Thermodynamics of higher spin black holes in 3D

We examine the thermodynamic properties of recently constructed black hole solutions in SL(3, R) x SL(3, R) Chern-Simons theory in the presence of a chemical potential for spin-3 charge, which acts as an irrelevant deformation of the dual CFT with W-3 X W-3 symmetry. The smoothness or holonomy conditions admit four branches of solutions describing a flow between two AdS(3) backgrounds corresponding to two different CFTs. The dominant branch at low temperatures, connected to the BTZ black hole, merges smoothly with a thermodynamically unstable branch and disappears at higher temperatures. We confirm that the UV region of the flow satisfies the Ward identities of a CFT with W-3((2)) x W-3((2)) symmetry deformed by a spin-3/2 current. This allows to identify the precise map between UV and HI thermodynamic variables. We find that the high temperature regime is dominated by a black hole branch whose thermodynamics can only be consistently inferred with reference to this W-3((2)) x W-3((2)) CFT.

Higher spin entanglement entropy from CFT

We consider free fermion and free boson CFTs in two dimensions, deformed by a chemical potential mu for the spin-three current. For the CFT on the infinite spatial line, we calculate the finite temperature entanglement entropy of a single interval perturbatively to second order in mu in each of the theories. We find that the result in each case is given by the same non-trivial function of temperature and interval length. Remarkably, we further obtain the same formula using a recent Wilson line proposal for the holographic entanglement entropy, in holomorphically factorized form, associated to the spin-three black hole in SL(3, R) x SL(3, R) Chern-Simons theory. Our result suggests that the order mu(2) correction to the entanglement entropy may be universal for W-algebra CFTs with spin-three chemical potential, and constitutes a check of the holographic entanglement entropy proposal for higher spin theories of gravity in AdS(3).

平台用高强度钢多次补焊及TIG熔修的疲劳分析

海洋石油平台在服役期内，由于受到各种环境载荷的交变作用，其受力的焊接构件不可避免地会出现疲劳裂纹。对出现的疲劳裂纹进行补焊修复，可以延长平台的使用期，带来巨大的经济和社会效益。本文通过实验研究，考察了多次补焊对海洋平台用高强度钢焊接接头疲劳性能的影响，以及是否可以通过TIG熔修工艺的采用提高补焊构件的疲劳寿命，达到延长补焊后平台的使用寿命，减少补焊次数的目的。本文涉及的主要研究内容如下：1、考察了多次补焊对焊接接头疲劳寿命的影响。通过对平台用高强度钢焊接接头初焊试样，以及重复三次补焊试样的疲劳实验，得到了各次补焊试样在对数正态分布和威布尔分布下的寿命估算式和考虑了存活率的R-S-N曲线。对实验结果进行了比较和分析，从而考察了多次补焊对焊接接头疲劳性能的影响。2、在每次补焊后，由于焊趾外移造成了焊趾角的变化，使得焊趾处的应力集中系数发生了变化。本文采用有限元方法计算了试样的应力场分布，得到了焊趾处的应力集中系数与焊趾角的关系。考虑到应力集中系数的变化后，对多次补焊试样疲劳实验的实验数据进行了重新处理。3、考察了多次补焊熔修对焊接接头疲劳寿命的影响。本文通过对平台用高强度钢焊接接头补焊及补焊熔修试样的疲劳实验，得到了多次补焊和补焊熔修试样对数正态分布和威布尔分布下的寿命估算式和考虑了存活率的R-S-N曲线。对实验结果进行了比较和分析，从而考察了补焊后采用TIG熔修工艺对焊接接头疲劳性能的影响。4、一次补焊后进行熔修处理可以极大的改善试样的疲劳性能，提高试样的疲劳寿命。但这一结果是在平焊位条件下得出了。为了将这一结果用于实际，还要考察实际操作中大量采用的立焊位条件下熔修的效果。本文完成了立焊位条件下补焊及补焊熔修试样的疲劳实验，得到了相应的S-N曲线。5、疲劳实验数据的处理中，大量采用威布尔分布作为数据统计的分布类型。但由于威布尔分布具有三个参数，给求解带来一定的困难。本文提出一种以在威布尔坐标纸上，数据分布的线形相关系数作为判据的求解威布尔参数的方法，并通过程序加以实现。为了对疲劳实验数据的处理更加方便和直观，编制了“疲劳实验数据处理程序“，将对疲劳实验数据的编辑、分布参数的求解、不同存活率下的疲劳寿命估算和各种分布类型图以及R-S-N曲线的绘制工作包括在该程序中。

Ancillary ligand effects : from zirconium(IV)-catalyzed homogeneous propylene polymerization to platinum(II)-mediated C-H bond activation

A series of C_s- and C₁-symmetric doubly-linked ansa-metallocenes of the general formula {1,1'-SiMe₂-2,2'-E-('ƞ⁵-C₅H₂-4-R¹)-(ƞ⁵-C₅H-3',5'-(CHMe₂)₂)}ZrC₂ (E = SiMe₂ (1), SiPh₂ (2), SiMe₂ -SiMe₂ (3); R¹ = H, CHMe₂, C₅H₉, C₆H₁₁, C₆H₅) has been prepared. When activated by methylaluminoxane, these are active propylene polymerization catalysts. 1 and 2 produce syndiotactic polypropylenes, and 3 produces isotactic polypropylenes. Site epimerization is the major pathway for stereoerror formation for 1 and 2. In addition, the polymer chain has slightly stronger steric interaction with the diphenylsilylene linker than with the dimethylsilylene linker. This results in more frequent site epimerization and reduced syndiospecificity for 2 compared to 1.

C₁-Symmetric ansa-zirconocenes [1,1 '-SiMe₂-(C₅H₄)-(3-R-C₅H₃)]ZrCl₂ (4), [1,1 '-SiMe₂-(C₅H₄)-(2,4-R₂-C₅H₂)]ZrCl₂ (5) and [1,1 '-SiMe₂-2,2 '-(SiMe₂-SiMe₂)-(C₅H₃)-( 4-R-C₅H₂)]ZrCl₂ (6) have been prepared to probe the origin of isospecificity in 3. While 4 and 3 produce polymers with similar isospecificity, 5 and 6 give mostly hemi-isotactic-like polymers. It is proposed that the facile site epimerization via an associative pathway allows rapid equilibration of the polymer chain between the isospecific and aspecific insertion sites. This results in more frequent insertion from the isospecific site, which has a lower kinetic barrier for chain propagation. On the other hand, site epimerization for 5 and 6 is slow. This leads to mostly alternating insertion from the isospecific and aspecific sites, and consequently, a hemi-isotactic-like polymers. In comparison, site epimerization is even slower for 3, but enchainment from the aspecific site has an extremely high kinetic barrier for monomer coordination. Therefore, enchainment occurs preferentially from the isospecific site to produce isotactic polymers.

A series of cationic complexes [(ArN=CR-CR=NAr)PtMe(L)]⁺[BF₄]⁺ (Ar = aryl; R = H, CH₃; L = water, trifluoroethanol) has been prepared. They react smoothly with benzene at approximately room temperature in trifluoroethanol solvent to yield methane and the corresponding phenyl Pt(II) cations, via Pt(IV)-methyl-phenyl-hydride intermediates. The reaction products of methyl-substituted benzenes suggest an inherent reactivity preference for aromatic over benzylic C-H bond activation, which can however be overridden by steric effects. For the reaction of benzene with cationic Pt(II) complexes, in which the diimine ligands bear 3,5-disubstituted aryl groups at the nitrogen atoms, the rate-determining step is C-H bond activation. For the more sterically crowded analogs with 2,6-dimethyl-substituted aryl groups, benzene coordination becomes rate-determining. The more electron-rich the ligand, as reflected by the CO stretching frequency in the IR spectrum of the corresponding cationic carbonyl complex, the faster the rate of C-H bond activation. This finding, however, does not reflect the actual C-H bond activation process, but rather reflects only the relative ease of solvent molecules displacing water molecules to initiate the reaction. That is, the change in rates is mostly due to a ground state effect. Several lines of evidence suggest that associative substitution pathways operate to get the hydrocarbon substrate into, and out of, the coordination sphere; i.e., that benzene substitution proceeds by a solvent- (TFE-) assisted associative pathway.

Germanene: a novel two-dimensional germanium allotrope akin to graphene and silicene

We have grown an atom-thin, ordered, two-dimensional multi-phase film in situ through germanium molecular beam epitaxy using a gold (111) surface as a substrate. Its growth is similar to the formation of silicene layers on silver (111) templates. One of the phases, forming large domains, as observed in scanning tunneling microscopy, shows a clear, nearly flat, honeycomb structure. Thanks to thorough synchrotron radiation core-level spectroscopy measurements and advanced density functional theory calculations we can identify it as a root 3 x root 3 R(30 degrees) germanene layer in conjunction with a root 7 x root 7 R(19.1 degrees) Au(111) supercell, presenting compelling evidence of the synthesis of the germanium-based cousin of graphene on gold.

Ultrabroad infrared luminescences from Bi-doped alkaline earth metal germanate glasses

We report on ultrabroad infrared (IR) luminescences covering the 1000-1700-nm wavelength region, from Bi-doped 75GeO(2) 20RO-5Al(2)O(3) 1B(2)O(3) (R = Sr, Ca, and Mg) glasses. The full width at half-maximum of the IR luminescences excited at 980 nm increases (315 -> 440 -> 510 nm) with the change of alkaline earth metal (Mg2+ -> Ca2+ -> Sr2+). The fluorescence lifetime of the glass samples is 1725, 157, and 264 mu s when R is Sr, Ca, and Mg, respectively. These materials may be promising candidates for broad-band fiber amplifiers and tunable laser resources.

Jogos narrativos de videogame: criação e manutenção do estado de imersão

O objetivo deste trabalho é entender como o jogo narrativo de aventura para videogame consegue atrair e manter a atenção do jogador, imergindo-o no mundo ficcional, em face dos inúmeros estímulos existentes a sua volta. É sugerida uma definição para o jogo narrativo de aventura e a imersão e, posteriormente, estabelece-se uma relação entre elementos presentes nos jogos e as estruturas que atraem a atenção do indivíduo. Para isso, consultou-se material produzido pelas duas principais linhas de estudos de jogos: Narratologia e Ludologia. O conteúdo teórico foi comparado e exemplificado através da prática de diversos jogos, principalmente do console Sony Playstation 3. O próprio conceito de jogo narrativo, a prática dos jogos e a relação percebida entre seus elementos e as ferramentas para criar e manter a atenção revelaram que o videogame, através dos jogos narrativos de aventura, representa um potente meio para criar e manter o estado de imersão sobre o jogador.

Custo-efetividade da Terapia Tripla para pacientes adultos portadores do genótipo 1 da hepatite C crônica.

As ações de prevenção, diagnóstico e tratamento da hepatite C crônica integram as agendas das políticas de saúde do Brasil e do mundo, pois se trata de uma doença com grande número de acometidos, com alto custo tratamento e que ocasiona graves desfechos e incapacidade, o que acaba por onerar seu custo social. Os protocolos clínicos e diretrizes terapêuticas demonstram os esforços de inúmeras entidades no combate da hepatite C, pois informam aos profissionais de saúde, pacientes e familiares e cidadãos em geral, qual seria a melhor forma, comprovada cientificamente, de se proceder frente a uma infecção desta natureza. Realizouse uma análise de custoefetividade, sob a perspectiva do SUS, das estratégias: tratamento e retratamento com a terapia dupla, tratamento com a terapia dupla e retratamento com a terapia tripla e tratamento com a terapia tripla. Através de modelo de simulação baseado em cadeias Markov foi criada uma coorte hipotética de 1000 indivíduos adultos, acima de 40 anos, de ambos os sexos, sem distinção declasse socioeconômica, com diagnóstico confirmado para hepatite C crônica, monoinfectados pelo genótipo 1 do VHC e com ausência de comorbidades. A simulação foi iniciada com todos os indivíduos portando a forma mais branda da doença, tida como a classificação histológica F0 ou F1 segundo a escala Metavir. Os resultados demonstram que as duas opções, ou seja, a terapia dupla/tripla e a terapia tripla estão abaixo do limiar de aceitabilidade para incorporação de tecnologia proposto pela OMS (2012) que é de 72.195 (R$/QALY) (IBGE, 2013; WHO, 2012). Ambas são custoefetivas, visto que o ICER da terapia dupla/tripla em relação alinha de base foi de 7.186,3 (R$/QALY) e o da terapia tripla foi de 59.053,8 (R$/QALY). Entretanto o custo incremental de terapia tripla em relação à dupla/tripla foi de 31.029 e a efetividade incremental foi de 0,52. Em geral, quando as intervenções analisadas encontramse abaixo do limiar, sugerese a adoção do esquema de maior efetividade. A terapia tripla, apesar de ter apresentado uma efetividade um pouco acima da terapia dupla/tripla, apresentou custo muito superior. Assim, como seria coerente a adoção de uma ou da outra para utilização no SUS, visto que este sistema apresenta recursos limitados, indicase a realização de um estudo de impacto orçamentário para obterse mais um dado de embasamento da decisão e assim poder apoiar o protocolo brasileiro existente ou sugerir a confecção de novo documento.

迷迭香（Rosmarinus officinalis L.）精油和抗氧化剂的研究

本文应用植物引种驯化，栽培学及植物化学的理论方法对引入我国的迷迭香（Rosmarinus officinalisL．）精油和抗氧化剂进行了研究．主要结果如下; 1、昆明地区的生态气候条件最适宜迷迭香生长。南京地区局部良好环境也能满足迷迭香正常生长需要。北京地区在保护栽培的情况下,迷迭香才能够安全越冬。 2、用GC-MS和GC-IR鉴定了迷迭香精油的23种成分。不同采收期精油成分含量变化有3种类型，即似单峰曲线，似8曲线和w曲线。一年生与二年生苗在精油成分含量上略有差异。与主要栽培国相比，我国不同引种地精油成分化学类型各具特点，北京地区α—蒎稀（31.58%）含量很高，南京地区富含樟脑（14.86%）乙酸龙脑酯（7.97%）和龙脑（6.90%）含量也相对较高，昆明地区则是α—蒎稀（24.32%）和1.8—桉叶油素（24.43%）含量并重。 乙酸龙脑酯含量的高低对精油香气质量优劣起关键作用。北京地区雨季来临收获（7月初）精油香气质量最好。南京地区，11月初精油香气质量也属优质。本实验未能得到高质量的昆明地区精油。 3、从迷迭香蒸油残渣中分离得到三种抗氧化成分，迷迭香酚( Rosrmanol)、鼠尾草酚(Carnosol)和迷迭香双醛（R0smadial），并用质谱，核磁做了鉴定．硫氰铁酸法、TBA法、AOM法检测了三种成分的抗氧化效能．Rosmanol对多双键不饱和脂肪酸抗氧化效果显著,Carnosol和BHT在不同双键脂肪酸中抗氧化效果稳定，Rosmadial的抗氧化效果则随不饱和双键数目的增加而降低。在猪油中，抗氧化效能的强度顺序为Rosmanol >carnosol>BR>Rosmadial。 抗氧化物质在植株体内是不断积累的。不同引种地迷选香抗氧化效能的强弱差异表现为昆明>北京>南京。 迷迭香的正己烷，两酮提取物抗氧化效能都是随着添加量的增加而增强、丙酮提取物的抗氧化效能优于正己烷提取物。 对迷迭香抗氧化剂提取工艺做了探讨，得到R-1，R—2，R-3三种小试样品，R-2，R-3的抗氧化效果优于BHT．B—l接近于BET。

臭蛙群三种蛙类核型及染色体带型的比较(英文)

本文比较了3种臭蛙,即云南臭蛙（R. andersonii）、无指盘臭蛙（R.grahami）和滇南臭蛙（R.tiennanensis）的核型、C-带和银染核仁组织者区（Ag-NORs）。结果表明,3种臭蛙的核型均为2n=26（NF=52）,由5对大型染色体和8对小型染色体组成,与蛙科大多数种类的核型相似,但是染色体形态和次缢痕的位置和数目有差异。其中,云南臭蛙和无指盘臭蛙的核型相似程度比较大,与其他已报道的臭蛙类的核型相差不大,而滇南臭蛙的核型比较特殊,与其他臭蛙类的核型存在显著差异。 C-带技术显示的结果表明,3种臭蛙所有染色体的着丝点都有比较显著的C-带,而居间区C-带和端点C-带却存在明显的差异。3种中,滇南臭蛙的C-带带型比较特殊。有趣的是在研究中还发现,云南臭蛙的早中期细胞（染色体很长）染色体上发现了很多结构异染色质区,除着丝点C-带外,几乎所有的染色体上都有居间区或端点C-带,而在晚中期细胞中所观察到的C-带数目却较少,除着丝点外,只在少数染色体上发现了C-带。 云南臭蛙和无指盘臭蛙的Ag-NORs位于第10对染色体的长臂上,与该染色体上的次缢痕位置相对应,而滇南臭蛙的Ag-NORs位于第6...

Growth and energy budget of F-2 'all-fish' growth hormone gene transgenic common carp

The growth and energy budget for F-2 'all-fish' growth hormone gene transgenic common carp Cyprinus carpio of two body sizes were investigated at 29.2 degrees C for 21 days. Specific growth rate, feed intake, feed efficiency, digestibility coefficients of dry matter and protein, gross energy intake (I-E), and the proportion of I-E utilized for heat production (H-E) were significantly higher in the transgenics than in the controls. The proportion of I-E directed to waste products [faecal energy (F-E) and excretory energy loss (Z(E) + U-E) where Z(E) is through the gills and U-E through the kidney], and the proportion of metabolizable energy (M-E) for recovered energy (R-E) were significantly lower in the transgenics than in the controls. The average energy budget equation of transgenic fish was as follows: 100 I-E = 19.3 F-E + 6.0 (Z(E) + U-E) + 45.2 H-E + 29.5 R-E or 100 M-E = 60.5 H-E + 39.5 R-E. The average energy budget equation of the controls was: 100 I-E = 25.2 F-E + 7.4 (Z(E) + U-E) + 35.5 H-E + 31.9 R-E or 100 M-E = 52.7 H-E + 47.3 R-E. These findings indicate that the high growth rate of 'all-fish' transgenic common carp relative to their non-transgenic counterparts was due to their increased feed intake, reduced lose of waste productions and improved feed efficiency. The benefit of the increased energy intake by transgenic fish, however, was diminished by their increased metabolism.

Complex networks constructed from irrational number sequences

In this paper, we construct (d, r) networks from sequences of different irrational numbers. In detail, segment an irrational number sequence of length M into groups of d digits which represent the nodes while two consecutive groups overlap by r digits (r = 0,1,...,d-1), and the undirected edges indicate the adjacency between two consecutive groups. (3, r) and (4, r) networks are respectively constructed from 14 different irrational numbers and their topological properties are examined. By observation, we find that network topologies change with different values of d, r and even sequence length M instead of the types of irrational numbers, although they share some similar features with traditional random graphs. We make a further investigation to explain these interesting phenomena and propose the identical-degree random graph model. The results presented in this paper provide some insight into distributions of irrational number digits that may help better understanding of the nature of irrational numbers.

园二色谱电化学及其在结构生物电化学研究中的应用

将生物电化学与目前生物学的主流学科一结构生物学相结合，形成了结构生物电化学，以研究生物大分子在电化学过程中的结构变化规律及其对其电化学活性，生物活性和生理功能的影响．将园二色谱与电化学技术相结合称为园二色谱电化学，是结构生物电化学研究中的重要工具之一，它不仅为结构生物学研究提供了新的途径，而且为生物电化学开辟了新的研究领域．本论文在结构生物电化学的这一新概念基础上，建立了园二色谱电化学方法研究结构生物电化学的实验方法，数据处理和理论分析方法，并开展了多种生物大分子的结构-电化学研究．主要完成的工作如下：在基础理论与方法方面：1．建立和完善不可逆体系中薄层光谱电化学数据处理的双对数方法，用于区别简单电化学过程的E，EC和髓机理，电非活性产物吸附的自封闭，自阻碍和自加速机理；与非线性回归相结合，从有限实验数据中最多可获得7个电化学过程的热力学和动力学参数；并应用于中性和碱性条件下去甲肾上腺素，乙醇溶液中维生素D2前体，碱性溶液中酪氨酸，中性溶液中抗坏血酸的电化学反应机理的CD谱电化学研究；2．建立了奇异值分解最小二乘方法，用于解析动态光谱数据，不仅能给出组份数，各组份的光谱，而且同时给出各组份分数的分布，并应用于去甲肾上腺素在电化学氧化还原过程中的CD谱的解析和机理研究；3．提出了微区近似概念，与显示差分方法相结合，建立了微区近似显示差分的数值模拟方法．应用于薄层电化学池中三维的铂网电极体系的电化学和光谱电化学行为的模拟，获得与实验值一致的结果，并对薄层厚度，网眼尺度对薄层行为的影响进行了模拟研究；4．以分子力学与半经验分子轨道方法相结合，研究吲哚酚衍生物的分子结构参数与其式电位之间的定量关系，预测衍生物的式电位，推测电化学反应的气态分子结构机理；在结构生物电化学研究方面：5．在结构生物电化学这一新概念基础上，建立了以CD谱电化学研究结构生物电化学的实验方法，与基础理论研究的结果相结合，进行生物大分子结构．电化学研究：6．在牛血清白蛋白的结构．电化学研究中发现：(1)正电场诱导SA二级结构变化，存在三种构象转化：α螺旋→反平行β折叠；β转角→平行β折叠；平行β折叠→反平行β折叠；(2)负电场诱导BSA二级结构的变化存在β折叠→α螺旋的构象转化；(3)负电场和BSA的电化学还原诱导BSA中双硫键构象的左手旋→右手旋转化；证明了天然BSA中17个双硫键近似有1／2为左手旋；(4)研究了BSA中双硫键的电化学还原为EC机理和参数；7．在DNA的结构-电化学研究中发现：(1)负电场诱导DNA的B_(10.4)→Z_(l0.2)结构变化；(2)DNA电化学还原诱导B_(10.2)→B_(lO.4)和B_(10.2)→C 结构变化; (3)B_(10.4), B_(10.2)和C型DNA可能是由B_(10.4)，右手-A和左手-A型DNA的不同组份的共存而形成的；(4)获得DNA电化学还原过程的参数；8．在血红蛋白的结构一电化学研究中发现：(1)电化学还原诱导血红蛋白的T→R构型转化，手性转化的伞翻转效应；(2)电场诱导血红蛋白的两种0c螺旋二级结构间的转化，属于电场诱导血红蛋白的部分变性；(3)获得血红蛋白电化学还原的包括R→T转换的EC机理和参数；9．在细胞色素c的结构-电化学研究中发现：(1)细胞色素c的二级和三级结构受电场和酪氨酸残基及血红素中Fe的电化学还原的影响，其中酪氨酸残基还原的影响较大；(2)细胞色素c的电化学还原没有发生构型转化现象；(3)细胞色素c参与二级结构变化的构象有α螺旋，平行β折叠，反平行β折叠和无规卷曲；各组份随电位的变化复杂；(4)获得细胞色素c电化学还原的机理和参数；10．肌红蛋白的结构-电化学研究中发现：(1)电化学还原诱导了肌红蛋白的T→R构型转化伴随着cD谱的峰位移，但没有象血红蛋白那样明显伞翻转效应，表明伞翻转效应是多个亚基共同作用的结果；(2)获得肌红蛋白电化学还原的EC机理，并伴随产物吸附的自阻碍过程及其参数．

直接甲醇燃料电池甲醇替代燃料的研究

论文主要研究了直接甲醇燃料电池（DMFC）中三种甲醇替代燃料，二甲氧基甲烷（DMM）、乙醇和乙二醇及导致阳极催化剂中毒的吸附CO（COad）在光滑R电极及几种新的R基催化剂电极上的电氧化行为。结合对催化剂的X射线光电子能谱（xPS）、X衍射(XRD)、扫描电子显微镜（SEM）和热重分析（TG）表征，初步探讨了几种新催化剂对三种甲醇替代燃料的电催化活性要高于碳载R（PtC）催化剂的原因。另外，还研究了用表面活化处理来提高阳极催化剂对甲醇氧化的电催化活性的方法。本论文得到的主要结果如下：1．在研究DMM在不同条件下，在不同R基催化剂电极上的电化学氧化行为的基础上，发现碳载R和TiO2（Pt-TiO2／C）复合催化剂对DMM氧化的电催化活性要优于Pt/C电极。而Pt-TiO2／C催化剂在吸附Ho3+(Pt-TiO2-Ho3+/C)或Eu3＋（Pt-TiO2-Eu3＋/C）后，对DMM氧化的电催化活性比Pt-TiO2／C电极高。表明TiO2、Eu3+和Ho3+对DMM的氧化都有很好的促进作用，这主要是它们都能为DMM的氧化在电极表面提供更多的含氧物种。由于DMM本身在这些催化剂电极上的氧化性能不好，而且DMM容易在酸性溶液中水解，生成甲醇和甲醛，因此，DMM不是一种好的甲醇替代燃料。2．无论在中性介质中还是在酸性介质中，Eu3＋和Ho3＋对乙醇在R／C电极上的电化学氧化反应都有较好的促进作用，而Eu3＋的促进作用要大于H3+，Eu3＋和H3+在酸性溶液中的促进作用要大于在中性溶液中。无论是中性溶液还是酸性溶液中，吸附CO（COad）在Pt／C催化剂电极上在较正的电位处有一个很大的氧化峰，而在R-Eu3＋／C或R-H3＋／C催化剂电极上在较负电位处有两个小的氧化峰，表明吸附的Eu3＋和Ho3+对cood在R／C催化剂电极上的氧化都有很好的促进作用，主要表现在使Cood的吸附强度降低和吸附量减少。XPs测量表明，当R／C电极表面吸附了Eu3＋或H了十后，使催化剂中Pt和c土的电子云密度变小，因此使Pt对coad的吸附强度减弱。由于Eu3＋或H03＋在电极上吸附不是物理吸附，而是化学吸附，因此，它们与Pt的结合具有相对的稳定性。乙醇电氧化的中间产物，如COad等能强烈地吸附在R上，因此会使R中毒。而Eu3＋或H矿"能降低Coad在R上地吸附强度，因此，Eu3＋或H3+能促进乙醇在Pt／C电极上的电化学氧化反应。Pt-TiO2／C催化剂对乙醇氧化的电催化活性要高于R／C催化剂，表明TiO2对乙醇在R／C电极上的电化学氧化反应也有较好的促进作用。XPS的测量表明，TiO2的加入并不改变Pt的电子状态，因此，TiO2能促进乙醇电氧化反应的主要原因是TIOZ能为乙醇氧化提供含氧物种。实验结果表明，Eu3＋或H3+对乙醇在R-TiO2／C电极上的电化学氧化反应也有一定的促进作用。这是由于Eu3＋或H3+改变了R的电子状态，降低了乙醇电氧化中间产物，COod在Pt上的吸附强度，而TIOZ提供了COod的氧化所必须的含氧物种。3．无论是酸性溶液中还是中性溶液中，乙二醇在R-TiO2／C电极上的氧化活性比在R／C电极上高。这表明TIOZ能促进乙二醇在Pt上的电氧化反应。进一步的实验表明，TIOZ对COad在Pt催化剂电极上氧化的促进作用并不明显。XPS测量表明，这是由于TIOZ并不改变R的电子状态。所以，TiO2对乙二醇在Pt上的电氧化的促进作用只是基于提供乙二醇电氧化所需的含氧物种。无论是酸性溶液中还是中性溶液中，乙二醇在R-WO3／C电极上的氧化活性都比在R／C电极上高。这表明W03能促进乙二醇在R上的电氧化反应。进一步的实验表明，R-WO3／C电极对Coad氧化的电催化活性也要高于R／C电极，XPS测量表明，WO3会降低Pt的电子云密度。所以，WO3对乙二醇在R上的电氧化的促进作用除了提供含氧物种外，还由于它能降低R的电子云密度而降低了乙二醇电氧化中间产物。4．用四氢吠喃和丙酮混合溶液浸泡法对电极进行表面处理后能使Pt／C和Pt-WO3／C电极对乙醇和乙二醇氧化的电催化活性有很大的提高。其原因可能是Pt／C和Pt一w03／C电极在经表面处理后，在电极制备过程中带来的表面活性剂等杂质由于溶解在混合溶液中而被除去，Nafion也可能在用混合溶液浸泡后会发生一定程度的结构变化，因此，使活性中心的位点增加，从而增加了催化剂的电催化活性。另外，经表面处理后，Pt／C和Pt-WO3／C电极的活性中心的结构有一定的变化，使COad的吸附强度降低而容易氧化，降低了COad对催化剂的毒化作用，因而提高了电极对乙醇和乙二醇氧化的电催化活性。

联萘基手性联吡啶的合成及其应用

本论文以手性联萘酚为手性源，合成一系列联蔡基手性联毗陡及其衍生物，歼探讨了部分手性配体在不对称催化氢转移等反应中的应用。同时，通过部分配体与金属离子配位合成了旋光纯手性金属配合物，并对其溶液性质进行了深入研究。主要工作和结论如下：利用Krohnke方法，从（R）-6-乙酞基-2，2'-二甲氧基-1，1'-联萘简洁地合成了6-[6-((R)-2,2'-二甲氧基-1，1'-联萘基）]-2，2'-联吡啶及其衍生物（R)-1a-e。在相似条件下，合成了6，6'-二［6-（2，2'-联吡啶基）］-1，1'-联萘衍生物（R）-27-b。利用Suztlki偶联反应，对化合物（R）-1e进一步进行修饰得到了高产率的6-芳基-6'-[6-((R)-2,2'-二甲氧基-1,1'-联萘基）〕-2，2'-联吡啶(R)-1f-i。通过（R）3-（4，4，5：5-四甲基-1，3，2-二唑硼烷基）2，2'-乙氧基-1,1'-联萘与6-溴-2，2'-联吡啶及其衍生物的Suzuki偶联合成了四种手性6-［3-（（R）-2，2'-乙氧基-1，1'-联萘基）］-2，2'-联吡啶衍生物（R）-3a-d。将（R）-27b与AgSO3CF3进行配位合成Ag（I）配位聚合物35。固态下，35具有M构型的无限单股螺旋结构，且每个Ag（I）中心的手性受到配体，扫联蔡基的控制，其构型为Λ。在用MS、CD、UV及NMR对配合物35的溶液性质进行深入研究时发现，在溶液中配合物35离解为剂聚体，同时齐聚体之间存在快速平衡，且平衡随浓度、温度等条件的不同而发生改变，配体的平衡构象也相应被调整。另外，合成了Ag（I）与(R)-1d的单核配合物34，其洛液表现出与配台物35相似的性质。探讨了1a-i在苯乙酮氢转移还原、苯乙烯环丙烷化等不对称催化反应中的应用。在这些反应中，大部分配体表现出很好的反应活性，但立体选择性比较差。以(S)3，3'-二（4，4，5．5-四甲基-1，3，2-唑硼烷基于-2，2'-二（甲氧亚甲氧基）-1,1'-联萘为原料与2-溴吡啶及其衍生物先进行Stlzuki偶联，再经水解反应较高产率地合成了C2-对称性新型（S）-3，3'-二吡啶丛联茶酚衍生物（S）-38a-d。