Synthesis, Oxidation and Photophysics of Perfluoroborated Tetrakis(pyrophosphito)diplatinate (II) and Density Functional Theory (DFT) Study of Electrochemical CO2 Reduction by Mn Catalysts

In the first part of this thesis (Chapters I and II), the synthesis, characterization, reactivity and photophysics of per(difluoroborated) tetrakis(pyrophosphito)diplatinate(II) (Pt(POPBF₂)) are discussed. Pt(POP-BF₂) was obtained by reaction of [Pt₂(POP)₄]^4- with neat boron trifluoride diethyl etherate (BF₃·Et₂O). While Pt(POP-BF₂) and [Pt₂(POP)₄]^4- have similar structures and absorption spectra, they differ in significant ways. Firstly, as discussed in Chapter I, the former is less susceptible to oxidation, as evidenced by the reversibility of its oxidation by I2. Secondly, while the first excited triplet states (T₁) of both Pt(POP-BF₂) and [Pt₂(POP)₄]^4- exhibit long lifetimes (ca. 0.01 ms at room temperature) and substantial zero-field splitting (40 cm^-1), Pt(POP-BF₂) also has a remarkably long-lived (1.6 ns at room temperature) singlet excited state (S₁), indicating slow intersystem crossing (ISC). Fluorescence lifetime and quantum yield (QY) of Pt(POP-BF₂) were measured over a range of temperatures, providing insight into the slow ISC process. The remarkable spectroscopic and photophysical properties of Pt(POP-BF₂), both in solution and as a microcrystalline powder, form the theme of Chapter II.

In the second part of the thesis (Chapters III and IV), the electrochemical reduction of CO₂ to CO by [(L)Mn(CO)₃]^- catalysts is investigated using density functional theory (DFT). As discussed in Chapter III, the turnover frequency (TOF)-limiting step is the dehydroxylation of [(bpy)Mn(CO)₃(CO₂H)]^0/- (bpy = bipyridine) by trifluoroethanol (TFEH) to form [(bpy)Mn(CO)₄]^+/0. Because the dehydroxylation of [(bpy)Mn(CO)₃(CO₂H)]^- is faster, maximum TOF (TOF_max) is achieved at potentials sufficient to completely reduce [(bpy)Mn(CO)₃(CO₂H)]⁰ to [(bpy)Mn(CO)₃(CO₂H)]^-. Substitution of bipyridine with bipyrimidine reduces the overpotential needed, but at the expense of TOF_max. In Chapter IV, the decoration of the bipyrimidine ligand with a pendant alcohol is discussed as a strategy to increase CO₂ reduction activity. Our calculations predict that the pendant alcohol acts in concert with an external TFEH molecule, the latter acidifying the former, resulting in a ~ 80,000-fold improvement in the rate of TOF-limiting dehydroxylation of [(L)Mn(CO)₃(CO₂H)]^-.

An interesting strategy for the co-upgrading of light olefins and alkanes into heavier alkanes is the subject of Appendix B. The proposed scheme involves dimerization of the light olefin, operating in tandem with transfer hydrogenation between the olefin dimer and the light alkane. The work presented therein involved a Ta olefin dimerization catalyst and a silica-supported Ir transfer hydrogenation catalyst. Olefin dimer was formed under reaction conditions; however, this did not undergo transfer hydrogenation with the light alkane. A significant challenge is that the Ta catalyst selectively produces highly branched dimers, which are unable to undergo transfer hydrogenation.

Efeitos cardiovasculares da transferência adotiva de linfócitos T reguladores em camundongos submetidos à infusão crônica de angiotensina II e de aldosterona

A angiotensina (Ang) II e aldosterona induzem hipertensão arterial por mecanismos em parte mediados pela imunidade adaptativa, envolvendo linfócitos T auxiliares respondedores (Tresp). Os linfócitos T reguladores (Treg) são capazes de suprimir os efeitos próinflamatórios do sistema imune. O presente estudo avaliou se a transferência adotiva de Treg é capaz de prevenir a hipertensão e a lesão vascular induzidas pela Ang II ou pela aldosterona, em dois protocolos distintos. No protocolo com Ang II, camundongos machos C57BL/6 sofreram a injeção endovenosa de Treg ou Tresp, sendo depois infundidos com Ang II (1μg/kg/min), ou salina (grupo controle) por 14 dias. No protocolo com aldosterona, um outro conjunto de animais sofreu injeções de Treg ou Tresp, sendo depois infundido com aldosterona (600μg/kg/d) ou salina (grupo controle), pelo mesmo intervalo de tempo. O grupo tratado com aldosterona recebeu salina 1% na água. Tanto o grupo Ang II como aldosterona apresentaram elevação da pressão arterial sistólica (43% e 31% respectivamente), da atividade da NADPH oxidase na aorta (1,5 e 1,9 vezes, respectivamente) e no coração (1,8 e 2,4 vezes, respectivamente) e uma redução da resposta vasodilatadora à acetilcolina (de 70% e 56%, respectivamente), quando comparados com os respectivos controles (P<0,05). Adicionalmente, a administração de Ang II proporcionou um aumento rigidez vascular (P<0,001), na expressão de VCAM-1 nas artérias mesentéricas (P<0,05), na infiltração aórtica de macrófagos e linfócitos T (P<0,001) e nos níveis plasmáticos das citocinas inflamatórias interferon (INF)-γ, interleucina (IL)-6, Tumor necrosis factor (TNF)-α e IL-10 (P<0,05). Ang II causou uma queda de 43% no número de células Foxp3+ no córtex renal, enquanto que a transferência adotiva de Treg aumentou as células Foxp3+ em duas vezes em comparação com o controle. A administração de Treg preveniu o remodelamento vascular induzido pela aldosterona, observado na relação média/lúmen e na área transversal da média das artérias mesentéricas (P<0,05). Todos os parâmetros acima foram prevenidos com a administração de Treg, mas não de Tresp. Estes resultados demonstram que Treg são capazes de impedir a lesão vascular e a hipertensão mediadas por Ang II ou por aldosterona, em parte através de ações antiinflamatórias. Em conclusão, uma abordagem imuno-modulatória pode prevenir o aumento da pressão arterial, o estresse oxidativo vascular, a inflamação e a disfunção endotelial induzidos por Ang II ou aldosterona.

Early life history studies of Yellowfin tuna, Thunnus albacares. I. Food selection of Yellowfin tuna, Thunnus albacares, larvae reared in the laboratory. II. Age validation and growth of Yellowfin tuna, Thunnus albacares, larvae reared in the laboratory

English: Food selection of first-feeding yellowfin tuna larvae was studied in the laboratory during October 1992. The larvae were hatched from eggs obtained by natural spawning of yellowfin adults held in sea pens adjacent to Ishigaki Island, Okinawa Prefecture, Japan. The larvae were fed mixed-prey assemblages consisting of size-graded wild zooplankton and cultured rotifers. Yellowfin larvae were found to be selective feeders during the first four days of feeding. Copepod nauplii dominated the diet numerically, by frequency of occurrence and by weight. The relative importance of juvenile and adult copepods (mostly cyclopoids) in the diet increased over the 4-day period. Rotifers, although they comprised 31 to 40 percent of the available forage, comprised less than 2.1 percent of the diet numerically. Prey selection indices were calculated taking into account the relative abundances of prey, the swimming speeds of yellowfin larvae and their prey, and the microscale influence of turbulence on encounter rates. Yellowfin selected for copepod nauplii and against rotifers, and consumed juvenile and adult copepods in proportion to their abundances. Yellowfin larvae may select copepod nauplii and cyclopoid juveniles and adults based on the size and discontinuous swimming motion of these prey. Rotifers may not have been selected because they were larger or because they exhibit a smooth swimming pattern. The best initial diet for the culture of yellowfin larvae may be copepod nauplii and cyclopoid juveniles and adults, due to the size, swimming motion, and nutritional content of these prey. If rotifers alone are fed to yellowfin larvae, the rotifers should be enriched with a nutritional supplement that is high in unsaturated fatty acids. Mouth size of yellowfin larvae increases rapidly within the first few days of feeding, which minimizes limitations on feeding due to prey size. Although yellowfin larvae initiate feeding on relatively small prey, they rapidly acquire the ability to add relatively large, rare prey items to the diet. This mode of feeding may be adaptive for the development of yellowfin larvae, which have high metabolic rates and live in warm mixed-layer habitats of the tropical and subtropical Pacific. Our analysis also indicates a strong potential for the influence of microscale turbulence on the feeding success of yellowfin larvae. --- Experiments designed to validate the periodicity of otolith increments and to examine growth rates of yellowfin tuna larvae were conducted at the Japan Sea-Farming Association’s (JASFA) Yaeyama Experimental Station, Ishigaki Island, Japan, in September 1992. Larvae were reared from eggs spawned by captive yellowfin enclosed in a sea pen in the bay adjacent to Yaeyama Station. Results indicate that the first increment is deposited within 12 hours of hatching in the otoliths of yellowfin larvae, and subsequent growth increments are formed dailyollowing the first 24 hours after hatching r larvae up to 16 days of age. Somatic and otolith gwth ras were examined and compared for yolksac a first-feeding larvae reared at constant water tempatures of 26�and 29°C. Despite the more rapid develo of larvae reared at 29°C, growth rates were nnificaifferent between the two treatments. Howeve to poor survival after the first four days, it was ssible to examine growth rates beyond the onset of first feeding, when growth differences may become more apparent. Somatic and otolith growth were also examined for larvae reared at ambient bay water temperatures during the first 24 days after hatching. timates of laboratory growth rates were come to previously reported values for laboratory-reared yelllarvae of a similar age range, but were lower than growth rates reported for field-collected larvae. The discrepancy between laboratory and field growth rates may be associated with suboptimal growth conditions in the laboratory. Spanish: Durante octubre de 1992 se estudió en el laboratorio la seleccalimento por larvaún aleta amarillmera alimentación. Las larvas provinieron de huevos obtenidosel desove natural de aletas amarillas adultos mantenidos en corrales marinos adyacentes a la Isla Ishigaki, Prefectura de Okinawa (Japón). Se alimentó a las larvas con presas mixtas de zooplancton silvestre clasificado por tamaño y rotíferos cultivados. Se descubrió que las larvas de aleta amarilla se alimentan de forma selectiva durante los cuatro primeros días de alimentación. Los nauplios de copépodo predominaron en la dieta en número, por frecuencia de ocurrencia y por peso. La importancia relativa de copépodos juveniles y adultos (principalmente ciclopoides) en la dieta aumentó en el transcurso del período de 4 días. Los rotíferos, pese a que formaban del 31 al 40% del alimento disponible, respondieron de menos del 2,1% de la dieta en número. Se calcularon índices de selección de presas tomando en cuenta la abundancia relativa de las presas, la velocidad de natación de las larvas de aleta amarilla y de sus presas, y la influencia a microescala de la turbulencia sobre las tasas de encuentro. Los aletas amarillas seleccionaron a favor de nauplios de copépodo y en contra de los rotíferos, y consumieron copépodos juveniles y adultos en proporción a su abundancia. Es posible que las larvas de aleta amarilla seleccionen nauplios de copépodo y ciclopoides juveniles y adultos con base en el tamaño y movimiento de natación discontinuo de estas presas. Es posible que no se hayan seleccionado los rotíferos a raíz de su mayor tamaño o su patrón continuo de natación. Es posible que la mejor dieta inicial para el cultivo de larvas de aleta amarilla sea nauplios de copépodo y ciclopoides juveniles y adultos, debido al tamaño, movimiento de natación, y contenido nutritivo de estas presas. Si se alimenta a las larvas de aleta amarilla con rotíferos solamente, se debería enriquecerlos con un suplemento nutritivo rico en ácidos grasos no saturados. El tamaño de la boca de las larvas de aleta amarilla aumenta rápidamente en los primeros pocos días de alimentación, reduciendo la limitación de la alimentación debida al tamaño de la presa. Pese a que las larvas de aleta amarilla inician su alimentación con presas relativamente pequeñas, se hacen rápidamente capaces de añadir presas relativamente grandes y poco comunes a la dieta. Este modo de alimentación podría ser adaptivo para el desarrollo de larvas de aleta amarilla, que tienen tasa metabólicas altas y viven en hábitats cálidos en la capa de mezcla en el Pacífico tropical y subtropical. Nuestro análisis indica también que la influencia de turbulencia a microescala es potencialmente importante para el éxito de la alimentación de las larvas de aleta amarilla. --- En septiembre de 1992 se realizaron en la Estación Experimental Yaeyama de la Japan Sea- Farming Association (JASFA) en la Isla Ishigaki (Japón) experimentos diseñados para validar la periodicidad de los incrementos en los otolitos y para examinar las tasas de crecimiento de las larvas de atún aleta amarilla. Se criaron las larvas de huevos puestos por aletas amarillas cautivos en un corral marino en la bahía adyacente a la Estación Yaeyama. Los resultados indican que el primer incremento es depositado menos de 12 horas después de la eclosión en los otolitos de las larvas de aleta amarilla, y que los incrementos de crecimiento subsiguientes son formados a diario a partir de las primeras 24 horas después de la eclosión en larvas de hasta 16 días de edad. Se examinaron y compararon las tasas de crecimiento somático y de los otolitos en larvas en las etapas de saco vitelino y de primera alimentación criadas en aguas de temperatura constante entre 26°C y 29°C. A pesar del desarrollo más rápido de las larvas criadas a 29°C, las tasas de crecimiento no fueron significativamente diferentes entre los dos tratamientos. Debido a la mala supervivencia a partir de los cuatro primeros días, no fue posibación, uando las diferencias en el crecimiento podrían hacerse más aparentes. Se examinó también el crecimiento somático y de los otolitos para larvas criadas en temperaturas de agua ambiental en la bahía durante los 24 días inmediatamente después de la eclosión. Nuestras estimaciones de las tasas de crecimiento en el laboratorio fueron comparables a valores reportados previamente para larvas de aleta amarilla de edades similares criadas en el laboratorio, pero más bajas que las tasas de crecimiento reportadas para larvas capturadas en el mar. La discrepancia entre las tasas de crecimiento en el laboratorio y el mar podría estar asociada con condiciones subóptimas de crecimiento en el lab

A Low-level Geographic Information System for coastal zone management, with application to Brunei Darussalam. Part II:: Economic analysis of trawling in Brunei Darussalam

Economic analysis of the trawl fishery of Brunei Darussalam was conducted using cost and returns analysis and based on an economic survey of trawlers and B:RUN, a low-level geographic information system. Profitability indicators were generated for the trawl fleet under various economic and operational scenarios. The results show that financial profits are earned by trawlers which operate off Muara, particularly those with high vessel capacity, and that these profits could be further enhanced. On the other hand, a similar fleet operating off Tutong would generate profits due mainly to high fish biomass. Trawling operations offshore are deemed financially unfeasible. Incorporating realistic opportunity costs and externalities for existing trawl operations off Muara results in economic losses.

Síntese e avaliação de hidrogéis à base de alginato e nanopartículas magnéticas preparadas in situ para remoção de Mn(II) e Ni(II) de efluente industrial

Esta Dissertação teve como objetivo,a síntese de hidrogéis à base de alginato e nanopartículas magnéticas (maghemita) preparadas in situ. Os hidrogéis foram preparados em diferentes concentrações de alginato de sódio (2 e 3% m/v), FeSO4 (0,3 e 0,5 mol L-1) e CaCl2 (0,1 e 0,3 mol L-1). As propriedades físico-químicas dos hidrogéis foram analisadas e, posteriormente, foram avaliados quanto à capacidade de remoção de íons Ni2+ e Mn2+ de soluções aquosas. Para caracterização das amostras foram utilizadas diversas técnicas de análises, tais como, análise granulométrica, microscopia óptica (OM), microscopia eletrônica de varredura (SEM), microscopia eletrônica de transmissão (TEM), magnetometria de amostra vibrante (VSM), espectroscopia na região do infravermelho por transformada de Fourier (FTIR), difratometria de raios-X (XRD), espectroscopia Mössbauer, e análise termogravimétrica (TGA). Foram preparados hidrogéis com morfologia predominantemente esférica e dimensões micrométricas (500 a 850 m), com átomos de Fe e Ca dispersos uniformemente em sua estrutura. Os hidrogéis apresentaram boa resistência térmica e comportamento superparamagnético. As amostras foram intumescidas em água deionizada durante um intervalo de tempo a fim de avaliar o grau de intumescimento (Q) para determinar a amostra com a melhor resposta para posterior aplica��ão em solução aquosa contendo íons metálicos (Ni2+ e Mn2+). Os resultados revelaram que a amostra cuja concentração de 3% m/v de alginato de sódio, 0,3 mol L-1 de FeSO4 e 0,3 mol L-1 de CaCl2 obteve maior Q (50%). Em consequência deste resultado, optou-se por utilizar estaamostra, na remoção de metais pesados presentes em soluções aquosas e em efluentes industriais. Vários parâmetros,tais como: tempo de contato,pH, concentração inicial do íon e massa de hidrogel foram estudados.Os resultados, para efluente sintético, revelaram que o tempo de equilíbrio foi de 60 minutos; a capacidade de remoção dos metais melhora com o aumento de pH (3 a 9), sendo máxima em pH 7;quanto menor a concentração inicial da solução iônica (50 a 500 mg L-1), maior a capacidade de remoção, 52% de Ni2+ e 49% de Mn2+ (concentração inicial de 50 mg L-1). No efluente industrial, a remoção foi de 61% de Ni2+ e 57% de Mn2+(300 mg de hidrogel). Os resultados encontrados revelaram que os hidrogéis magnéticos produzidos à base de alginato têm potencial uso no tratamento de efluentes industriais contaminados com metais pesados

I.小麦非叶器官碳酸酐酶活性与定位分析II.镉毒害导致芦苇胚性细胞死亡的激素调控研究

第一部分： 通过生理测定和化学染色分析了冬小麦品种小堰54和京411的叶片和非叶片组织的碳酸酐 酶活性。叶片碳酸酐酶活性(CA)在挑旗时期达到最大值，之后减少到最小，而在饱粒期又呈 增加趋势。从灌浆期到饱粒期，颖片和内稃的CA���性均减少，而外稃和种皮的CA���性均增加。在饱粒期，小堰54的叶片、颖片、外稃和种皮CA���性均高于京411。组织化学染色表明，CA���要分布在旗叶的叶肉细胞叶绿体中，也分布在非叶片组织颖片、外稃和内稃的叶肉和维管束鞘细胞的胞质中。这些结果表明，小麦非叶组织叶肉和维管束鞘细胞的胞质中的CA���能对饱粒期冬小麦的C4光合途径起作用。饱粒期小堰54的C02传递到Rubisco酶速率和抗旱性较京411高。 第二部分： 以继代培养的芦苇胚性细胞为材料，利用台盼兰拒染法检测了悬浮细胞死亡过程，并利用石蜡切片法及苏木精染色法观察了不同浓度镉对芦苇细胞的毒害作用。1000μM的CdCl2迅速导致芦苇悬浮细胞死亡，200μM的CdClz在接种后第5天引起悬浮细胞死亡，100μM的CdCl2在接种后第7天引起悬浮细胞死亡，≤50μM的CdClz在接种后7天不引起悬浮细胞死亡。同时对不同浓度镉处理的芦苇胚性细胞的内源植物激素和可溶性蛋白质进行分析，≤50μM的镉浓度显著地降低胚性细胞内IAA、ZR、GA3和GA4的含量，却提高ABA的含量，抑制可溶性蛋白质的合成：≥100μM的镉浓度显著地提高IAA、ZR、GA3和GA4的含量，却降低ABA的含量，促进可溶性蛋白质的合成。这些结果表明，镉的毒害至少包括镉浓度决定的两种细胞死亡机制，高浓度的镉(1000μM)引起的细胞死亡应当为坏死，而100μM的镉引起植物悬浮细胞发生程序性死亡。在较高浓度(≥100μM)的镉处理下，芦苇细胞内内源IAA、ZR、GA3和GA4的浓度较高，可能调控可溶性蛋白质的合成而促进细胞发生程序化死亡。

光系统II放氧复合物的光组装研究

本论文研究了一系列具有不同配位环璄的锰化合物与去锰的PSII的光组装过程，得到了以下主要结果： 1. 分别对两组二核锰化合物与去锰的PSII 颗粒进行了重组研究。第一组的两个二核锰化合物中，锰原子具有相同的外围配体、氧化还原状态，但是不同的连接方式;而第二组的两个二核锰化合物中，锰原子具有相同的连接方式、氧化还原状态，但是不同的外围配体。实验结果表明，锰化合物中两个锰原子之间的连接方式及外围配体的不同都可以导致锰簇光组装效率的不同，但这两种因素引起的光组装效率的差异比锰原子的氧化还原状态引起的差别要小的多。因此我们推断，锰原子的氧化还原状态是影响光组装效率最重要的因素之一。 2. 选择了三个四核锰化合物与去锰PSII 颗粒进行重组，测定其电子传递与放氧活性。研究结果表明，具有较少配体和较小分子的两个化合物H568和WM01具有较高的重组活性，而另一个化合物Z342的活性较低。这说明化合物配体的数目以及分子的大小影响了光组装效率。另外, 化合物H568和WM01在重组过程中对CaCl2也比Z342更敏感，推测这可能是因为这两个锰化合物中有更多的的羧基可以与Ca2+发生相互作用，而这种作用有助于锰的配位，进而促进光组装。 3. 研究了Mn/Ca���簇合物与去锰的PSII 颗粒的光重组, 研究发现，尽管化合物wwg-27本身就含有Ca���成分，但它在与光系统II的光组装过程中仍然表现为外源Ca���要的趋势，而且这一化合物也表现了比MnCl2更高的光组装效率。 4. 研究了MnCl2与去锰PSII 颗粒的重组过程中，组氨酸和酪氨酸的存在对光组装效率的影响。 研究结果表明，加入一定量的组氨酸和酪氨酸均可以明显的提高样品的放氧活性，并且这两种氨基酸对光组装效率的影响均与pH值有关。

Nutritive value of fishes of Lake Tanganyika: II. Mineral composition

The composition of the minerals in three economically important fish species of Lake Tanganyika was determined. From the analyses there does not appear to be significant difference in the composition for the three species. Beside the major elements: Ca, P, K, Na, Mg, Cl, Fe, Al and Zn, eighteen trace elements were determined. The presence of the bones in the fish is especially nutritionally important for the following elements: Ca, P, Br, Sr, Mn and Mg.

铕（II）等低价稀土离子在氧化物基质中光谱特征及其变化规律

近年来，围绕低价稀土离子开展的研究工作越来越多，尤其重视铕(II)、钐（II）和镱(II)的研究，以期获得短波可调固体激光晶体或高效率发光材料。由于4f~n到4f~(n-1)5d'组态的d-f跃迁是属于宇称允许的跃迁，所以它的发射要比4f~n壳层内的受迫电偶极跃迁强得多。这可以保证对泵浦的有效吸收，提高光泵效率。而4f~n组态内部的f-f锐线发射可以实现激光振荡，有利于提高储能，降低阀值。所以深入了解4f~n和 4f~(n-1)5d'体系在基质晶场中的行为以及基质环境对稀土离子发光特征的影响，对于寻找和设计新的激光和发光材料有着极为重要的意义。 本文从理论上讨论了晶场效应和化学键性质对铕(II)、钐(II)等稀土离子发光性质的影响。采用高温固相反应的方法合成了一系列铕(II)、钐(II)激活的氧化物基质荧光材料。结合光谱实验数据建立了晶格环境对铕(II)的 4f~65d'能级影响的表观模型和定量计算公式。为了研究4f~65d'激发态的性质，我们采用改进的Slater法计算了铕(II)和配体氧的有关轨道能量。利用静电晶场模型讨论了4f~65d'能带劈裂幅度(△E)与Eu-O键距(R)的关系，量子化学计算表明5d能级在晶场中的劈裂(△E)与R~5成反比。碱金属和碱七金属磷酸盐基质中铕的光谱数据证实了上述结论。在该基质中铕的4f~65d'能带的劈裂幅度随Eu-O键距增加而变小。在MeSO_4:Eu~(2+) (Me = Ca, Sr，Ba)中，随碱七金属离子半径增大，其发射和激发截止波长均有规律地向短波区移动。这是由于当铕(II)占据较大半径阳离子格位时，将受到较小的晶场影响。其体系的荧光寿命数据也证实了这一点。运用统计热力学原理讨论了4f~(n-1)5d'与 4f~n激发态能级的相对位置对低价稀土离子d-f和f-f跃迁发射的影响。在Ba_(1-x)Mg_(1+x)(SO_4):Eu~(2+)中，适当增大Mg~(2+)离子含量，线一带两种发射强度比R = I (f-f)/I(d-f) 明显增大。Ba_(0.4)Mg_(1.6)(SO_4)_2:Eu~(2+)的f-f锐线发射强度最大。在Ba_(1-x)Sr_xMg(SO_4)_2:Eu~(2+)中，铕(II)的f-f强度随x增大而变小，d-f发射峰则随x增加而发生红移。运用“电子云扩展效应”和鲍林化学键原理解释了，在Na_(3-x)(PO_4)_(1-x)(SO_4)_x:Eu~(2+)和Na_(2-x)CaSi_(1-x)P_xO_4:Eu~(2+)体系中，随X值在固溶区内变大，铕(II)的发射光谱逐渐移向短波区的现象。为了研究稀七离子的取代格位对其光谱性质的影响，我们合成了K_2Mg_2(SO_4)_3:Eu~(2+)单晶化合物。并经四圆衍射仪解出了结构。铕(II)在单晶中占据Mg_1~(2+)格位，与KMgF_3:Eu~(2+)相比，它将受到更强的晶场作用使4f~65d'能带劈裂幅度变大，又通过计算可知，Eu-O键的共价性比Eu-F键更强，因而在K_2Mg_2(SO_4)_3中Eu~(2+) 4f~65d'重心更低一些。综上所述，K_2Mg_2(SO_4)_3:Eu~(2+)的发射能级(E_(em)~m)要比KMgF_3:Eu~(2+)的发射能级更低。光谱实验数据证实了这一结论。用245 nm激发， K_2Mg_2(SO_4)_3:Eu~(2+)发兰光，最大中心处于400 nm。而KMgF_3:Eu~(2+)发紫色或近紫外光(E_(em)~m = 363 nm)，并且在后者是观察到Eu~(2+)离子的f-f跃迁锐线发射。采用高温氢气还原法制备了SmF_2和SmCl_2作为离子激活源。钐(II)激活的硫酸盐材料的荧光光谱数据表明，在室温条件下该基质中钐(II)的荧光光谱均为4f~55d' → 4f~6跃迁的宽带发射。论文对铕(II)，钐(II)等低价稀土离子的4f~(n-1)5d'激发态性质和稀七离子在基质中的格位取代以及电荷补偿效应也作了较为详细的讨论。

复合氟化物中Eu（II）和某些稀土离子之间能量传递的研究

掺稀土离子的碱土稀土复合氟化物和ABF_3钙钛矿型氟化物是重要的激光和发光材料。Eu(II)是重要的激活离子。利用Eu(II) d→f跃迁的宽带发射和f→f跃迁的锐线发射，Eu(II)作为短波紫外激光材料手荧光材料的激活剂是优良的候选新。因此，如能找到某种敏化剂对Eu(II)产生能量传递，提高d→f或f→f跃迁发射效率，那么对Eu(II)的潜在应用具有重要的实际和理论意义。人们对Eu(II) d-f、f-f跃迁性度和实现f-f跃迁的条件以及Eu(II)对其它离子的纯量传递已进行了许多深入的研究。然而，人们对其它离子对Eu(II)的纯量传递的研究和报道则甚少。本文从研究Eu(II)和Ce(III)在xMF_2-yYF_3 （M = Ca���Sr，Ba；x = 0，1，2，3；y = 0，1，2，3，4，5）和ABF_3（A = K~+，Ba~(2+)；B = Mg~(2+)，Ca~(2+)，Li~+）两体系中的光谱变经规律入手，比较和分析了Eu(II)和Ce(III)的光谱行为及期 影响因素，特别是仔细地考察了氧对Eu(II)光谱的影响。通过比较和分析，指出Ce(III)对Eu(II)产生能量传递的可能性，寻求两新相互敏化的合适的基质。在复合氟化物体系中首次实现了Ce(III)对Eu(II)的能量传递。根据Dexter能量传递共振理论讨论和分析了Ce(III)对Eu(II)能量传递机理和可能传递途径，提出了能量传递模型，估算了各种传递过程的几率，获取了一些有益启示。同时，对Eu(II)和Tb(III)之间的能量传递也做了初步讨论。与某些基质中Tb(III)可对Ce(III)产生能量传递不同，在讨论体系中没有观察到Tb(III)对Eu(II)的能量传递。

Highly efficient electrochemiluminescence of functionalized tris(2,2 '-bipyridyl)ruthenium(II) enrichment of its co-reactants

An enhanced electrochemiluminescence (ECL) efficiency is obtained from the ruthenium complex tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) by introduction of an ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF(4)). Upon addition of 1% (v/v) BMImBF(4) to 0.1 mm Ru(bpy)(3)(2+) solution, a maximum increase in ECL intensity is obtained both at an indium tin oxide (ITO) electrode (15-fold) and at a glassy carbon (GC) electrode (5- to 64old). Furthermore, upon addition of 1% (v/v) BMImBF4 to 5 pm Ru(bpy)(3)(2+)/100 mm co-reactant systems at a GC electrode, IL adsorption occurs at the electrode surface, which results in a change of the polarity of the electrode surface. Such functionalization greatly improves the functions of both Ru(bpy)(3)(2+) and ionic liquids, as is demonstrated in the sensitive and selective concentration enrichment of the Ru(bpy)(3)(2+) co-reactants.

Syntheses and ethylene polymerization behavior of supported salicylaldimine-based neutral nickel(II) catalysts

Two novel salicylaldimine-based neutral nickel(II) complexes, [(2,6-iPr(2)C(6)H(3))NCH(2-ArC6H3O)]Ni(PPh3)Ph (6, Ar = 2-(OH)C6H4; 8, Ar = 2-OH-3-(2,6-iPr(2)C(6)H(3)NCH)C6H3), have been synthesized, and their structures have also been confirmed by X-ray crystallography, elemental analysis, and H-1 and C-13 NMR spectra. An important structural feature of the two complexes is the free hydroxyl group, which allows them to react with silica pretreated with trimethylaluminum under immobilization by the formation of a covalent bond between the neutral nickel(II) complex and the pretreated silica. As active single-component catalysts, the two complexes exhibited high catalytic activities up to 1.14 and 1.47 x 10(6) g PE/mol(Ni)center dot h for ethylene polymerization, respectively, and yielded branched polymers. Requiring no cocatalyst, the two supported catalysts also showed relatively high activities up to 4.0 x 10(5) g PE/mol(Ni)center dot h and produced polyethylenes with high weight-average molecular weights of up to 120 kg/mol and a moderate degree of branching (ca. 13-26 branches per 1000 carbon atoms).

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.