蕨类植物铁芒萁（Dicranopteris dichotoma）体内稀土元素的分布及其光合特性的研究

为了阐明蕨类植物铁芒萁(Dicranopteris dichotoma Bernh.)体内稀土元素的分布及其光合特性，采用电感耦合等离子质谱分析了中国江西省龙南县轻、重稀土矿区和非矿区铁芒萁植物体内的稀土元素含量，并采用透射电子显微镜对其叶片细胞内的稀土元素进行精确定位。还比较系统的研究了自然条件下的铁芒萁与高浓度稀土元素处理条件下的非稀土元素富集植物黄瓜(Cucumis sativus Linn)的光合特性。结果表明： 1、0.5 mmol•L-1 LaCl3处理黄瓜后，可以诱导激发能向PS II分配。1和2 mmol•L-1 LaCl3处理黄瓜后，对黄瓜幼苗抑制作用表现在对其生长率，光合放氧活性和叶绿体完整率的抑制。这是由于LaCl3对黄瓜细胞结构和叶绿体膜结构的破坏所致。其表现为对类囊体膜结构的破坏，而导致PS II光合活性下降，并最终抑制黄瓜生长。 2、铁芒萁可以富集稀土元素，轻、重稀土矿区铁芒萁植物稀土元素的分布规律为叶片>根>土壤>茎>叶柄，非矿区铁芒萁植物稀土元素的分布规律为叶片>根>茎>叶柄。稀土元素在铁芒萁体内的运输和迁移过程中，发生了明显的分异作用，茎、叶柄、叶片中的重稀土相对贫乏，叶片中可以富集高浓度的轻稀土元素。 3、稀土元素可以进入完整的铁芒萁表皮细胞和叶肉细胞中，但多以沉淀的形式聚集在一起。非矿区铁芒萁叶绿体中的稀土元素含量约占其叶片中含量的5％。轻稀土矿区铁芒萁叶绿体中的稀土元素含量约占其叶片中含量的10％。部分稀土元素定位于富含PS II的基粒片层上。 4、铁芒萁富集稀土元素受环境和遗传特性的双重影响，但主要由其自身的生理、生化特性决定。其富集稀土元素的机制是隔离稀土元素在细胞壁、液泡中和分泌结合物质使稀土元素成为沉淀沉积下来，从而避免对光合活性的破坏。 5、与非矿区铁芒萁相比，轻稀土矿区植物叶绿体膜的全链电子传递速率增加了34.9％，PS II的电子传递活性增高了252.9％，PS I的电子传递活性增加了16.8％。轻稀土矿区铁芒萁全链电子传递活性的增加主要来自PS II电子传递活性的大幅提高，这可能与其调节激发能更多向PS II分配，提高PS II反应中心色素蛋白复合体（67.0％）和捕光色素蛋白复合体的含量相关。 6、与非矿区铁芒萁相比，重稀土矿区植物叶绿体膜的全链电子传递速率增加了46.3％，PS II的电子传递活性增高了23.8％，PS I的电子传递活性增加了60.4％。重稀土矿区铁芒萁电子传递活性的提高主要来自PS I电子传递活性的大量增加，这可能与其PS I反应中心蛋白复合体含量的提高（60.0％）有关。 铁芒萁富集并吸收稀土元素主要是由自身的理化特性决定的。它能够将稀土元素以沉淀的形式固定在细胞内部，并通过改变生理代谢来避免高浓度稀土元素对其光合作用的影响。可以在治理稀土元素污染的环保工程中用作植物修复材料。

Studies on the toxic effects of La3+ to Tetrahymena thermophila by microcalorimetry

The toxic effects of La3+ on Tetrahymena thermophila have been studied by microcalorimetry at 28 degrees C. The metabolic rate constant (r) and peak time were linked to the concentration of La3+. The changes of metabolic rate constant indicated that low-concentration La3+ (0-75 mg/L) had no significant effects on the metabolism of Tetrahymena cells but high-concentration La3+ (100-175 mg/L) could inhibit their metabolism. From the results obtained by cell counting and fluorescence depolarization measurements, the inhibition of metabolism resulted from the decrease in cell number and the reduction in cell membrane fluidity. According to the results, it is clear that the metabolic mechanism of Tetrahymena cells has been changed with the addition of high-concentration La3+. In addition, microcalorimetry of Tetrahymena could be a sensible, easy-to-use, and convenient method for monitoring the potential effects of rare earth elements on cells and the freshwater ecosystem.

色谱法分离稀土元素和生物小分子的研究

本论文利用高效离心分配色谱仪进行了稀土元素抗、忆、斓的分离研究和菱角壳中黄酮类化合物的分离研究；探讨了氨基酸在双水相体系中的分配行为；利用气相色谱一质谱法测定了野生菱角壳中的多糖类化合物的组成；利用高效制备色谱法对野生菱角壳中的黄酮类和生物碱类化合物分别进行了制备分离的研究。1．首次采用新型梭酸类萃取剂CA-12（仲辛基苯氧基乙酸）的庚烷溶液作为固定相，以氯乙酸一氢氧化钠混合溶液为流动相，利用高效离心分配色谱（HPCPC）分离伉、铭、斓，考察了流动相酸度、流速及HPCPC转速对分离效率的影响，通过梯度PH洗脱，实现了杭、忆、悯的基线分离，并对CA-12萃取金属离子的机理进行了探讨，同时利用HPCPC，对黄酮类化合物进行了分离研究，优选出溶剂系统（正己烷一乙酸乙醋一甲醇一水）的最佳配比，实现了混合物的分离。2．首次对四种氨基酸在聚乙二醇（PEG）一磷酸盐双水相体系中的分配行为进行了研究。考察了PEG分子量、磷酸盐溶液的pH值对相图的影响，测定了两相的组成、密度和折射率等参数，并对缓冲溶液的pH值、盐离子的存在和氨基酸的支链结构对氨基酸在双水相中分配比的影响进行了探讨。3．用乙醇分级沉淀法，首次从野生菱角壳中提取出多糖化合物。通过Molisch试验、红外光谱、核磁共振波谱分析确定了多糖的存在，用气相色谱一质谱法，确定了菱角壳多糖化合物的单糖组成。首次从野生菱角壳中提取出黄酮类化合物和生物碱类化合物，利用高效制备液相色谱（HPLC），通过考察流动相的组成配比、流速、检测波长等分离条件对分离效果的影响，优选出最佳色谱分离条件和制备条件，分离制备出四个黄酮化合物和三个生物碱化合物单组分，经化学法、红外光谱、质谱法和核磁共振法等初步确定了黄酮类化合物和生物碱类化合物的基本结构单元。

Theoretical study of p-d hybridization in Co perovskite

The real-space recursion method and unrestricted Hartree-Fock approximation have been applied to calculate the density of states of various Co perovskite, CeCoO3, SrCoO3 and Sr1-xCexCoO3. We have studied the magnetically ordered states of these Co perovskites in an enlarged double cell, and find its various magnetic structures due to the occupancy of 3d band and its interaction with neighboring Co ions. In this study, we have studied the p-d hybridization of the three Co perovskites, we find t(2g) electrons are localized and the flat e(g) band is responsible for the itinerant behavior, and although the rare earth elements itself contribute little to the DOS at the Fermi energy, the DOS at Fermi energy and the magnetic moment changed consequently because of different valence of Co ions in these compounds and p-d hybridization effect is very important. (C) 2009 Elsevier B.V. All rights reserved.

Structure stability and strengthening mechanism of die-cast Mg-Gd-Dy based alloy

Mg-8Gd-1Dy-0.3Zn (wt.%) alloy was prepared by high-pressure die-casting technique. The thermal stability, mechanical properties at temperature range from room temperature to 573 K and strengthening mechanism was investigated. The results showed that the die-cast state alloy was mainly composed of fine cellular equiaxed grain. The fine porosity-free skin region was related to the aggregation of rare earth elements. The long lamellar-shaped stacking compound containing Zn and polygon-shaped precipitate were observed along the grain boundaries. The die-cast sample exhibited high mechanical properties and good thermal stability until 523 K.

Highly uniform and monodisperse beta-NaYF4 : Ln(3+) (Ln = Eu, Tb, Yb/Er, and Yb/Tm) hexagonal microprism crystals: Hydrothermal synthesis and luminescent properties

beta-NaYF4:Ln(3+) (Ln = Eu, Tb, Yb/Er, and Yb/Tm) hexagonal microprisms with remarkably uniform morphology and size have been synthesized via a facile hydrothermal route. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and photoluminescence (PL) spectra as well as kinetic decays were used to characterize the samples. It is found that sodium citrate as a shape modifier introduced into the reaction system plays a critical role in the shape evolution of the final products. Furthermore, the shape and size of the products can be further manipulated by adjusting the molar ratio of citrate/RE3+ (RE represents the total amount of Y3+ and the doped rare earth elements such as Eu3+, Tb3+, Yb3+/Er3+, or Yb3+/Tm3+). Under the excitation of 397 nm ultraviolet light, NaYF4:xEu(3+) (x = 1.5, 5%) shows the emission lines of Eu3+ corresponding to D-5(0-3) -> F-7(J) (J = 0-4) transitions from 400 to 700 nm (whole visible spectral region) with different intensity, resulting in yellow and red down-conversion (DC) light emissions, respectively.

Density functional studies of diatomic LaO to LuO

Bond distances, vibrational frequencies, electron affinities, ionization potentials, dissociation energies and dipole moments of the title molecules in neutral, positively and negatively charged ions were studied by use of density functional method. Ground electronic state was assigned for each molecule. The bonding patterns were analyzed and compared with both the available data and across the series. It was found that besides ionic component, covalent bonds are formed between the metal s, d and f orbitals and oxygen p orbitals. Contrary to the well known lanthanide contraction, the bond distance is not regular from LaO to LuO for both neutral and charged molecules. An obvious population at 5d orbital was observed through the lanthanide series. 4f electrons also participate the chemical bonding for CeO to NdO and TbO to TmO. For EuO, GdO, YbO and LuO, 4f electrons tend to be localized. The spin multiplicity is regular for neutral and charged molecules. The spin multiplicity of the charged molecules can be obtained by -1 (or +1 for TbO+, DyO+, YbO- and YbO+) compared with the corresponding neutral molecules.

Structure and mechanical properties of Mg-Zn-RE system alloys

The lightest density of Mg has stimulated renewed interest in Mg based alloys for applications in the automotive, aerospace and communications industries. However, Mg in the pure form has relatively low strength, limited ductility and is susceptible to corrosion. Great efforts have been made to improve the mechanical properties of Mg alloys. Alloying Mg with other elements is one of the most important methods. An important class of Mg alloys is the Mg-Zn-RE system (RE = rare earth elements). In recent few decades, a series of new Mg-Zn-RE system alloys have been obtained, and detailed the structure and mechanical properties of the alloys. In this paper, the structure and mechanical properties of the Mg-Zn-RE alloys have been summarized. It showed that these alloys have high strength and they are prospected to be widely used in the future.

Extraction kinetics of Sc(III), Y(III), La(III) and Gd(III) from chloride medium by Cyanex 302 in heptane using the constant interfacial cell with laminar flow

The extraction kinetics of Sc, Y, La and Gd(III) from the hydrochloric acid medium using Cyanex 302 (hereafter HL) in heptane solution have been measured by the constant interfacial cell with laminar flow. Reaction regions are explored at liquid-liquid interface. Extraction regimes are deduced to be diffusion-controlled for Sc(Ill) and mixed controlled for Y, La and Gd(Ill). Extraction mechanisms are discussed according to the dimeric model of Cyanex 302 in non-polar solution. From the temperature dependence of rate measurement, the values of E-a, Delta H-+/-, Delta S-+/- and Delta G(300)(+/-) are calculated and it is found that the absolute values of these parameters keep crescent trend for Sc, Y, La and Gd(III). At the same time, it is found that it can easily achieve the mutual separation among the Sc, Y and La(III) with kinetics extraction methods.

Influence of structure and lonic radius on solubility limit in the Mg-Re systems

The relationship between structure, ionic radius and electronegativity and solubility of the various rare-earth elements in Mg was studied. It is found that light RE(La-Sm, Eu, Yb) have more complicated phase relation with Mg but the heavy RE(Gd-Lu, Sc) have the similar crystal structure with magnesium. Also it is found that the less electronegativity difference between Mg and RE is, the more solubility limit of RE in Mg is. The fact of the RE solubility decreased in magnesium with lowering temperature suggests that there is a possibility of Mg supersaturated solid solution formation and it will decomposition during aging. According to the rule, an megnesium alloy with higher strength feature was developed. Their mechanical properties are UTS 347MPa, YTS 290MPa and elongation 12.5% at room temperature.

Separation of yttrium from heavy lanthanide by CA-100 using the complexing agent

The selective extraction of yttrium front heavy lanthanide by liquid-liquid extraction using CA-100 in the presence of the complexing agent, such as EDTA, DTPA, and HEDTA was investigated. The extraction of heavy lanthanide in the present of the complexing agent was Suppressed when compared to that of Y because of the masking effect, but the selective extraction of Y was enhanced. All complexing agents formed 1: 1 complex with rare earth elements (RE), and only free rare earth ions could take part in the extraction. The condition for separation was obtained by exploring the effects of the complexing agent concentration, the extractant concentration, pH and the equilibration time on the extraction of the heavy rare earth elements.

Study on mechanism of interaction between Eu3+ and microperoxidase-11

The interaction mechanism between Eu3+ and microperoxidase-II (MP-11) in the aqueous solution was investigated using the UV-vis absorption spectroscopy, cyclic voltammetry and electrospray ionization mass spectrometry. It was found that one Eu3+ ion can coordinate with two carboxyl oxygen of two propionic acid groups of the heme group in the MP-11 molecule, leading the increase in the nonplanarity of the porphyrin ring and exposure degree of Fe(III) in the heme group. Therefore, the reversibility of the electrochemical reaction and the electrocatalytic activity of MP-11 for the reduction of oxygen are increased.

Selective separation of yttrium by CA-100 in the presence of a complexing agent

The selective separation of Y from yttrium solution containing small heavy rare earth (HRE) impurities (Ho, Er, Tm, Yb, Lu) by liquid-liquid extraction using CA-100 in the presence of a water-soluble complexing agent of ethylenediaminetetraacetic acid (EDTA) was experimentally studied at 298K. Experiments were carried Out in two feeds, Feed-I: [RE](f) = 4.94 x 10(-3) M, Y = 98.5%, HRE (Ho, Er, Tm, Yb, Lu) = 1.5%; Feed-II: [RE](f) = 4.94 x 10(-3) M, Y = 99.9%, HRE (Ho, Er, Tm, Yb, Lu) = 0.1%, as a function of equilibrium pH (pH(eq)), the concentration ratio of [EDTA]:[HRE impurities]. It was shown that the extraction of HRE in the presence of EDTA was suppressed when compared to that of Y because of the masking effect, while the selective extraction of Y was enhanced and the separation factors increased to maximum at appropriate condition for Feed-I: Y/Ho = 1.53, Y/Er = 3.09, Y/Tm = 5.61, Y/Yb = 12.04, Y/Lu = 27.51 at pH 4.37 and [EDTA]:[HRE impurities] = 4: 1, for Feed-II: Y/Ho = 1.32, Y/Er = 1.91, Y/Tm = 2.00, Y/Yb = 3.05, Y/Lu = 3.33 at pH 4.42 and [EDTA]: [HRE impurities] = 8:1. The separation and purification of Y by this method was discussed.

Kinetics of Y(III) stripping for the system Y/HCl/Cyanex 272-P507/heptane with constant interfacial area cell with laminar flow

Kinetics and mechanism of stripping of yttrium(III) previously extracted by mixtures of bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272, HA), and 2-ethylhexyl phosphonic acid mono-2-ethylhexl ester (P507, HB) dissolved in heptane have been investigated by constant interfacial-area cell by laminar flow. The corresponding equilibrium stripping equation and equilibrium constant were obtained. The studies of effects of the stirring rate and temperature on the stripping rate show that the stripping regime is dependent on the stripping conditions. The plot of interfacial area on the rate has shown a linear relationship. This fact together with the strong surface activity of mixtures of Cyanex 272 and P507 at heptane-water interfaces makes the interface the most probable locale for the chemical reactions. The stripping rate constant is obtained, and the value is compared with that of the system with Cyanex 272 and P507 alone. It is concluded that the stripping ability with the mixtures is easier than that of P507 due to lower the activation energy of the mixtures. The stripping rate equation has also been obtained, and the rate-determining steps are the two-step interfacial chemical reactions as predicted from interfacial reaction models.