氟化物体系新型无机闪烁材料制备特性及若干基础问题研究

本文综述了无机闪烁材料研究的进展，着重了氟化物体系中几种新型无机闪烁材料的制备、性能及辐照损伤等特性。运用B－S法生长了BaF_2及BaF_2:Ce晶体，研究了其室温以上的TSL特性，发现BaF_2的TSL曲线是由381K和402K的双峰结构组成Ce的掺入使TSL强度降低，同时提高了其抗辐照性能。运用高温固相反应法合成了KMgF_3、KCaF_3、BaLiF_3微晶，用TSL和ESR研究了其辐照损伤及其恢复情况。纠正了文献中对KMgF_3热释峰归属的错误，发现在KMgF_3、KCaF_3中杂质Al~(3+)一方面引入新的缺陷而导致新的热释峰，另一方面抑制了F心的形成。在BaLiF_3中La~3、Yb~(3+)的掺入会抑制F心，同时使H心增强，观察到了大剂量（10~8Rad）辐照时BaLiF_3中FA心形成及其在加热和紫外光照射时向F心的转化。发现它们的X射线辐照损伤极易恢复，而γ射线辐照损伤则较难恢复。通过对ESR峰高与Eu掺杂浓度的研究，运用数学拟合法求得了Eu~(3+)掺入KMgF_3制备KMgF_3:Eu~(2+)的饱和掺杂浓度为0.29mol%。首次发现BaLiF_3:Eu~(2+)的PSL现象，并证明它是一种很有发展前途的新型X射线存贮材料。运用B－S法探索了KMgF_3、BaLiF_3、单晶生长工艺，用X射线四园衍射法发现La~(3+)、Tm~(3+)掺入KMgF_3时分另占据K~+、Mg~(2+)的格位，用SEM观察了浓H_2SO_4cf KMgF_3单晶的侵蚀形貌和BaLiF_3单晶生长中经常出现的包裹体。研究了LaF_3:Ce~(3+)的发光特性及其它三价稀土离子的共掺杂对Ce~(3+)发光特性的影响，发现其它三价稀土离子的共掺杂都会使Ce~(3+)的发光猝灭，并分别归结为能量传递和电荷转移。用B－S法生长了CeF_3单晶，但因原料纯度低，衰减常数和光子产额都比文献值要低，说明在闪烁晶体制备时，提高原料纯度是十分必要的。

中国新疆塔里木河中下游河流廊道的景观生态学研究

中国西部干旱区是干旱区研究的天然实验场。塔里木河是西部干早区重要的生态河流。塔里木河中下游尉犁一若羌段以沙地景观为基质，以河渠、公路、防护林为连接廊道，草地、盐碱地、湿地、耕地为镶嵌斑块，是典型的干旱区河流廊道景观区域，是南疆第一大城市库尔勒与未来重建的新楼兰的唯一景观廊道，在塔里木河流域的可持续发展中起着重要的连通作用。本文以塔里木河下游绿色走廊为主体的塔里木河中下游河流廊道区域为研究对象，在区域景观生态特征的认识和景观生态建设方略的探讨上，具有重要意义。本文在景观生态学的应用研究中，注重其理论体系的构建。（1）全面收集国内外景观生态学研究的最新进展，提出景观生态学研究的核心研究框架与原理，阐明景观生态学研究的热点和新的领域。干旱区多功能景观研究，有着极其广阔的理论与实践上的创新潜力。根据以往研究成果，揭示中国西部干旱区的景观生态特征，展望其关键研究领域的前景和方向，其中绿洲研究、湿地研究、廊道研究和景观生态建设研究，各具特有的角度，又有相互的联系，最具景观生态学研究的特质和潜质。（2）收集卫星影像资料并进行解译（1980年MS航片校正、1990年TM、2000年TM），以土地利用类型为基础，以塔里木河中下游河流廊道区域现状为参照，建立了干早区河流廊道景观区域景观生态分类体系，结合野外植被和土壤调查，以及相关图件，全面研究了各类研究区景观的土壤和植物生态属性与功能特征。（3）通过景观格局指数的计算，以及景观类型的转换矩阵，揭示20世纪80年代以来区域廊道景观格局的变化过程与趋势，结合区域水资源、生态及人文变化，对变化的驱动力因子进行研究。在区域景观尺度上，构建景观生态空间分析模式，包括格局指数分析、转移矩阵分析和空间过程分析，并以此寻求区域景观格局变化的驱动力。（4）应用景观生态学原理，确定景观生态功能区划的原则，构建其区划系统。据此划分了三个景观生态功能类型区：①尉犁一卡拉水库段塔里木河一孔雀河中游城镇一绿洲农业区，②卡拉水库一大西海子水库塔里木河下游上中段农垦绿洲区，③大西海子水库一台特玛湖一若羌塔里木河下游下段一车尔臣河下游生态重建和恢复区。通过景观格局指数，对比不同功能区的景观生态差异；根据不同景观生态功能区，不同宽度的河流廊道缓冲带景观格局指数的分析，以及次一级廊道指数的计算，揭示景观廊道区域相关指数的变化规律及其廊道效应。（5）根据干旱区景观生态特点，建立干旱区生态环境质量评价概念模型，以研究区为案例，提出基于遥感和GIS的景观生态环境质量现状与预警指标体系，采用层次分析法，对塔里木河中下游以河流廊道为特征的研究区域进行景观生态评价分析。（6）在了解廊道区域景观时空变化驱动力的基础上，对不同的生态治理方式的景观生态效应进行分析，提出塔河中下游河流廊道区域“大塔里木河”景观生态建设的总体原则（包括减少对沙地基质的干扰，充分利用和适度开发草地资源，保护和恢复湿地景观的多功能性，畅通输水过程以稳定和增加植被覆盖及其多样性与经济性，通过节水灌溉和重视排水减轻次生盐渍化程度），及其相应的景观生态工程设计，确定不同景观生态功能区的景观生态建设与设计的模式与途径（包括生态恢复、生境更新与调整、生态功能重建和生态移民）。

基于RS和GIS黄河三角洲水禽生境因子变化分析

将影响水禽生境选择的因子划分为水、食物、隐蔽物和干扰4类.用遥感(RS)和地理信息系统(GIS)软件对黄河三角洲地区3期TM数据进行处理,对各生境因子采取一定的分类方法,得出该地区3个时期各生境因子图.通过面积、斑块数变化及转移矩阵的分析可以看出,各生境因子的结构发生了明显的变化,变化表现为干扰加重,积水地区面积增大,谷物草籽面积及适宜隐蔽物范围减少.人类的有意识活动(干扰)是引起各生境因子发生变化的主要驱动力.生境因子变化对水禽生境既有正面影响,又有负面影响.图9表5参30

岷江上游典型时期景观格局变化及驱动力初步分析

岷江上游地区是我国一个重要的大尺度、复合型生态过渡带 ,也是一个生态系统脆弱区 ,研究其景观格局的变化 ,对于构筑我国的生态格局安全具有十分重要的意义 .本研究利用岷江上游地区 1986、1995、2 0 0 0年 3个时期的TM影像 ,分析了 3个时期的景观特征以及变化 .结果表明 ,岷江上游整体景观水平以草地景观为基质、森林景观以及其他景观类型作为斑块镶嵌其中 .森林景观面积经历了从 1986～1995年的上升 ,而后到 2 0 0 0年的下降过程 ;草地景观高盖度草面积不断减少 ;同时 ,森林景观和草地景观斑块总数一直增加 ,破碎化趋势明显 .岷江上游景观格局变化的驱动因子主要是日益增加的人口数量而导致的人为干扰 ,包括对土地利用方式与利用强度的改变、森林资源的掠夺性开采、草地资源的过度放牧以及气候、土壤等自然因素的变化 .

稀土离子在CdSiO_3基质中的多光色长余辉发光

利用高温固相法合成了系列稀土离子掺杂的CdSiO_3:RE~(3+)(RE=Y,La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu)多光色长余辉磷光体。XRD分析结果表明在1050℃下烧结3小时的产物为单相。稀土掺杂CdSiO_3磷光体具有良好的发光性能。引入Y~(3+),La~(3+),Gd~(3+),Lu~(3+)以及Ce~(3+),Nd~(3+),Ho~(3+),Er~(3+),Tm~(3+),Yb~(3+)可获得一个最大发射中心位于420 nm附近的缺陷发光宽带,引入 Pr~(3+),Sm~(3+),Eu~(3+),Tb~(3+),Dy~(3+)时,除了产生约420 nm的蓝紫色缺陷发光外同时产生很强的稀土离子特征发光,这两种发光混合导致不同的余辉颜色。

谷胱甘肽与稀土离子作用的~(13)C NMR研究

本文利用顺磁稀土离子的诱导化学位移变化的性质,研究了多官能团配体谷胱甘肽(GSH)与稀土的配位作用.在水溶液中GSH通过分子两端的羧基负离子与稀土形成遥爪配位结构.谷氨酸端和甘氨酸端羧基与Eu~(3+)的配位稳定常数分别为12.5±0.1L/mol和100.0±0.5L/mol.从~(13)C化学位移的pH变化曲线求得谷氨酸端和甘氨酸端羧基解离的pK_a值分别为2.20±0.02和3.50±0.04.对Dy~(3+)、Ho~(3+)、Er~(3+)、Tm~(3+)和 Yb~(3+)作用下,GSH的~(13)C位移数据分析表明,配体与这些离子形成同构的配合物,分子两端羧基均可能以双齿形式与稀土配位.

双甘肽稀土配合物溶液结构的~(13)C~1H NMR研究

关于双甘肽的~(13)C化学位移行为及其与稀土离子的配位作用前人有过报导。但有关水溶液中双甘肽稀土配合物的结构仍不清楚。本文测定了在重稀土离子Dy~(3+)、Ho~(3+)、Er~(3+)、Tm~(3+)和Yb~(3+)作用下双甘肽~(13)C和~1H的顺磁诱导位移,研究了水溶液中双甘肽稀土配合物的组成及结构。1 实验部分

水溶液中羟脯氨酸稀土配合物的NMR研究

测定了在11种稀土离子(La~(3+)、Pr~(3+)、Nd~(3+)、Eu~(3+)、Tb~(3+)、Dy~(3+)、Ho~(3+)、Er~(3+)、Tm~(3+)、Yb~(3+)和Lu~(3+)存在下羟脯氨酸~(13)C的诱导位移和抗磁性稀土配合物体系的~(1)H化学位移与偶合常数。对配合物构象分析表明,在水溶液中羟脯氨酸以空间位阻小的“外向”构象存在,通过羧基与稀土离子形成双齿配位结构,Ln~(3+)-O键长为2.1。在水溶液中巳配位的与游离的氨基酸和水分子间的快速配位交换平衡导致稀土氨基酸配合物具有有效轴对称性。

蛋氨酸稀土配合物构象的~(13)C NMR研究

本文测量了在7种不同稀土离子(La~(3+)、Pr~(3+)、Nd~(3+)、Dy~(3+)、Ho~(3+)、Er~(3+)和Tm~(3+))的水溶液中蛋氨酸~(13)C稀土诱导位移。利用稀土诱导位移对蛋氨酸稀土配合物构象的模拟结果表明,蛋氨酸通过离子化的羧基与稀土离子配位,Ln~(3+)—O长度为2.7A在配合物中,蛋氨酸以伸展状态存在,C_0-C_α-C_β-C_γ和C_α-C_β-C_γ-S成反式构象,C_β-C_γ-S-C_δ成旁式构象。根据稀土诱导位移方法建立的构象模型符合~1H邻位质子偶合常数和~(13)C顺磁弛豫速率的结果。

Domain swapping in the human histamine H-1 receptor

G-protein-coupled receptors (GPCRs) represent the largest family of receptors involved in transmembrane signaling. Although these receptors were generally believed to be monomeric entities, accumulating evidence supports the presence of GPCRs in multimeric forms. Here, using immunoprecipitation as well as time-resolved fluorescence resonance energy transfer to assess protein-protein interactions in living cells, we unambiguously demonstrate the occurrence of dimerization of the human histamine H-1 receptor. We also show the presence of domain-swapped H-1 receptor dimers in which there is the reciprocal exchange of transmembrane domain TM domains 6 and 7 between the receptors present in the dimer. Mutation of aspartate(107) in transmembrane (TM) 3 or phenylalanine(432) in TM6 to alanine results in two radioligand-binding-deficient mutant H-1 receptors. Coexpression of H-1 D(107)A and H-1 F(432)A, however, results in a reconstituted radioligand binding site that exhibits a pharmacological profile that corresponds to the wildtype H-1 receptor. Interestingly, the H-1 receptor radioligands [H-3] mepyramine and [H-3]-(-)- trans-1-phenyl-3-N, N-dimethylamino-1,2,3,4-tetrahydronaphthalene show differential saturation binding values (B-max) for wild-type H-1 receptors but not for the radioligand binding site that is formed upon coexpression of H-1 D(107)A and H-1 F(432)A receptors, suggesting the presence of different H-1 receptor populations.

Synthesis and magnetic characterization of TmCo(2)B(2)C

A new quaternary intermetallic borocarbide TmCo(2)B(2)C has been synthesized via rapid-quench of an arc-melted ingot. Elemental and powder-diffraction analyses established its correct stoichiometry and single-phase character. The crystal structure is isomorphous with that of TmNi(2)B(2)C (I4/mmm) and is stable over the studied temperature range. Above 7 K, the paramagnetic state follows modified Curie-Weiss behavior (chi = C/(T - theta) + chi(0)) wherein chi(0) = 0.008(1) emu mol(-1) with the temperature-dependent term reflecting the paramagnetism of the Tm subsystem: mu(eff) = 7.6(2) mu(B) (in agreement with the expected value for a free Tm(3+) ion) and theta = -4.5(3) K. Long-range ferromagnetic order of the Tm sublattice is observed to develop around similar to 1 K. No superconductivity is detected in TmCo(2)B(2)C down to 20 mK, a feature which is consistent with the general trend in the RCo(2)B(2)C series. Finally, the influence of the rapid-quench process on the magnetism (and superconductivity) of TmNi(2)B(2)C will be discussed and compared to that of TmCo(2)B(2)C.

Structural and optical properties on thulium-doped LHPG-grown Ta(2)O(5) fibres

Structural, spectroscopic and dielectric properties of thulium-doped laser-heated pedestal Ta(2)O(5) as-grown fibres were studied. Undoped samples grow preferentially with a single crystalline monoclinic structure. The fibre with the lowest thulium content (0.1 at%) also shows predominantly a monoclinic phase and no intra-4f(12) Tm(3+) recombination was observed. For sample with the highest thulium amount (1.0 at%), the appearance of a dominant triclinic phase as well as intraionic optical activation was observed. The dependence of photoluminescence on excitation energy allows identification of different site locations of Tm(3+) ions in the lattice. The absence of recombination between the first and the ground-state multiplets as well as the temperature dependence of the observed transitions was justified by an efficient energy transfer between the Tm(3+) ions. Microwave dielectric properties were investigated using the small perturbation theory. At a frequency of 5 GHz, the undoped material exhibits a dielectric permittivity of 21 and for thulium-doped Ta(2)O(5) samples it decreases to 18 for the highest doping concentration. Nevertheless, the dielectric losses maintain a very low value. (C) 2008 Elsevier Ltd. All rights reserved.

Synthesis, characterization and spectroscopic investigation of new tetrakis(acetylacetonato)thulate(III) complexes containing alkaline metals as countercations

In this work a series of tetrakis complexes C[Tm(acac)(4)] where C(+) = Li(+) Na(+) and K(+) countercations and acac = acetylacetonate ligand were synthesized and characterized for photoluminescence investigation The relevant aspect is that these complexes are water-free in the first coordination sphere The emission spectra of the tetrakis Tm(3+)-complexes present narrow bands characteristic of the (1)G(4)->(3)H(6) (479 nm) (1)G(4)->(3)F(4) (650 nm) and (1)G(4) ->(3)H(5) (779 nm) transitions of the Tm(3+) ion with the blue emission color at 479 nm as the most prominent one The lifetime values (tau) of the emitting (1)G(4) level of the C[Tm(acac)(4)] complexes were 344 360 and 400 ns for the Li(+) Na(+) and K(+) countercations respectively showing an increasing linear behavior versus the ionic radius of the alkaline ion An efficient intramolecular energy transfer process from the triplet state (T) of the ligands to the emitting (1)G(4) state of the Tm(3+) ion is observed This fact together with the absence of water molecules in first coordination sphere allows these tetrakis Tm(3+)-complexes to act as efficient blue light conversion molecular devices (c) 2010 Elsevier B V All rights reserved

Influência da elevaçáo transitória e da elevaçáo sustentada da pressáo arterial sobre a primeira derivada temporal da pressáo ventricular.

PURPOSE--To analyze the influence of transient and sustained elevations of arterial pressure (AP) on the rate of rise of the left ventricular pressure (dp/dt). METHODS--Thirteen anesthetized, thoracotomized and mechanically ventilated dogs, submitted to pharmacological autonomic block (oxprenolol-3 mg/kg plus atropine-0.5 mg/kg). The AP elevation was obtained by mechanical constriction of the descending thoracic aorta. Two protocols were applied to all animals: Transient Arterial Hypertension (TAH) and Sustained Arterial Hypertension (SAH) and the following variables were evaluated: heart rate (HR), systolic (LVSP) and end diastolic (LVEDP) left ventricular pressure and dp/dt. In TAH the variables were analyzed in the basal condition (To) and at the maximal value of AP attained during the transient pressure elevation (TM). In the protocol SAH the variables were evaluated in the conditions: Control (Ho), hypertension 1 (H1) and hypertension 2 (H2). RESULTS--Considering all conditions, there were no significant differences among the values of HR. In the protocol TAH, the LVSP varied from 133 +/- 22 mmHg to 180 +/- 27 mmHg, whereas in SAH the values of LVSP were as follow: HO = 129 +/- 25 mmHg; H1 = 152 = 23 mmHg; H2 = 182 +/- 24 mmHg. LVEDP changed in both protocols: To = 7 +/- 2 mmHg; TM = 13 +/- 2 mmHg (p < 0.05); Ho = 7 +/- 2 mmHg; H1 = 10 +/- 2 mmHg; H2 = 14 +/- 3 mmHg (p < 0.05). During TAH there was no difference between the values of dp/dt (To = 3.303 +/- 598 mmHg/s; TM = 3.350 +/- 653 mmHg/s; p > 0.05), however, there were increases of the dp/dt during SAH (Ho = 3.233 +/- 576 mmHg/s; H1 = 3.831 +/- 667 mmHg/s; H1 = 4.594 +/- 833 mmHg/2; p < 0.05). CONCLUSION--The values of dp/dt are not influenced by transient elevation of AP. Sustained increase of AP activates cardiac adjustments, which results in elevation of dp/dt, by stimulation of contractile state. Probably, the inotropic intervention mechanism is the length dependent activation due to the Frank-Starling mechanism.

Tm3+ and Tm3+-Ho3+ doped fluorogermanate glasses for S-band amplifiers

Two series of glasses with composition (mol%) 70PbGeO3- 15PbF2-15CdF2, the first one with different Tm 3+ contents (0.2, 0.4, 0.6 and 0.8 mol%) and the second one with 0.2 mol% Tm3+ and different Ho3+ contents (0.1, 0.5, 1.0 and 1.5 mol%), have been prepared and some of their spectroscopic properties studied. Absorption in the visible-near infrared and emission in the near infrared region of the electromagnetic spectrum have been obtained. Concerning emission at the 1.4-1.5 μm region, optimization of rare earth ions content leads to 0.2 and 0.5 mol% for Tm3+ and Ho3+, respectively. We discuss potential application of these compositions. © 2005 Elsevier B.V. All rights reserved.