LiMgAlF_6 : Tm~(3+) 的合成与光谱特性

采用高温固相反应法，ＬｉＦ／ＭｇＦ２／ＡｌＦ３＝１２０／１１０／１００，烧结温度为１００８Ｋ，烧结时间为４ｈ，在流动的高纯Ａｒ中合成了ＬｉＭｇＡｌＦ６：Ｔｍ３＋。对其结构和发光特性进行了研究。

High-yield extraction of endohedral rare-earth fullerenes

The technique of high-temperature high-pressure extraction with pyridine has been successfully utilized to extract a wide variety of endohedral rare-earth fullerenes of the type Ln@C-2n (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb). Ln@C-80, Ln@C-82, and Ln(2)@C-80 for most of the rare-earth metals can be produced with high-yield and selectively extracted from the carbon-are evaporation soot. Metallofullerenes containing Sm, Eu, and Yb (which could have +2 oxidation states) are especially difficult to extract. Some possible reasons for the high-yield extraction are discussed. The laser desorption mass spectrometric characterization results indicate a relationship between the extraction yields of metallofullerenes and the oxidation states and ionic radii of the rare-earths.

3,4－聚异成二烯的合成及所得聚合物结构与性能表征

近二十多年来，在异成二烯的络合催化聚合中，由Ni、Co、Ti及稀土等过渡金属元素络合物组成的催化体系，研究报道得很多，有些已投入工业生产。但由最常见的过渡金属元素铁络合物组成的催化体系，对异成二烯聚的聚合却不多见。本工作研究了三乙酰基丙酮铁为主催化剂，烷基铝为助催化剂，添加含氮类给电子试剂组成三元体系，对异成二烯聚合的催化作用。Fe(a cac)_3 - Al(i-Bu)_3二元体系不能引起异成二烯聚合，而加入少量的含氮类给电子试剂如邻菲啰啉、α,α'－联吡啶等，催化活性显著提高。聚合活性与含氮类给电子试剂的性质有关，并随着下列顺序依次递减：邻菲啰啉、α,α'－联吡啶、对苯二胺、邻苯二胺，对硝基苯胺、邻硝基苯胺；吡啶和已二胺对催化活性的提高几乎没有贡献。烷基铝的不同对催化活性也有明显的影响。其活性顺序为：Al(i-Bu)_3 approx Al Eτ_3 > Al(i-Bu)_2H。首次合成了结晶的3,4－聚异成二烯，3,4－链节含量为70％左右时，Tm为121 ℃左右， Tc为65 ℃左右，透射电镜下观察到结晶的3,4－聚异成二烯具有球晶状结构。初步研究了铁系三元催化体系的反应机理，设想铁化合物和烷基铝生成的烷基铁必须与含氮类给电子试剂作用才能形成活性中心；可见光谱和催化活性实验数据证实了含氮类给电子试剂参与活性中心的形成，并起着稳定活性中心的作用。本文详细地研究了Fe(a cac)_3 - phen - Al(i-Bu)_3催化体系对异成二烯的聚合，考察了起始单体浓度、聚合温度，催化剂总用量以及催化剂各组分配比对聚合速率、聚合物的特性粘数和链节结构的影响，从实验结果讨论了Fe(a cac)_3 - phen - Al(i-Bu)_3体系催化异成二烯的聚合机理，并进行了一些动力学的基本计算，得到了与实验结果基本相符的结果，解释了一些实验现象。铁系聚异成二烯橡胶的表征工作未见诸文献，本工作对铁系聚异成二烯生胶的结晶、力学、流变及阻尼性能作了较系统的研究，并对硫化胶的物理机械性能，弹性及阻尼性能作了初步的表征。铁系聚异成二烯橡胶在室温具有较好的阻尼性能，并且生热值和冲击弹性均较低，可作为室温阻尼材料使用。

5，10，15，20－四（对－山嵛酸乙酯－α－氧代苯基）卟啉LB膜结构研究

５，１０，１５，２０－四（对－山嵛酸乙酯－α－氧代苯基）卟啉ＬＢ膜结构研究王海水，曾广赋，谷淑珍，席时权（中国科学院长春应用化学研究所长春１３００２２）利用ＬＢ膜技术将分子组装成有序的分子单层或多层体系，研究膜内分子间相互作用和分子的结构，对了解结构...

STUDIES ON OLEFIN-COORDINATING TRANSITION-METAL CARBENE COMPLEXES .20. SYNTHESIS OF 1,3-CYCLOHEXADIENE(DICARBONYL) [ETHOXY(ARYL)-CARBENE]IRON COMPLEXES AND THEIR PHOSPHINE ADDUCTS - CRYSTAL-STRUCTURE OF C6H8(CO)2FEC(OC2H5)C6H4CH3-O

Reaction of 1,3-cyclohexadiene(tricarbonyl)iron (1) with ortho-substituted aryllithium reagents ArLi (Ar=o-CH3C6H4, o-CH3OC6H4, o-CF3C6H4) in ether at low temperature, and subsequent alkylation of the acylmetalates formed with Et3OBF4 in aqueous solution at 0-degrees-C or in CH2Cl2 at -60-degrees-C gave the 1,3-cyclohexadiene(dicarbonyl)[ethoxy(aryl)carbene]iron complexes (eta4-C6H8)(CO)2FeC(OC2H5)Ar (3, Ar = o-CH3C6H4; 4, Ar = o-CH3OC6H4), and the isomerized product (eta3-C6H8)(CO)2FeC(OC2H5)C6H4CF3-o (5), respectively, among which the structure of 3 has been established by an X-ray diffraction study. Complex 3 is monoclinic, space group P2(1) with a = 8.118(4), b = 7.367(4), c = 14.002(6) angstrom, beta = 104.09(3)-degrees, V = 812.2(6) angstrom3, Z = 2, D(c) = 1.39 g cm-3, R = 0.056, and R(w) = 0.062 for 976 observed reflections. Complexes 3 and 5 were converted into the chelated allyliron phosphine adducts(eta3-C6H8)(CO)2(PR31)FeC(OC2H5)Ar (6, Ar = o-CH3C6H4, R1 = Ph; 7, Ar = o-CH3C6H4, R1 = OPh; 9, Ar = o-CF3C6H4, R1 = Ph), by reaction with phosphines in petroleum ether at low temperatures.

5,10,15,20-四(对-乙酯苯基)卟啉LB膜的结构

对卟啉类化合物LB膜的结构、电性质和气敏性的研究已见报道。本文利用膜天平和UV-Vis分光光度计研究了标题化合物在气-液界面上的成膜特性、分子间相互作用和LB膜的结构。5,10,15,20-四(对-乙酯苯基)卟啉(TPEPP)由5,10,15,20-四(对-氰苯基)卟啉和乙醇酯化得到。元素分析测定值与计算值相符。λ(CHCl_3,nm):421,515,550,590,645;ν(KBr压

稀土三氟乙酸络合物的快原子轰击质谱研究

本文首次报道Ln(OOCCF_3)_3(Ln=Pr、Nd、Sm、Eu、Gd、Tb、Ho、Er、Tm、Yb、Lu在甘油(G)中的正负离子FAB谱、总结了其离子特征。通过亚稳分析、探讨了某些离子的碎裂方式,提出了Ln(Ⅱ)→Ln(Ⅰ)可能的还原变价机制。

YP_5O_(14):Er~(3+),Tm~(3+)晶体的合成

研究了水热法合成晶体,浓度配比、生长温度对晶体生长习性的影响.合成了一系列化学计量比的Y_(1-x-0.3)Er_(0.3)Tm_xP_5O_(14)(x=0.01～0.1)晶体,观察和分析了晶体的缺陷及成因,测定和讨论了晶体结构.

New sphingolipids with a previously unreported 9-Methyl-C-20-sphingosine moiety from a marine algous endophytic fungus Aspergillus niger EN-13

Asperamides A (1) and B (2), a sphingolipid and their corresponding glycosphingolipid possessing a hitherto unreported 9-methyl-C-20-sphingosine moiety, were characterized from the culture extract of Aspergillus niger EN-13, an endophytic fungus isolated from marine brown alga Colpomenia sinuosa. The structures were elucidated by spectroscopic and chemical methods as (2S,2'R,3R,3'E,4E,8E)-N-(2'-hydroxy-3'-hexadecenoyl)-9-methyl-4,8-icosadien-1,3-diol (1) and 1-O-beta-D-glucopyranosyl-(2S,2'R,3R,3'E,4E,8E)-N-(2'-hydroxy-3'-hexadecenoyl)-9-methyl-4,8-icosadien-1,3-diol (2). In the antifungal assay, asperamide A (1) displayed moderate activity against Candida albicans.

Development of the East Asian monsoon: Mineralogical and sedimentologic records in the northern South China Sea since 20 Ma

We here reconstruct the past change of the East Asian monsoon since 20 Ma using samples from Ocean Drilling Program (ODP) Site 1146 in the northern South China Sea based On a multi-proxy approach including a monomineralic quartz isolation procedure, identification of clay minerals by X-ray Diffraction (XRD) and grain-size analysis of isolated terrigenous materials. Terrigenous supply to ODP Site 1146 was dominated by changes in the strength of multiple sources and transport processes. Grain-size data modeled by an end-member modeling algorithm indicate that eolian dust from the and Asian inland and fluvial input have contributed on average 20% and 80% of total terrigenous material to ODP Site 1146, respectively. Specifically, about 40-53% of the total (quartz+feldspar) and only 6-11% of the total clay is related to eolian supply at the study site. Detailed analysis of the sedimentary environment, and clay minerals combined with previous studies shows that smectite originates mainly from Luzon, kaolinite from the Pearl River and illite and chlorite from the Pearl River, Taiwan and/or the Yangtze River. The proportion and mass accumulation rate (MAR) of the coarsest end-member EM1 (interpreted as eolian dust), ratios of (illite+chlorite)/smectite, (quartz+feldspar)% and mean grain-size of terrigenous materials at ODP Site 1146 were adopted as proxies for East Asian monsoon evolution. The consistent variation of these independent proxies since 20 Ma shows three profound shifts in the intensity of East Asian winter monsoon relative to summer monsoon, as well as aridity of the Asian continent, occurred at similar to 15 Ma, similar to 8 Ma and the youngest at about 3 Ma. In comparison, the summer monsoon intensified contemporaneously with the winter monsoon at 3 Ma. The phased uplift of the Himalaya-Tibetan plateau may have played a significant role in strengthening the Asian monsoon at similar to 15 Ma, 8 Ma and 3 Ma. (C) 2007 Elsevier B.V. All rights reserved.

Grain-size records at ODP site 1146 from the northern South China sea: Implications on the east Asian monsoon evolution since 20 Ma

273 samples from Ocean Drilling Program (ODP) Site 1146 in the northern South China Sea (SCS) were analyzed for grain-size distributions using grain-size class vs. standard deviation method and end-member modeling algorithm (EMMA) in order to investigate the evolution of the East Asian mon-soon since about 20 Ma. 10-19 mu m/1.3-2.4 mu m, the ratio of two grain-size populations with the highest variability through time was used to indicate East Asian winter monsoon intensity relative to summer monsoon. The mass accumulation rate of the coarsest end member EM1 (eolian), resulting from EMMA, can be used as a proxy of winter monsoon strength and Asian inland aridity, and the ratio of EM1/(EM2+EM3) as a proxy of winter monsoon intensity relative to summer monsoon. The combined proxies show that a profound enhancement of East Asian winter monsoon strength and winter monsoon intensity relative to summer monsoon occurred at about 8 Ma, and it is possible that the summer monsoon simultaneously intensified with winter monsoon at 3 Ma. Our results are well consistent with the previous studies in loess, eolian deposion in the Pacifc, radiolarians and planktonic foraminifera in the SCS. The phased uplift of the Himalaya-Tibetan Plateau may have played a significant role in strengthening the Asian monsoon at 8 Ma and 3 Ma.

三峡工程截流后长江口海区表层悬沙分布与河口锋带特征

本文收集了三峡截流前后长江口海区1988－2007年间十二景landsat TM遥感影像并进行了表层悬浮泥沙含量的反演，定性的描述了长江口海区洪、枯季的表层悬沙扩散外界和高浑浊水域范围的变化趋势，分析了河流泥沙输移入海形态的变化特征及表层悬沙浓度的变化特征。 通过对2002-2004年在长江口滨外区表层悬浮体取样数据的实验室处理，揭示了三峡截流后表层悬沙的分布特征；通过多船同步定点观测捕捉到了长江口河口锋带的位置并分析了河口锋带的动力特征，结果表明：长江口河口锋位于（122o10′E，30o50′N）至（122o20′E，31o00′N）一线附近，在河口锋带位置有着较为强烈的河海相互作用，流速不符合典型的对数流速曲线，河水与海水的相互消长局限于海面以下5m的表层范围，在河口锋面区悬浮泥沙为泥沙流伏在海水之上输运。长江口悬沙体浓度由于三峡蓄水作用表现为下降趋势，悬浮体扩散范围相比截流前向口门后退，长江口滨外区羽状锋带随之向口门后退。 利用二维潮流数值模型较成功地模拟出了每个季度长江河口外的流场情况及河口锋带的发育情况，模拟表明：春、夏、秋三季河口锋带较易出现，且小潮期间发育最好。冬季长江河口海洋动力较强，易于发生海水入侵，尤其是北支；夏季是长江三角洲的主要建设期，锋带作用的存在使得泥沙大部分在锋带的内外区域沉积；春秋两季是平衡期；冬季主要是冲刷的时期。

基于微波图像的辽东湾海冰典型要素信息提取

业务化海冰遥感监测的要素主要包括海冰类型、海冰厚度和海冰范围（冰缘线）。本文针对辽东湾海冰的特点，结合星载合成孔径雷达（SAR）、机载微波辐射计（ABMR）和星载微波辐射计遥感图像观测辽东湾海冰，发展海冰要素探测算法，提取海冰类型、海冰厚度和冰缘线信息。 海冰类型SAR信息提取方面，首先分析了双极化ENVISAT ASAR数据不同极化方式的海冰探测能力。然后利用SAR图像，结合同步TM数据和航空照片，开展辽东湾地区不同类型海冰的电磁特性研究。研究结果表明，SAR图像可较好地区分沿岸固定冰、平整冰和碎冰堆积区，但在探测初生冰方面并不可靠，探测结果与海冰生长阶段以及海冰周围环境条件有关。根据SAR图像中海冰类型的分析，将PCNN神经网络用于海冰SAR图像的分割和海冰分类，并对PCNN做了简化和改进。经SAR图像分类结果测试，简化和改进后的PCNN可较好地区分SAR图像中的海冰类型。通过分析了PCNN网络各参数对SAR图像分割结果的影响，指出了各参数的取值范围，并在此基础上建立了基于PCNN神经网络的海冰SAR图像半自动分类判读系统。 海冰厚度机载微波辐射计信息提取方面，推导了非相干模式的ABMR海冰厚度反演模型，并首次得到了模型中高阶亮温辐射项的计算表达式。通过对模型的分析，指出ABMR只能测量一定范围内的海冰厚度。其中，最大海冰探测厚度不仅决定于ABMR的波长，而且还受到仪器精度的限制；最小海冰探测厚度只与仪器的波长有关。在此基础上，定量计算了我国几种常用波长ABMR的海冰厚度探测范围。并结合辽东湾海冰冰情等级，指出适合不同海冰冰情等级的ABMR的选择。最后分析了海冰厚度反演模型的影响因素和模型的适应范围。 海冰边缘线星载微波辐射计信息提取方面，首次将PSSM算法用于AMSR数据，提取辽东湾海冰边缘线信息，可得到空间分辨率为2.5km、重复周期为1d的辽东湾海冰边缘线信息。通过提取结果与Jason-1高度计和SAR探测海冰边缘线的比较，验证了PSSM方法探测辽东湾海冰边缘线的有效性。 论文的最后对全文做了总结，并提出和讨论了需要进一步开展的工作。

焦脱镁叶绿酸-a甲酯20-meso-1-位的亲电取代反应

利用焦脱镁叶绿酸-a甲酯与亲电试剂发生的取代反应，在焦脱镁叶绿酸-a甲酯的20-meso-位上分别引进硝基和卤原子，得到了20-meso位取代的焦脱镁叶绿酸衍生物．所合成的新叶绿素-a衍生物均经UV，IR，~1H NMR及元素分析证明其结构．另外，对叶绿素-a卟吩环上的芳香性和相应的化学反应活性也进行了讨论，提出了可能的亲电取代反应机理．

自治水下机器人控制方法研究及滑模模糊控制的应用研究

本论文在参阅大量国内外文献的基础上，进行了两方面的研究工作：自治水下机器人控制方法研究和滑模模糊控制的应用研究。全文分两部分对所做工作进行，总结论述。在第一部分“滑模模糊控制方法在自治水下机器人中的应用研究”中，本文总结了自治水下机器人控制方法的新进展；研究了模糊滑模控制和滑模模糊控制的原理，并针对6000米自治水下机器人“cR－01”的数学模型进行了仿真。仿真结果表明滑模与模糊控制相结合的方法减少了模糊控制规则的数目，参数较易调整，而且可以消除普通滑模控制中的颤振现象。在仿真的基础上进行了滑模模糊控制水池实验，对实验结果进行了分析。实验结果表明，滑模模糊控制可以大大提高自治水下机器人控制系统的性能。在第二部分“自治水下机器人控制方法研究”中，本文进行了解祸控制、BackStepping控制、“CR－01’，控制方法的仿真和水下机器人六自由度仿真的研究。分析了自治水下机器人运动中存在的藕合作用，就解祸控制进行了分析和仿真，仿真结果表明解藕控制可以很好地实现同一平面内各祸合变量的解藕。分析了BackStepping鲁棒控制算法，在自治水下机器人运动存在模型摄动和外界千扰时进行了仿真，仿真结果表明基于全状态反馈的B ackStepping控制算法具有很强的鲁棒性，对模型摄动和干扰有较强的适应性。在进行论文工作的过程中，作者建立了大量的基于MATLAB TM下S INIULINKIrm的6000米自治水下机器人"CR－01”的控制方法仿真模块。本文建立了一个全自由度的自治水下机器人仿真模块，为路径规划和高层使命仿真打下了基础。