Synthesis and properties of novel regioirregular polyimides from easily synthesized asymmetrical dichlorophthalimide monomers

New asymmetrical aromatic dichlorophthalimide monomers containing pendant groups (trifluoromethyl or methyl) were conveniently prepared from inexpensive and commercially available compounds. With these monomers, a new class of soluble polyimides with a regioirregular structure within the polymer backbone was obtained by the Ni(0)-catalyzed polymerization method. The structures of the polymers were confirmed by various spectroscopic techniques. The polyimides displayed better solubility and higher thermal stability than the corresponding regular polyimides. In addition, fluorinated polyimides in this study had low dielectric constants ranging from 2.52 to 2.78, low moisture absorptions of less than 0.59%, and low thermal expansion coefficients between 10.6 and 19.7 ppm/degrees C. The oxygen permeability coefficients and permeability selectivity of oxygen to nitrogen of the films were in the ranges of 2.99-4.20 barrer and 5.55-7.50, respectively. We have demonstrated that the synthetic pathway for polyimides provides a successful approach to increasing the solubility and processability of polyimides without sacrificing their thermal stability.

Temperature and pressure dependence of phase separation of trans-decahydronaphthalene/polystyrene solution

The cloud-point temperatures (T-c1's) of ti-ans-decahydronaphthalene (TD)/polystyrene (PS, M-w = 270 kg/mol) solutions were determined by fight scattering measurements over a range of temperatures (1-16 degreesC), pressures (100-900 bar), and compositions (4.2-21.6 vol% polymer). The system phase separates upon cooling and the T-c1 was found to increase with the rising pressure for the constant composition. In the absence of special effects this finding indicates positive excess volumes. The special attention was paid to the demixing temperatures as a function of the pressure for the different polymer solutions and the plots in the T-volume fraction plane and P-volume fraction plane. The cloud-point curves of polymer solutions under changing pressures were observed for different compositions, demonstrates that the TD/PS system exhibits UCST (phase separation upon cooling) behavior. With this data the phase diagrams under pressure were calculated applying the Sanchez-Lacombe (SL) lattice fluid theory. Furthermore, the cause of phase separation, i.e., the influence of Flory-Huggins (FH) interaction parameter under pressure was investigated.

Simultaneous determination of 2-aminothiazole, 2-aminobenzothiazole and 2-mercaptobenzothiazole by capillary electrophoresis with end-column amperometric detection

Capillary electrophoresis with amperometric detection is evaluated for the simultaneous determination of 2-aminothiazole (A), 2-amino-benzothiazole (AB), 2-mercaptobenzothiazole (AM). The cyclic voltammogram, hydrodynamic voltammogram, effect of pH, concentration of buffer and separation voltage on the separation and the detection were studied. The conditions were optimized as follows: 50 mM phosphate buffet; pH 6.0, 2s at 17.5 kV sample injection, separation at 17.5 kV, 1.2 V as detection potential. The method provided low detection limit as 0.5 mu M, 0.05 mu M and 0.01 mu M, wide linear range 2-200 mu M, 10-200 mu M and 0.025-100 mu M for A, AB, and AM, respectively. The variations in peak current and migration time for 15 consecutive injections of a standard containing 5 mu M each compound were 3.7, 2.1, and 3.9%, and 1.2, 0.8, and 1.2%, for A, AB and AM, respectively. This method was employed to analyze river water.

Effects of heteropoly acids and surfactant on electrochemiluminescence of tris(2,2 '-bipyridine) ruthenium(II)

The effects of heteropoly acids and Triton X-100 on electrochemiluminescence (ECL) of Ru(bpy)(3)(2+) are investigated. Triton X-100 prevents the oxidation of oxalate and results in an increase of the ECL signal. H5SiW11VO40 prevents the direct oxidation of oxalate and makes the electrochemical behavior of Ru(bpy)(3)(2+) less reversible, which leads to a decrease of the ECL signal. In contrast, H3PMo12O40 has negligible effect on ECL intensity. Some possible reasons for the effects on the ECL of Ru(bpy)(3)(2+) are discussed based on the adsorption of SiW11VO405- on electrode surface and the ion association between SiW11VO405- and Ru(bpy)(3)(2+). The signal of ECL decreases linearly with the concentration of heteropoly acid in the range from 2x10-6 to 1x10(-4) mol l(-1). The results indicate that ECL of RU(bpy)(3)(2+) is a potential sensitive and selective detection method for heteropoly acids and hence for the elements comprised in them.

Structure, electric and magnetic properties of new compounds CdYMWO7 (M = Cr and Mn)

Two new compounds with the formula of CdYMWO7 (M = Cr, Mn) were prepared by solid state reaction. They crystallized with orthorhombic structure with the cell parameters of a = 11.7200 Angstrom, b = 7.1779 Angstrom, c = 6.9805 Angstrom (CdYCrWO7), and a = 11.7960 Angstrom, b = 6.1737 Angstrom, c = 7.6530 Angstrom (CdYMnWO7). These compounds are insulators with high resistivities at room temperature. The temperature dependence of the magnetic susceptibility of CdYMWO7 (M = Cr and Mn) show Curie-Weiss Law's behaviors from 80 to 300 K. The magnetic moments at room temperature fit very well with those corresponding to Cr3+ and Mn3+ ions. This suggests that both Cr and Mn ions exist in + 3 oxidation state in CdYMWO7 compounds. (C) 1998 Elsevier Science Ltd. All rights reserved.

Oxygen permeating properties of the mixed conducting membranes without cobalt

A new series of mixed conducting oxides, Sr10-n/2BinFe20Om (n = 4, 6, 8, 10), were synthesized by a solid state reaction method, and they have high oxygen permeability. The oxygen permeation rate at 1150 K is 0.41 ml(STD)/ cm(2).min for n = 6 and 0.90 ml(STD)/cm(2).min for n = 10, which is two times higher than that for Sr1-xBixFeO3 (x = 0.5). For the Sr1-xBixFeO3 (x = 0.1, 0.3, 0.5) series, the oxygen flux increases with increasing Bi content. (C) 1998 Elsevier Science Ltd.

Induction of triploidy in large yellow crocker Pseudosciaena crocea (Richardson, 1846): effects of pressure shocks and growth performance in the first rearing year

The precociously sexual maturation in large yellow crocker Pseudosciaena crocea has become a serious problem. In an attempt to solve this problem, the production of sterile triploids could be an effective strategy. In this study, triploid P. crocea was obtained by subjecting fertilized eggs to pressure shock. Flow-cytometry analysis was used to assess ploidy level. In terms of triploid rate and hatching rate, the optimal conditions of pressure shock for triploidy induction in P. crocea were 7500 psi for 3 min shock at 3 min after fertilization at 20 degrees C. With the application of these parameters, 100% triploid fish were produced. During the first rearing year, triploid P. crocea had a similar growth performance compared with its diploid counterpart before the age of 8 months and showed a significant advantage at the age of 10 and 12 months in body weight and body length (P < 0.05). At the age of 12 months, the carcass weight of triploids was markedly higher than that of diploid control, and gonadal somatic index was significantly lower than that of their diploid control. During the first rearing year, survival in triploid group was 76.44%, inferior to its diploid control (83.21%).

An acidic polysaccharide with xylose branches from Porphyra yezoensis

An acidic polysaccharide (PY3) was isolated from the hot water extract of the red algae Porphyra yezoensis by successive column chromatographies over DEAE-cellulose and Sephadex G-200. PY3 with an average molecular weight of 1.8x10(5) was demonstrated to be composed of galactose (Gal), 3,6-anhydrogalactose (3,6-AnGal), 6-OSO3-galactose (6-OSO3-Gal) and xylose (Xyl) in an approximate molar ratio of 25 : 15, 10, 1. In view of Smith degradation and methylation and on the basis of spectral evidence including those of IR, GC, GC-MS, and H-1 and C-13 NMR, the most probable repeating unit of PY3 could be proposed as [(1-->3)beta -D-Gal(1 --> 4)alpha -L-3,6-AnGal](3)-[(1 --> 3)beta -D-Gal(1 --> 4)alpha -L-6-OSO3-Gal](2) with a xylose moiety at the C-6 of one of every twenty-five beta -D-Gal residues. To our knowledge, PY3 was shown to be the first porphyran possessing occasional xylose branches.

栉孔扇贝C型凝集素-2(CfLec-2)基因的克隆和分析

栉孔扇贝是我国北方一种重要的贝类养殖品种。自1997年以来爆发的栉孔扇贝大规模死亡，给地区经济造成了重大损失并且已经严重威胁着扇贝养殖业的健康发展。然而，到目前为止，对扇贝免疫防御分子机理的了解还很少，深入研究扇贝免疫应答的分子机制是认识和了解病害发生和实现病害控制的重要途径。本研究采用了EST大规模测序和3’RACE的方法，从栉孔扇贝cDNA文库中克隆到一个凝集素基因CfLec-2，并对功能进行了研究。 CfLec-2 cDNA全长708bp，5’非翻译区(Untranslated Region, UTR)含有59bp，3’非翻译区含有163bp，具有典型的多聚腺苷酸加尾信号序列AATAAA和多聚腺苷酸尾巴，开放阅读框(Open Reading Frame, ORF )含有486bp，编码162个氨基酸残基，该多肽的理论分子量为16.8 kDa，等电点为4.54。利用SignalP分析，发现其信号肽的剪切位置在VEA-QSL之间。经BLASTP比对分析可知，CfLec-2基因编码的蛋白与人的Brevican，Anguilla japonica的C-type lectin-1和C-type lectin-2， Rattus norvegicus的CD23有较高的相似性，其中与Brevican的一致性有37%。Clustal W多序列比对发现该多肽具有标准长型C型凝集素所必须的6个保守半胱氨酸和相对保守的糖识别位点。用SMART(Small Modular Architecture Research Tool)软件分析发现其具有一个保守的糖识别结构域(Carbohydrate-recognition Domain, CRD)，氨基酸序列上第49、125、141、149位置上的半胱氨酸参与形成糖识别结构域，而位于N末端的第21和32位上的两个半胱胺酸形成额外的一个二硫键，位于115、116和117上的Glu、Pro、Asp则构成了糖识别位点。 将编码CfLec-2成熟肽段的cDNA序列克隆进pET32a(+)载体中，并在大肠杆菌Rosetta-gami(DE3)中重组表达CfLec-2。重组蛋白利用其具有的His tag纯化并复性后发现CfLec-2可以凝集溶血葡萄球菌，且凝集过程不需要钙离子的参与。并且，CfLec-2对大肠杆菌TOP10F’有微弱的抑菌活性，对溶壁微球菌、溶血葡萄球菌和鳗弧菌则没有抑菌活性。这一结果说明，CfLec-2可能不仅参与对入侵微生物的识别过程，而且可能作为效应分子起到了直接杀灭入侵微生物的作用。 本研究发现CfLec-2具有和以前在栉孔扇贝报道的CFLec-1完全不同的功 能，说明栉孔扇贝利用不同的凝集素来识别不同的病原，同时也暗示栉孔扇贝中可能有更多不同功能的凝集素有待发现。研究结果丰富和发展了海水无脊椎动物免疫学的内容，对进一步了解扇贝固有免疫的机制，实现养殖扇贝疾病防治具有重要参考价值。

黄海纤毛虫的丰度和生物量

海洋浮游纤毛虫是在海洋中浮游生活的一类单细胞原生动物，主要是指寡毛类纤毛虫(Oligotrich ciliates)，隶属原生动物界(Protozoa)、纤毛门(Ciliophora)、寡毛纲(Oligotrichea)，分属于Oligotrichina 和Tintinnina两个亚纲。它们个体微小，粒径在5-200 µm之间，是微型浮游动物和海洋微食物环(Marine Microbial Food Web)的重要组成部分。 2006年4月至2007年12月，在黄海(包括胶州湾)采样分析海洋浮游纤毛虫的种类组成(砂壳纤毛虫)、丰度和生物量，分析纤毛虫在这一海区的季节变化和空间变化。 纤毛虫丰度和生物量的研究方法为：Rosette采水器(胶州湾用Niskin采水器)采集水样，取1 L水样，加Lugol’s试剂固定(终浓度1%)，Utermöhl方法100倍镜检。测量虫体的体长、体宽，按最接近的几何形状(圆柱体、球体和圆锥体)计算体积。生物量由体积乘转换系数(0.19 pgC/µm3)得到，砂壳纤毛虫的肉体体积按照壳体积的1/3近似。 本文的结果表明，胶州湾各站纤毛虫平均丰度于6月达到全年最高值6065 ind./L，12月为全年丰度最低值843 ind./L。平均生物量8月达全年最高值(18.5 µg C/L)，6月为全年最低值(0.6 µg C/L)。砂壳纤毛虫种丰富度于8月达到最高值，共发现25种砂壳纤毛虫，1月种类最少(6种)。湾内站位的纤毛虫平均丰度比湾外的高(6月和8月除外)。砂壳纤毛虫在纤毛虫总丰度中的比例较小，平均为25%，范围为8-57%，分别于1月和8月达到最低和最高值。 两次冷水团大面调查结果表明，4月表层纤毛虫平均丰度(1490 ind./L)要高于10月(972 ind./L)。10月表层纤毛虫生物量0.14-5.33 µg C/L，14194站、15694站和15894站生物量较高，为4.08-5.33 µg C/L。无壳纤毛虫优势种Laboea strobila在两个航次中均呈现斑块分布，4月航次丰度0-10000 ind./L，10月航次丰度11-350 ind./L；砂壳纤毛虫优势种Ptychocylis obtusa仅在4月航次发现，最大丰度2895 ind./L，10月航次未发现。4月航次砂壳纤毛虫有百乐拟铃虫(Tintinnopsis beroidea)，丰度为0-1920 ind./L；卡拉直克拟铃虫(Tintinnopsis karajacensis)，丰度很小(10-93 ind./L)。10月航次砂壳纤毛虫优势种Tintinnidium primitivum，丰度为35-700 ind./L；也出现了尖底类瓮虫(Amphorellopsis acuta)和网纹虫(Favella spp.)，但丰度不大(0-210 ind./L)；运动类铃虫(Codonellopsis mobilis)、筒状拟铃虫(Tintinnopsis tubulosoides)和Eutintinnus sp.丰度也较低(35-105 ind./L)；Craterella torulata丰度为0-120 ind./L，主要分布于15694站。10月航次已经出现了温跃层，位于30 m左右水层，纤毛虫主要分布于温跃层之上。 六次黄海断面航次表明：温跃层在5月已经出现，到12月消失。在有温跃层的5月、6月、8月、9月，纤毛虫主要分布于温跃层(30 m左右)之上。其中8月份航次纤毛虫丰度最高，表层平均丰度3103 ind./L。12月份纤毛虫丰度最低，表层平均丰度406 ind./L。纤毛虫生物量春夏季为0.02-5.5 µg C/L，冬季为0.04-1.99 µg C/L。小型无壳纤毛虫占优势，砂壳纤毛虫东方拟铃虫(Tintinnopsis orientalis)、筒状拟铃虫、运动类铃虫、Craterella torulata和Tintinnidium primitivum几乎在各个航次均有分布。

Chemical characteristics of a polysaccharide from Porphyra capensis (Rhodophyta)

The structure of a polysaccharide from the red seaweed, Porphyra capensis, growing along the coast of Namibia and South Africa was investigated. Algae growing at different sites and collected at different times gave a polysaccharide extract with similar chemical components. FTIR and NMR spectral analysis showed that the polysaccharide from P. capensis had a typical porphyran structure. It has the linear backbone of alternating 3-linked beta-D-galactose and 4-linked alpha-L-galactose-6-sulfate or 3,6-anhydro-alpha- L-galactose units. The ratio of alpha-L-galactose-6-sulfate and the 3,6-anhydrogalactose is 121, as reflected by a H-1 NMR spectrum. A high degree of methylation occurred at the C-6 position of the D-galactose units. The degree of methylation was 0.64 for the D-galactose residues. (C) 2005 Elsevier Ltd. All rights reserved.

末次盛冰期以来中国陆地生态系统碳储量变化研究

Carbon is an essential element for life, food and energy. It is also a key element in the greenhouse gases and therefore plays a vital role in climatic changes. The rapid increase in atmospheric concentration of CO_2 over the past 150 years, reaching current concentrations of about 370 ppmv, corresponds with combustion of fossii fuels since the beginning of the industrial age. Conversion of forested land to agricultural use has also redistributed carbon from plants and soils to the atmosphere. These human activities have significantly altered the global carbon cycle. Understanding the consequences of these activities in the coming decades is critical for formulating economic, energy, technology, trade, and security policies that will affect civilization for generations. Under the auspices of the International Geosphere-Biosphere Programme (IGBP), several large international scientific efforts are focused on elucidating the various aspects of the global carbon cycle of the past decade. It is only possible to balance the global carbon cycle for the 1990s if there is net carbon uptake by terrestrial ecosystems of around 2 Pg C/a. There are now some independent, direct evidences for the existence of such a sink. Policymarkers involved in the UN Framework Convention on Climate Change (UN-FCCC) are striving to reach consensuses on a 'safe path' for future emissions, the credible predictions on where and how long the terrestrial sink will either persist at its current level, or grow/decline in the future, are important to advice the policy process. The changes of terrestrial carbon storage depend not only on human activities, but also on biogeochemical and climatological processes and their interaction with the carbon cycles. In this thesis, the climate-induced changes and human-induced changes of carbon storage in China since the past 20,000 years are examined. Based on the data of the soil profiles investigated during China's Second National Soil Survey (1979-1989), the forest biomass measured during China's Fourth National Forest Resource Inventory (1989-1993), the grass biomass investigated during the First National Grassland Resource Survey (1980-1991), and the data collected from a collection of published literatures, the current terrestrial carbon storage in China is estimated to -144.1 Pg C, including -136.8 Pg C in soil and -7.3 Pg C in vegetation. The soil organic (SOC) and inorganic carbon (SIC) storage are -78.2 Pg C and -58.6 Pg C, respectively. In the vegetation reservoir, the forest carbon storage is -5.3 Pg C, and the other of-1.4 Pg C is in the grassland. Under the natural conditions, the SOC, SIC, forest and grassland carbon storage are -85.3 Pg C, -62.6 Pg C, -24.5 Pg C and -5.3 Pg C, respectively. Thus, -29.6 Pg C organic carbon has been lost due to land use with a decrease of -20.6%. At the same time, the SIC storage also has been decreased by -4.0 Pg C (-6.4%). These suggest that human activity has caused significant carbon loss in terrestrial carbon storage of China, especially in the forest ecosystem (-76% loss). Using the Paleocarbon Model (PCM) developed by Wu et al. in this paper, total terrestrial organic carbon storage in China in the Last Glacial Maximum (LGM) was -114.8 Pg C, including -23.1 Pg C in vegetation and -86.7 Pg C in soil. At the Middle Holocene (MH), the vegetation, soil and total carbon were -37.3 Pg C, -93.9 Pg C and -136.0 Pg C, respectively. This implies a gain of-21.2 Pg C in the terrestrial carbon storage from LGM to HM mainly due to the temperature increase. However, a loss of-14.4 Pg C of terrestrial organic carbon occurred in China under the current condition (before 1850) compared with the MH time, mainly due to the precipitation decrease associated with the weakening of the Asian summer monsoon. These results also suggest that the terrestrial ecosystem in China has a substantial potential in the restoration of carbon storage. This might be expected to provide an efficient way to mitigate the greenhouse warming through land management practices. Assuming that half of the carbon loss in the degraded terrestrial ecosystem in current forest and grass areas are restored during the next 50 years or so, the terrestrial ecosystem in China may sequestrate -12.0 Pg of organic carbon from the atmosphere, which represents a considerable offset to the industry's CO2 emission. If the ' Anthropocene' Era will be another climate optimum like MH due to the greenhouse effect, the sequestration would be increased again by -4.3 - 9.0 Pg C in China.

中国南北方泥盆纪腕足化石碳、氧、锶同位素研究

海相碳酸盐岩C、O、Sr 同位素研究是地球化学重要的示踪手段之一。它可以为认识地质历史时期的气候变化，海水原始碳、氧、锶同位素组成，陆地和海洋生物盛衰的长期变化特征，以及碳、氧等元素的外生循环等一些重大的基础学科问题提供重要的依据。研究表明：腕足化石因具有较强抵抗成岩后生作用能力、分布广泛、便于操作等原因被认为是较为理想的研究样品之一。 本论文对来自中国南、北方泥盆纪不同沉积单元腕足化石碳、氧、锶同位素组成进行测试，探讨中国南、北方不同沉积单元腕足化石碳、氧、锶同位素差异。从地球化学角度对我国泥盆纪海平面变化，海洋生物盛衰、陆地风化强度以及构造运动研究进行诠释。 中国泥盆系沉积类型齐全，从南到北，分布着不同构造单元条件下沉积而成的地层。华南泥盆系属地台型稳定沉积类型，四川龙门山地区泥盆系形成于冒地槽构造单元中，而中国北方泥盆系为优地槽活动构造单元的产物。三类构造单元的地壳活动和火山活动不同，生活在其中的腕足壳体碳、氧、锶同位素组成是否存在差异？不同构造单元的海平面变化、海洋生物盛衰以及陆地风化强度是否不同。 研究中通过上述不同沉积单元腕足化石碳、氧、锶同位素组成详细研究，得出以下几点认识： 1) 在腕足化石保存鉴定过程中：微体结构实验显示南、北方剖面腕足化石壳体结构保存完整，有着明显的纤维层和棱柱层结构，但北方剖面腕足化石微裂隙较多，有着不少后期物质充填。在阴极灯照射下，南方剖面腕足化石基本不发光，仅因少量裂隙中后期物质充填有着微弱发光现象存在。北方剖面腕足化石基本上都有着轻微发光现象，尤其内蒙古地区腕足化石。微量元素Fe、Mn、Sr 含量及其Mn/Sr 值表明南、北方剖面腕足化石绝大多数符合腕足保存完好的标准。表明：南方剖面腕足化石保存完好，可以用于的碳、氧、锶同位素组成研究。北方剖面腕足化石保存程度较差，其同位素信息可能遭受成岩蚀变作用的影响，特别是容易遭受蚀变影响的氧同位素组成。 2) 成岩后生作用总是导致碳酸盐岩全岩样品中碳、氧、锶同位素组成发生变化，无法保存原始的同位素信息。腕足化石同碳酸盐岩全岩碳、氧、锶同位素对比表明：碳酸盐岩全岩样品中碳、氧同位素组成都低于腕足化石样品中同位素组成，锶同位素组成正好相反，但在不涉及定量化研究的前提下，碳、锶同位素基本上可以代表着地质历史时期碳、锶同位素变化趋势。也即是说可以利用碳酸盐岩全岩样品进行碳、锶同位素演化趋势研究。至于碳酸盐岩全岩样品中氧同位素组成，低于腕足化石氧同位素组成达 -2‰～-3‰。在目前常用于氧同位素古温度的研究中差异太大。因此，建议不要利用碳酸盐岩全岩样品中氧同位素组成进行古温度研究。 3) 碳同位素组成变化可以指示有机碳的埋藏情况。中国南、北方剖面腕足化石碳同位素研究表明：腕足化石中碳同位素组成基本上在 -2‰ ～ 4‰之间变化，北方剖面较低，南方剖面较高。其碳同位素Locfit 演化对比显示：北方剖面碳同位素演化同华南以及四川龙门山剖面中碳同位素演化有着许多相似之处，表明北方海域有机碳埋藏情况同南方海域有机碳埋藏情形基本一致。分析表明：四川龙门山以及华南剖面泥盆纪时期有着三次有机碳高速埋藏时期，可能受海平面变化以及与之有关的生物繁盛状况共同控制。至于北方剖面碳同位素组成相对较低，一方面可能由于腕足化石保存方面的原因，在成岩蚀变作用影响下北方剖面腕足碳同位素组成较低。另一方面，北方地区较多的火山活动，释放大量含有较多12C 的CO2，融入海水发生同位素交换，导致北方地区碳同位素组成较低。 4) 由于北方剖面存在遭受成岩蚀变作用影响的可能，北方剖面腕足化石壳体氧同位素平均组成(-11.75‰ ~ -21.13‰)明显低于四川龙门山剖面(-5.14‰ ~-7.20‰)、华南剖面(-4.35‰ ~ -10.31‰)氧同位素平均组成，无法对水岩反应控制海洋中氧同位素组成给出肯定的答案。但腕足化石保存完好的四川龙门山剖面和华南剖面氧同位素组成(氧同位素素组成埃姆斯阶为-7.20‰、-7.58‰；吉维特阶-5.62‰、-4.60‰；氟拉斯阶-5.18‰、-4.35‰)显示：优地槽沉积单元的龙门山海域同稳定地台沉积单元的华南海域氧同位素一致，甚至较低，表明水岩反应根本无法控制海洋中氧同位素组成。 5) 四川龙门山剖面下泥盆统埃姆斯阶氧同位素组成为 -9.9‰～-4.5‰，明显低于世界上其他地区同时期腕足化石的氧同位素组成，其差异达 -3‰~-4‰。微量元素Fe、Mn 的演化趋势以及氧同位素演化趋势显示：龙门山海域在埃姆斯阶时期同广阔海域之间海水交流不畅通，其氧同位素组成受淡水河流注入的影响。根据氧同位素古温度计估算(假定古海水δ18O 值为 -3‰SMOW)，姆斯阶时期温度高达52℃，远远超过生物所能生存的极限，印证龙门山海域埃姆斯阶氧同位素组成受淡水河流注入的影响。艾菲尔阶～氟拉斯阶，龙门山海域的温度为21℃ ～33℃，表明龙门山海域为典型的低纬地区热带气候。 6) 早泥盆纪时期，锶同位素比值较高，显示风化作用较为强烈；可能是由于加里东造山作用的影响，大量陆地的暴露，促进风化作用的进行。其后，锶同位素组成逐渐降低指示风化作用变弱。锶同位素降低可能由于海底扩展运动造成幔源锶的增加，同时引起海平面上升，引起陆地风化面积的减少，导致风化作用的减弱。幔源锶增加和陆源锶的减少，造成锶同位素比值的不断下降。早泥盆世晚期－中泥盆世，锶同位素组成显示风化作用(强度较低)和构造运动稳定。可能原因为在海平面较高时海侵－海退幅度较小，幔源锶和陆源锶之间达到均衡。中泥盆世后期，锶同位素组成显示：风化作用程度较强。可能由于该时期温度的缓慢上升，导致风化作用加强，陆源锶输入增多引起的。 7) 不同沉积单元腕足化石碳、氧、锶同位素对比表明：局部的区域环境对碳、氧、锶同位素有影响。在考虑利用不同剖面进行地质历史时期某时段碳、氧、锶同位素数据叠加构建完整同位素演化曲线时；对于碳同位素，相同沉积单元条件下，辨别出长时间变化和局部影响时可以应用于同位素演化曲线的构建。而不同沉积单元的碳同位素组成存在差异，不能应用于碳同位素曲线的构建。不同沉积单元氧同位素组成存在较大差异，相同沉积单元的氧同位素组成同样也存在较大差别，表明局部环境对氧同位素组成影响较大，氧同位素曲线的构建最好避免多个剖面的叠加。锶同位素比值，不同沉积单元在长期演化趋势上基本一致，在排除局部环境因素的影响下可以进行多剖面锶同位素演化曲线的构建。

The study of oxygen spillover and back spillover on Pt/TiO2 by a potential dynamic sweep method

Oxygen spillover and back spillover on Pt/TiO2 catalysts have been studied by a potential dynamic sweep method. The characteristics of I-V profiles of Pt/TiO2 electrodes in the three potential sweep regions are different from those of Pt and TiO2 electrodes. The catalytic role of Pt/TiO2 in oxygen spillover and back spillover is identified. It decreases, and the electrochemical oxygen adsorption (or desorption) increases with elevating temperature of hydrogen post-treatment of Pt/TiO2; to a certain extent (hydrogen post-treatment of Pt/TiO2 at 700 degrees C), the control step of oxygen electrode process (anodic oxidation or cathodic reduction) changes from oxygen diffusion to electrochemical oxygen adsorption or desorption, respectively. Increasing the amount of Pt supported on TiO2 enhances the processes of oxygen spillover and back spillover. (C) 1999 Elsevier Science B.V. All rights reserved.

Restructuring and redispersion of silver on SiO2 under oxidizing/reducing atmospheres and its activity toward CO oxidation

The effects of oxygen-hydrogen pretreatments of nanosilver catalysts in cycle mode on the structure and particle size of silver particles, and subsequently the activity of the catalyst toward CO oxidation (or CO selective oxidation in the presence of H-2) are reported in this paper. Ag/SiO2 catalyst with silver particle sizes of ca. 6 similar to 8 nm shows relatively high activity in the present reaction system. The adopting of a cycle of oxidation/reduction pretreatment has a marked influence on the activity of the catalyst. Oxygen pretreatment at 500 degrees C results in the formation of subsurface oxygen and activates the catalyst. As evidenced by in-situ XRD and TEM, the following H-2 treatment at low temperatures (100 similar to 300 degrees C) causes surface faceting and redispersing of the silver particles without destroying the subsurface oxygen species. The subsequent in-situ FTIR and catalytic reaction results show that CO oxidation occurs at -75 degrees C and complete CO conversion can be obtained at 40 degrees C over such a nanosilver catalyst pretreated with oxygen at 500 degrees C followed by H-2 at 100 degrees C. However, prolonged hydrogen treatment at high temperatures (> 300 degrees C) after oxygen pretreatment at 500 degrees C induces the aggregation of silver particles and also depletes so much subsurface oxygen species that the pathway of CO oxidation by the subsurface oxygen species is inhibited. Meanwhile, the ability of the catalyst to adsorb reactants is greatly depressed, resulting in a 20 similar to 30% decrease in the activity toward CO oxidation. However, the activity of the catalyst pretreated with oxygen at 500 degrees C followed by hydrogen treatment at high temperatures (> 300 degrees C) is still higher than that directly pretreated with H,. This kind of catalytic behavior of silver catalyst is associated with physical changes in the silver crystallites because of surface restructuring and crystallite redispersion during the course of oxygen-hydrogen pretreatment steps.