衡预测等方面的应用.     

Gas phase intramolecular proton transfer in cationized glycine and chlorine substituted derivatives (M-Gly, M = Na+, Mg2+, Cu+, Ni+, and Cu2+): existence of Zwitterionic structures?

The intramolecular proton transfer in cationized glycine and chlorine substituted derivatives with M = Na+, Mg2+, Ni+, Cu+, and Cu2+ has been studied with the three parameter B3LYP density functional method. The coordination of metal cations to the oxygens of the carboxylic group of glycine stabilizes the zwitterionic structure. For all monocations the intramolecular proton transfer occurs readily with small energy barriers (1-2 kcalmol(-1)). For the dication Mg2+ and Cu2+ systems, the zwitterionic structure becomes very stable. However, whereas for Mg2+, the proton transfer process takes place spontaneously, for Cu2+ the reaction occurs with an important energy barrier. The substitution of the hydrogens of the amino group by chlorine atoms decreases the basicity of nitrogen, which destabilizes the zwitterionic structure. For monosubstituted glycine complexed with Na+, the zwitterionic structure still exists as a minimum, but for disubstituted glycine no minimum appears for this structure. In contrast, for Mg2+ complexed to mono- and disubstituted glycine, the zwitterionic structure remains the only minimum, since the enhanced electrostatic interaction with the dication overcomes the destabilizing effect of the chlorine atoms.     

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.     

不同阳离子(NH_4~+,Na~+,K~+,Ca~(2+))溴化物对商用SCR催化剂化学中毒影响机制研究（英文）

燃煤飞灰中的碱金属和碱土金属对NH_3-SCR催化剂的活性有显著的影响.近年来,研究者针对碱金属/碱土金属氧化物对SCR催化剂中毒作用开展了大量研究.另一方面,研究普遍认为,含溴化合物对提高SCR催化剂汞氧化性能具有明显促进作用.目前为止,针对碱金属/碱土金属溴化物对SCR催化剂影响的系统研究较少.我们课题组系统研究了不同阳离子的溴化物(NH_4Br,NaBr,KBr和CaBr_2)对商用V_2O_5-WO_3/TiO_2催化剂性能的影响.与未中毒样品相比,KBr中毒后的催化剂(记为L-KBr)上NO_x转化率明显下降,而NaBr和CaBr_2中毒的催化剂(分别记为L-NaBr和L-CaBr)上的SCR活性也有一定程度的降低.另外L-NaBr,L-KBr和L-CaBr催化剂的N_2选择性较差.XPS结果显示,KBr中毒后化学吸附氧(O_α)比例减小;同时,KBr中毒后还原性和表面酸度降低,这些可能是导致L-KBr催化剂的活性和N_2选择性变差的主要原因.对于L-CaBr催化剂,中毒后化学吸附氧O_α比例有所增加,这与H2-TPR结果显示可还原性增强一致.O_2-TPO结果显示,L-CaBr催化剂可氧化性降低,说明CaB_r2中毒还是影响到催化剂表面的氧化还原循环.催化剂CaBr_2中毒后表面被覆盖减少了反应活性位数量,但表面酸性的增强可能会抵消活性位点损失带来的负面影响.NH_3氧化结果显示,NH_3在L-CaBr催化剂表面发生过氧化反应,特别是高温下生成较多N_2O,降低N_2选择性,这可能是高温下L-CaBr催化剂SCR活性和N_2选择性下降的重要原因.CO_2-TPD结果表明,L-KBr和L-CaBr催化剂表面碱性强度增加,可能有助于增加NO_x物种的吸附量.基于以上活性评价和表征分析结果,我们尝试建立了不同溴化物中毒的催化剂表面酸碱性、氧化还原和催化性能之间的关系.     

五元体系Li^+, Na^+, K^+, Mg^2^+/SO~4^2^- - H~2O 25℃相关 系的研究

用等温溶解平衡法研究了五元体系Li~+,Na~+,K~+,Mg~(2+)/SO_4~(2-)-H_2O25℃溶解度,测得了平衡溶液的密度,获得了该五元体系25℃溶解度相图的十个无变量点和十种平衡固相.十个单盐结晶区分别对应于原始组分K_2SO_4,Li_2SO_4·H_2O,MgSO_4·7H_2O,水合物Na_2SO_4·10H_2O,复盐3K_2SO_4·Na_2SO_4,Na_2SO_4·MgSO_4·4H_2O,Li_2SO_4·3Na_2SO_4·12H_2O,2Li_2SO_4·Na_2SO_4·K_2SO_4,Li_2SO_4,K_2SO_4和K_2SO_4·MgSO_4·6H_2O,此外没有产生新的复盐或固溶体.用现代电解质溶液理论-Pitzer模型校验该体系的溶解度测定值,结果令人满意.     

五元体系Li^+, Na^+, K^+, Mg^2^+/SO~4^2^- - H~2O 25℃相关 系的研究

用等温溶解平衡法研究了五元体系Li^+,Na^+,K^+,Mg^2^+/SO~4^2^--H~2O25℃溶解度,测得了平衡溶液的密度,获得了该五元体系25℃溶解度相图的十个无变量点和十种平衡固相。十个单盐结晶区分别对应于原始组分K~2SO~4,Li~SO~4.H~2O,MgSO~4.7H~2O,水合物Na~2SO~4.10H~2O,复盐3K~2SO~4.Na~2SO~4,Na~2SO~4.MgSO~4.4H~2O,Li~2SO~4.3Na~2SO~4.12H~2O,2Li~2SO~4.Na~2SO~4.K~2SO~4,Li~2SO~4.K~2SO~4和K~2SO~4.MgSO~4.6H~2O,此外没有产生新的复盐或固溶体。用现代电解质溶液理论---Pitzer模型校验该体系的溶解度测定值,结果令人满意。