Specific Adsorption of Trace Amounts of Calcium and Strontium by Hydrous Oxides of Iron and Aluminum1

Freshly prepared Fe and Al hydrous oxide gels and the amorphous product of heating gibbsite selectively adsorbed traces of Ca and Sr from solutions containing a large excess (∼1M) of NaNO3. The fraction of the added Ca (Sr) adsorbed depended principally on the suspension pH, the amount of solid present, and to a lesser extent on the NaNO3 concentration. Significant Ca and Sr adsorption occurred on the Fe and Al gels, and heated gibbsite, at pH values below the points of zero charge (8.1, 9.4, and 8.3±0.1, respectively), indicating specific adsorption. The pH (± 0.10) at which 50% of the Ca was adsorbed (pH50) occurred at pH 7.15 for the Fe gel (0.093M Fe), 8.35 for the Al gel (0.093M Al), and 6.70 for the heated gibbsite (0.181M Al); for Sr, the pH50 values were 7.10, 9.00, and 6.45, respectively. For the Fe gel and heated gibbsite, an empirical model based on the law of mass action described the pH dependence of adsorption reasonably well and suggested that for each Ca or Sr fraction adsorbed, approximately one proton was released. Failure of the Al gel to fit this model may have resulted from its rapid aging.

Synthesis and characterization of white-light-emitting polyfluorenes containing orange phosphorescent moieties in the side chain

Two orange phosphorescent iridium complex monomers, 9-hexyl-9-(iridium (III)bis(2-(4'-fluorophenyl)-4-phenylquinoline-N, C-2')(tetradecanedionate-11,13))-2,7-dibromofluorene (Br-PIr) and 9-hexyl-9-(iridium(III)bis(2-(4'-fluorophenyl)-4-methylquinoline-N, C-2')(tetradecanedionate-11,13))-2,7-dibromofluorene (Br-MIr), were successfully synthesized. The Suzuki polycondensation of 2,7-bis(trimethylene boronate)-9,9-dioctylfluorene with 2,7-dibromo-9,9-dioetylfluorene and Br-Plr or Br-MIr afforded two series of copolymers, PIrPFs and MIrPFs, in good yields, in which the concentrations of the phosphorescent moieties were kept small (0.5-3 mol % feed ratio) to realize incomplete energy transfer. The photoluminescence (PL) of the copolymers showed blue- and orange-emission peaks. A white-light-emitting diode with a configuration of indium tin oxide/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/PIr05PF (0.5 mol % feed ratio of Br-PIr)/Ca/Al exhibited a luminous efficiency of 4.49 cd/A and a power efficiency of 2.35 lm/W at 6.0 V with Commission Internationale de L'Eclairage (CIE) coordinates of (0.46, 0.33). The CIE coordinates were improved to (0.34, 0.33) when copolymer MIr10PF (1.0 mol % feed ratio of Br-MIr) was employed as the white-emissive layer. The strong orange emission in the electroluminescence spectra in comparison with PL for these kinds of polymers was attributed to the additional contribution of charge trapping in the phosphorescent dopants.

Morphology of high impact polypropylene particles

Morphological features of isotactic polypropylene (iPP) and high impact polypropylene (hiPP) particles produced in a multistage polymerization process were investigated by field-emission electron microscopy (FESEM) and transmission electron microscopy (TEM) techniques. Study was mainly focused on architecture of iPP particle and distribution of elastomer phase (EPR) within the preformed iPP matrix. The iPP particle is an agglomerate of many subglobules (ca. several to hundred microns in diameter), while the subglobule in turn is formed by a great deal of primary globules (ca. 100 nm in diameter). Large macropores between the subglobules and finely distributed micropores within the subglobule constitute a network of pore inside the iPP particle. Ethylene/propylene comonomers can diffuse into the macro- and micropores and copolymerize on catalyst active sites located on periphery of the pores, forming elastomer phase inside.

Species of rare earth(III) and calcium(II) in the presence of L-aspartic acid and L-arginine

Rare earth (III)-Asp-Arg and Ca(II)-Asp-Arg systems were studied by potentiometric titration under physiological conditon. The species of each system were determined. The distribution of Tb (III) and Ca(II) species was discussed, as well as in the quaternary system of Tb(III)-Ca(II)-Asp-Arg.

Application of the Sanchez-Lacombe lattice fluid theory to the system pvme/ps and model calculations

Cloud point curves reported in the literature for five representatives of the system poly(vinyl methyl ether)/polystyrene were evaluated theoretically by means of the Sanchez-Lacombe lattice fluid theory. The measured phase separation behavior can be described within experimental error using only one adjustable parameter (quantifying the interaction between the unlike mers). The Flory-Huggins interaction parameters calculated from this theoretical description depend in good approximation linearly on composition (volume fractions) and on the inverse temperature. An evaluation of these data yields a maximum heat effect which is almost one order of magnitude less (ca. -0.25 J/cm(3)) than obtained via Hess's cycle (dissolution of the components and of the blend) from calorimetric measurements. Model calculations on the basis of the present theory demonstrate that the critical points shift to a different extent upon a certain relative change in the molar mass of the blend components. The sensitivity of the calculated phase diagrams against changes in the scaling parameter decreases in the following order: interaction energies between unlike mers, differences in the scaling temperatures, pressures and densities.

Studies on water-swellable elastomer .1. Synthesis and characterization of amphiphilic polymer

A new amphiphilic polymer i.e., polyethylene glycol (PEG) grafted crystalline neoprene, which was used as compatibilizer to improve the compatibility of elastomer and water-absorbent resin, has been investigated. The synthesis was based on the reaction between chlorine in neoprene and sodium salts of PEG. PEGs with molecular weights of 600 and 2000 were used. The grafting percent and the PEG content were calculated through elemental analysis of chlorine in the resulted copolymers. The maximum grafting percent of copolymers was ca. 24.80%. The molecular parameters such as number-average molecular weight and the average number of grafting chains on one CR backbone were also calculated and discussed. (C) 1996 John Wiley & Sons, Inc.

Photosynthetic bicarbonate utilization in Porphyra haitanensis (Bangiales, Rhodophyta)

The activities of carbonic anhydrase (CA) and photosynthesis of Porphyra haitanensis were investigated in order to see its photosynthetic utilization of inorganic carbon source. Both intra- and extra-cellular CA activities existed in the thallus. CA inhibitors, acetazolamide (AZ) and ethoxyzolamide (EZ), remarkably depressed the photosynthetic oxygen evolution in seawater of pH 8.2 and 10.0, and EZ showed stronger inhibition than AZ. The observed net photosynthetic rate In seawater of pH 8.2 was much higher than that of CO2 supply theoretically derived from spontaneous dehydration of HCO3-. P. haitanensis also showed a rather high pH compensation point (9.9). The results demonstrated that P. haitanensis could utilize bicarbonate as the external inorganic carbon source for photosynthesis. The bicarbonate utilization was closely associated with HCO3- dehydration catalyzed by extracellular CA activity. The inorganic carbon composition in seawater could well saturate the photosynthesis of P. haitanensis. The low K-m value and compensation points for inorganic carbon reflected the existence of CO2-concentrating mechanism in this alga.

PLANKTON AND SESTON STRUCTURE IN A SHALLOW, EUTROPHIC SUBTROPICAL CHINESE LAKE

The seasonal dynamics in the nutrient concentrations, chlorophyll-a amount (Chl-a), total algal volume (CV), Chl-a/CV ratio, seston structure were studied at two sampling stations in a shallow, highly eutrophicated subtropic lake (the Guozheng Hu area of the East Lake) on the plain of the middle basin of the Chang Jiang (the Yangtze River) of China. The lake ecosystem of the Guozheng Hu area is dominated by two planktivorous fishes (silver carp and bighead carp), phytoplankton and zooplankton. Macrophytes are extremely scarce in this area. Concentrations of the total dissolved nitrogen and phosphorus in the Guozheng Hu area in 1990 were very high. Fish yield, of which, more than 90 % was composed of silver carp and bighead carp in the Guozheng Hu area was very high (ca. 1140 kg/ha or 45.6 g/m3 in 1990). Grazing pressure by the fishes on the plankton community is considered to be rather strong. The annual average biomass of zooplankton was ca. 1/3 - 1/2 that of phytoplankton. On the average, dry matter in the living plankton only constituted ca. 3-7 % of the total dry seston, and plankton carbon only constituted ca. 5 - 10 % of the seston carbon. The present results indicate that, in the Guozheng Hu area of the East Lake, of the organic part of the seston, detritus is quantitatively an important constituent, while living plankton is only a very small component.

川西地区几种优势苔藓植株元素含量及其时空差异性

揭示苔藓植株元素含量及其时空差异性是深入开展利用苔藓植物指示环境和筛选理想监测藓种的科学基础。采用微波消解（ICP-AES）方法对九寨沟自然遗产地原始林景点停车场周围三个采样带：I为停车场植被小岛（PS），向外约120 m半径为II带（D120），再向外距离约1,000 m为III带（D1000）和3个方向上的大羽藓和毛尖青藓2种苔藓中13种元素（A1, S, Ca, P, Cu, Fe, K, Mg, Mn, Pb, Ni,Zn和Cd）含量进行了测定和比较，并对采自边坡方向（PS-3）上2005和2007年的4种苔藓植物（南木藓、大羽藓、平藓和厚角絹藓）也进行了13种元素含量的测定和比较。同时对九寨沟自然遗产地、黄龙自然遗产地、夹金山和梦笔山的冷杉原始林4个地区的3种苔藓中（大羽藓、锦丝藓和塔藓）的A1、Ca���Cu、Fe、K、Mg、P、Zn、C和N 10种元素含量进行测定和比较。 对大羽藓和毛尖青藓2种苔藓植物内13种元素的测定发现：1）同种苔藓对不同元素的富集能力不同。A1、Ca���K、Mg和P的元素含量在苔藓中的富集较其他元素的要高。2）不同种苔藓植物对同种元素的富集能力不同，毛尖青藓较大羽藓能够监测出更多的元素；对于被检测出的元素，毛尖青藓监测出的累积量大于大羽藓，其中累积量最大的元素是Ca���10 874.286 μg.g-1.year-1，最小的是Cu元素为5.438 μg.g-1.year-1。对05年和07年的平藓、大羽藓、南木藓和厚角絹藓元素含量的测定表明：元素在两年中的积累量是不同的。综合分析表明，苔藓生物监测方法可有效监测景点停车场机动车尾气中排放出的典型元素（如Cu、Pb、Ni、Zn、Cd等）含量，而毛尖青藓较大羽藓能更可靠的监测九寨沟自然遗产地单景点汽车尾气金属元素种类及其排放量。 对4个地区3种苔藓10种元素监测发现：1）Ca���Mg、Zn、K和Cu元素在黄龙地区的含量高于在其它地区的含量；P元素在梦笔山地区的含量为最高；Fe和Al元素在夹金山地区的含量高于在其它地区的含量。2）C元素在其它因素一致的情况下，进行不同年龄间的元素含量比较，结果显示元素含量在各年龄间并不存在明显的差异性；N元素含量与年龄的差异出现在黄龙林下及林窗的塔藓、九寨沟林下的锦丝藓及塔藓和梦笔山的塔藓中，而在锦丝藓中未出现元素含量与年龄的差异性；塔藓能检测出更多的元素种类其含量与年龄间存在显著差异，锦丝藓检测到的元素种类次之；除锦丝藓（锦丝藓在林窗中几乎检测不到元素含量与年龄间的差异性）外，其他两种藓在林窗中能检测出的元素种类大于在林下的检测种类。3）元素含量与生境间存在差异性的元素分别有：黄龙大羽藓中的Ca���P和Mg元素；九寨锦丝藓中的Zn元素；夹金山塔藓中的Al、Fe和Zn元素；梦笔山大羽藓中的Al、Fe和Mg元素及锦丝藓中的Ca���素。4）区域、年龄和生境因素对苔藓植株元素含量均达到了显著水平，但两两之间及三者之间的交互作用由于元素种类的不同存在差异。综合分析表明，苔藓植物中的元素含量受年龄、区域的影响较生境的更大。 The revelation of mosses elements content and its spatiotemporal differences is the scientific foundation of moss monitoring. To determine the feasibility of moss monitoring metal depositions derived from travel bus emiss ions in scenic spot, we collected one year-growth samples of two mosses Brachythecim piligerum and Thuidium cymbifolium with different distance (island center, 120m，1000m ) and different direction (north, south and east) far from parking site island from Yuanshilin Spot at Jiuzhaigou World Nature Heritage in the Western Sichuan of China and determined thirteen element （A1, S, Ca, P, Cu, Fe, K, Mg, Mn, Pb, Ni, Zn, Cd）contents by ICP-AES analysis method. And picked 4 kinds of mosses (Macrothamnium macrocarpu m（Reinw. etHornsch.）Fleisch.，Thuidium cymbifolium，Entodon concinnus (De Not.) Par., Neckera pennata) from the direction PS-3 in 2005 and 2007, determined 13 element contents. Collected 3 kinds of moss (Thuidium cymbifo lium, Actinothuidium Hookeri (Mitt.) and Hyolcomium splendens (Hedw.) from Jiuzhaigou natural heritage, Huanglong natural heritage, Mt. Jiajin and Mt. Mengbi in primeval forest with two habitat (undergrowth and forest gap), determined element contents of A1, Ca, Cu, Fe, K, Mg, P, Zn, C and N. We found that, 1) The elements content are difference in same type of moss. Content of A1, Ca, K, Mg and P are higher than others. 2) While the contents of A1, S, Ca, P, Cu, Fe, K and Zn had significant correlation with the different distances from parking site, the nearer the distance was, the more accumulation was; 2) Comparing to Thuidium cymbifolium, Brachythecium piligerum can test more elements which contents show the significant correlation with distances. And Brachythecium piligerum can have greater element accumulation than Thuidium cymbifolium. The element contents in two years (2005 and 2007) are different. The present study found that moss can reliably bio-indicate metal deposition from traffic emissions in one scenic spot and Brachythecium piligerum is a good moss for bio-indicating element content from traffic emissions at Jiuzhaigou World natural Heritage. Determined the 10 element contents in 4 areas through 3 kinds of moss we found that, 1) Ca, Mg, Zn, K and Cu element content is higher in the Huanglong area than in other areas, The P element content in Mt. Jiajin is higher than other areas, Fe and Al element content is higher in the Mt. Jiajin than in other areas. 2) The content of C had no significant correlation with age. As for N, this significant correlation found in Hyolcomium splendens (Hedw.) with 2 habitat in Huanglong, Actinothuidium Hookeri (Mitt.) and Hyolcomium splendens (Hedw.) with undergrowth in Jiuzhai, Hyolcomium splendens (Hedw.) in Mt. Mengbi. The types of elements which content showt he significant correlation are most in Hyolcomium splendens (Hedw.) and least in Thuidium cymbifolium. Except Actinothuidium Hookeri (Mitt.), the types of elements that content had significant correlation with age in forest gap are more than in undergrowth. 3) The elements which content had significant correlation with habitat are P, Ca and Mg in Thuidium cymbifolium in Huanglong, Zn in Actinothuidium Hookeri (Mitt.) in Jiuzhai, Al, Fe and Zn in Hyolcomium splendens (Hedw.) in Mt. Jiajin, in Mt. Mengbi Al, Fe and Mg in Thuidium cymbifolium and Ca in Actinothuidium Hookeri (Mitt.). 4）The region, the age and the habitat factor has coeffect element content. The correlationship between element contents and the age, the region is closer than habitat.

Preparation and characterization of poly(piperazineamide) composite nanofiltration membrane by interfacial polymerization of 3,3 ',5,5 '-biphenyl tetraacyl chloride and piperazine

Most nanofiltration (NF) membranes are composite and have a polyamide thin film prepared by interfacial polymerization. Their performances mainly correlate the structure of the thin film and monomers used for its preparation. In this work, a novel thin-film composite (TFC) nanofiltration membrane was successfully prepared from 3,3',5,5'-biphenyl tetraacyl chloride (mm-BTEC) and piperazine (PIP) through interfacial polymerization. Attenuated reflectance infrared (ATR-IR) and X-ray photoelectronic spectroscopy (XPS) were used to characterize the chemical composition of the membrane surface. The membrane performance was optimized by studying preparation parameters including monomer concentration, reaction time, and pH of aqueous phase.

DETERMINATION OF THE RATE-CONSTANT OF A CATALYTIC REACTION USING A PARALLEL INCIDENT SPECTROELECTROCHEMICAL CELL

The possibility of determining the rate constant of a catalytic reaction using a parallel incident spectroelectrochemical cell was investigated in this work. Various spectroelectrochemical techniques were examined, including single-potential-step chronoabsorptometry, single-potential-step open-circuit relaxation chronoabsorptometry and double-potential-step chronoabsorptometry. The values determined for the kinetics of the ferrocyanide-ascorbic acid system are in agreement with the reported values. The parallel incident method is much more sensitive than the normal transmission method and can be applied to systems which have smaller molar absorptivities, larger rate constants or lower concentrations.

地幔压力下CaSiO3 Perovskite状态方程和弹性常数的第一性原理研究

In the past decade density functional theory (DFT) has made its way from a peripheral position in quantum chemistry to center. Of course the often excellent accuracy of the DFT based methods has provided the primary driving force of this development. This dissertation is devoted to the study of physical and chemical properties of planetary materials by first-principle calculation. The concerned properties include the geometry, elastic constants and anisotropy. In the first chapter, we give a systematic introduction to theoretical background and review its progress. Development of quantum chemistry promotes the establishment of DFT. Theorem of Hohenberg-Kohn is the fundament of DFT and is developed to Kohn-Sham equation, which can be used to perform real calculations. Now, new corrections and extensions, together with developed exchange-correlation, have made DFT more accurate and suitable for larger systems. In the second chapter, we focus on the calculational methods and technical aspects of DFT. Although it is important to develop methods and program, external package are still often used. At the end of this chapter, we briefly some widely used simulation package and the application of DFT. In the third chapter, we begin to focus on properties of real materials by first principles calculation. We study a kind of minerals named Ca perovskite, investigate its possible structure and anisotropy at Earth’s mental condition. By understanding and predicting geo-physically important materials properties at extreme conditions, we can get the most accurate information to interpret seismic data in the context of likely geophysical processes.

水热条件下钾长石碱性分解反应机理的实验研究

It is well known that our country is short of water-soluble potassium, but rich in insoluble potassium ores. Based on the work of the formers, using the orthogonal and monofactor experiments, the author optimized the production technology of micro-porous potassium silicon calcium mineral fertilizer by non-stirring hydrothermal chemical reaction when the alkaline earth booster CaO was available. The influences of temperature、time、reactant ratio and water-solid ratio on the dissolution rate of production’s elements were studied by orthogonal experiments, and the production technology was further optimized by monofactor experiments. By XRD、SEM、EDS and dissolving experiments, it was systematically studied that the effects of the reactant ratio、reaction time and reaction temperature on the properties of the production obtained by the hydrothermal reaction between KAlSi3O8 and CaO. The results showed that：when changing of the reaction condition, the reaction productions included tobermorite、 hibschite、α-C2SH and K2Ca(CO3)2; among which, K2Ca(CO3)2 was not the first production containing potassium, but K2Ca(CO3)2 was synthesized by the reaction among KOH、Ca(OH)2 and CO2. Whether the phase was synthesized was related to not only the reaction condition, but also their physicochemical properties; when the reaction condition was changed, the changes of different phases were different. The results of XRD and dissolution rate experiments explained the dissolution characteristic of every element of hydrothermal productions very well, and the relation between the dissolution rate of element and the phase of productions poured a good illumination on the production technology. The results of SEM and EDS showed that: hydrogarnet looked like spherical, and its surface was covered by some productions including K phase and Ca���Si phase; but the morphology of tobermorite was platy or lamellar or needlelike, and parts of Si in the structure of tobermorite were substituted by Al，and some K+ cations were inserted into the Ca interlayer of tobermorite at the same time. It was the first time that the interface between KAlSi3O8 and Ca(OH)2 was observed directly by SEM and EDS after the hydrothermal reaction, and the mechanism of hydrothermal reaction of KAlSi3O8 and Ca(OH)2 was further discussed. These results indicated that: the Ca-KAlSi3O8 intermediate compound was formed at first, and some K was released into the solution and KOH was produced at the same time; the C-S-H phase appeared before hydrogarnet, and then hydrogarnet was synthesized when the chemical reaction was carried on; if the reaction was carried on furthermore, α-C2SH、tobermorite and other C-S-H phases of different atom ratio appeared. The author found that the structure of KAlSi3O8 would be more drastically destroyed if there were some reactants, such as Ca(OH)2 which reacted with KAlSi3O8 and new phases were formed after the hydrothermal reaction between KAlSi3O8 and alkaline solution of equal ionic strength was finished. With the combination of calcination and hydrothermal reaction methods, the dissolution rate of products were greatly improved when the hydrothermal reaction was carried out after KAlSi3O8 and CaCO3 were calcined. Furthermore, the author has tentatively explored how to evaluate the effects of the differences of the activity of lime on the dissolution properties of hydrothermal products.

黄土中可溶盐含量及意义

The concentrations of K~+,Na~+,Ca~(2+),Mg~(2+),F~-,Cl~-,NO_3~-,SO_4~(2-) and HCO_3~- in Lantian, Binxian, Ningxian, Qingyang, Mubo and Jiyuan loess sections by last interglacial on China Loess Plateau and its conductance are determinated. The results are: According to the average ions concentration in different sections, the soluble salts in south sections are mainly transported from land dusts which fall with rain, but the most salts in north sections are released from minerals by soil formation. The spatial changes of dominating soluble salts ,gypsum in south sections and Glauber'salt and fluorite in north sections, indicates the different arid degrees on Loess Plateau. The north sections are more arid than south, so that the diffluent ions become the main component in soluble salts. The salts enriched in Stage2 and 4, the arid and cold paleoclimate period, in south loess sections because that the soluble ions were swept by water, although they sedimented in warm period. On north Loess Plateau, as evaporation became the determinative factor on salts sediment, the soluble matter enriched in Stage 1,3 and 5, the warm and humid paleoclimate period. According to the conductance of different oxygen isotope period in loess sections, on Stage 1 and 5, the salts enrichment were charged by temperature and participate at the same time, so its concentrations are high on central Loess Plateau; on Stage2,3 and 4, the salts concentrations in south sections are higher than north because their weak movement. The diffluent ions are not sensitive to climate changes on China Loess Plateau, but Ca~(2+), Mg~(2+), NO_3~-SO_4~(2-) are sensitive.