2,3'-联吡啶还原合成毒藜碱、安那他品和异毒藜碱

本论文从2，3'-联吡啶出发，利用两个吡啶环上氮的反应活性差异，选择性合成了单烷基盐1-甲基-2，3，-联吡啶盐、1-甲基-1，一氧-2，3，-联吡啶盐和1'-甲基／节基2，3气联吡啶盐，还原单烷基盐合成了天然生物碱毒黎碱、安那他品和异毒黎碱及其衍生物：对异毒黎碱的合成由还原N，-节基盐后脱节基简化为一步实现还原和脱节基直接得到异毒黎碱。通过用（R）-BINOL和（S）-BINOL对N，-节基异毒黎碱拆分得到了旋光纯的N，-节基异毒黎碱和异毒黎碱，-N，-节基异毒黎碱的旋光度［a］D20：-61．50（c＝2．0，乙醇），卜异毒黎碱的旋光度fa］D20：-14．4"（c-1．0，乙醇）；将C关异毒黎碱用（RMTPA和（s）MT队衍生为Mosher酞胺，应用Mosllel方法确定了C）异毒黎碱手性中心的绝对构型为R型，即（R）-C）异毒黎碱，同时发现，由（R）一MTPA合成的Mosller酞胺中顺式旋转异构体占优。而通常在环胺的Mosller酞胺中，是反式旋转异构体占优。这一例外被MollteCarlo模型模拟计算结果解释：稀溶液中C卜异毒黎碱的Moshel－酞胺，顺式构型能量上比反式更有利。不对称合成天然生物碱更具有挑战性。对异毒黎碱还原合成中的呱l淀烯类中间体，用BINAP-灿催化体系进行了催化不对称还原的合成研究，氢化N'-节基-1，，4，，5，，6，-四氢一2，3，一联吡陡时得到了最高为21．5％的对映体选择性，而对N'-节基一1，，2'，5'，6，-四氢-2，3'一联吡陡的氢化则只得到了不超过10．0％的对映体选择性。

Syndiotactically enriched 1,2-selective polymerization of 1,3-butadiene initiated by iron catalysts based on a new class of donors

A series of phosphoryl (P=O) contained compounds: triethylphosphate (a), diethyl phenyl phosphate (b), ethyldiphenylphosphate (c) triarylphosphates (d and h-m), triphenylphosphine oxide (e), phenyl diphenylphosphinate (f) and diphenyl phenylphosphonate (g) have been prepared. Iron catalysts, which are generated in situ by mixing the compounds with Fe(2-EHA)(3) and (AlBu3)-Bu-i in hexane, are tested for butadiene polymerization at 50 degrees C. Phosphates donated catalysts have been, unprecedently, found to conduct extremely high syndiotactically (pentad, rrrr=46.1-94.5%) enriched 1,2-selective (1,2-structure content=56.2-94.3%) polymerization of butadiene.

Fe(2-EHA)(3)/Al(i-Bu)(3)/hydrogen phosphite catalyst for preparing syndiotactic 1,2-polybutadiene

Polymerizing 1,3-butadiene into syndiotactic 1,2-polybutadiene with art iron(III) catalyst system has been investigated. Activity of the catalyst was affected by the type of cocatalyst alkylaluminum and the phosphorus compound as an electron donor, molar ratio of catalyst components, and their aging sequence and aging time of the catalyst. The microstructure and configuration of the polymer was decided by the catalyst components, the higher [Al]/[Fe] molar ratio tending to yield syndiotactic 1,2-polybutadiene, while the higher [P]/[Fe] molar ratio favors the formation of amorphous 1,2-polybutadiene.

Toluene dioxygenase-catalysed oxidation route to angular cis-monohydrodiols and other bioproducts from bacterial metabolism of 1,2-dihydrobenzocyclobutene and derivatives

A mutant strain (UV4) of the soil bacterium Pseudomonas putida, containing toluene dioxygenase, has been used in the metabolic oxidation of 1,2-dihydrobenzocyclobutene 12 dagger and the related substrates 1,2-dihydrobenzocyclobuten-1-ol 13 and biphenylene 33. Stable angular cis-monohydrodiol metabolites (1R,2S)-bicyclo[4.2.0]octa-3,5-diene-1,2 7, (1S,2S,8S)-bicyclo[4.2.0]octa-3,5-diene-1,2,8-triol 8 and biphenylene-cis-1,8b-diol 9, isolated from each of these substrates, have been structurally and stereochemically assigned. The structure, enantiopurity and absolute configuration of the other cis-diol metabolites, (2R,3S)-bicyclo[4.2.0]octa-1(6),4-diene-2,3-diol 14 and cis-1,2-dihydroxy-1,2-dihydrobenzocyclobutene 16, and the benzylic oxidation bioproducts, 1,2-dihydrobenzocyclobuten-1-ol 13, 1,2-dihydrobenzocyclobuten-1-one 15 and 2-hydroxy-1,2-dihydrobenzocyclobuten-1-one 17, obtained from 1,2-dihydrobenzocyclobutene and 1,2-dihydrobenzocyclobuten-1-ol, have been determined with the aid of chiral stationary-phase HPLC, NMR and CD spectroscopy, and stereochemical correlation. X-Ray crystallographic methods have been used in the determination of absolute configuration of the di-camphanates 27 (from diol 7) and 32 (from diol 9), and the di-MTPA ester 29 (from diol 14) of the corresponding cis-diol metabolites. The metabolic sequence involved in the formation of bioproducts derived from 1,2-dihydrobenzocyclobutene 12 has been investigated.

Fulvalene cyclopentadienyl titanium and zirconium(III) and -(IV) complexes. X-Ray crystal structure of [{Ti(η5-C5H5) Cl}2 (μ-O)(μ-η5-η5-C10H8)]

The reaction of the fulvalene titanium(III) hydride [{Ti(η5-C5H5)(μ-H)}2(μ-η5-η5-C10H8)] (1) with chlorine leads to [{Ti(η5-C5H5)(μ-Cl)}2(μ-η5-η5-C10H8)] (3) and [{Ti(η5-C5H5)Cl2}2(μ-η5-η5-C10H8)] (4). The reaction of 3 with azobenzene, in wet toluene, gives [{Ti(η5-C5H5)Cl}2(μ-O)(μ-η5-η5-C10H8)] (5) and 1,2-diphenyl hydrazine. The alkylation of 4 and the analogous zirconium complex [{Zr(η5-C5H55)Cl2}2(μ-η5-η5-C10H8)] (2) with LiCH2SiMe3 or LiCH3 permits isolation of the tetraalkyl derivatives [{M(η5-C5H5)(CH2SiMe3)2}2(μ-η5-η5-C10H8)] (M  Ti (6); Zr (8)) and [{Ti(η5-C5H5)(CH3)2}2(μ-η5-η5C10H8)] (7). All the new fulvalene compounds were characterized by IR, and 1H and 13C NMR spectroscope, and mass spectra and 5 by X-ray diffraction. The structure of 5 is very similar to that of the comparable TiIV compound [{Ti(η5-C5H5)2Cl}2(μ-O)] except for the smaller TiOTi angle (159.4° against 173.81°) and a significant deviation from linearity.

Fast-timing study of the l-forbidden 1/2(+) -> 3/2(+) M1 transition in Sn-129

The levels in Sn-129 populated from the beta(-) decay of In-129 isomers were investigated at the ISOLDE facility of CERN using the newly commissioned ISOLDE Decay Station (IDS). The lowest 1/2(+) state and the 3/2(+) ground state in 129Sn are expected to have configurations dominated by the neutron s(1/2) (l = 0) and d(3/2) (l = 2) single-particle states, respectively. Consequently, these states should be connected by a somewhat slow l-forbidden M1 transition. Using fast-timing spectroscopy we havemeasured the half-life of the 1/2(+) 315.3-keV state, T-1/2 = 19(10) ps, which corresponds to a moderately fast M1 transition. Shell-model calculations using the CD-Bonn effective interaction, with standard effective charges and g factors, predict a 4-ns half-life for this level. We can reconcile the shell-model calculations to the measured T-1/2 value by the renormalization of the M1 effective operator for neutron holes.

(Z)-1[2-(苯基二溴化锡基)乙烯基]-1-环己醇的合成及晶体结构

报道了标题化合物〔C14H18Br2OSn〕的合成及晶体结构。该晶体属于单斜晶系，空间点群为P21/c，晶胞参数a=11.711(2)，b=9．114（2），c=16．864（3）A，β=102.94（1）°，V=1604.55（0）A3，Mr=480．78，Z=4，Dc=1．99g／cm3，u=65．20cm－1，F（000）=919，R=0．050，Rw=0．050．晶体结构由直接法解出。标题化合物分子中的锡原子被配体的2个碳、2个溴和1个氧原子配位，配位原子呈畸变的三角双锥构型，环已基为椅式构象，五员杂环为信封构象。

Web 1, 2 and 3

Lecture on IA and webdesign (1 & 2 of 3). Web 2 talk I reference Aral Balkan - talk video is included here from his presentation at the Norwegian developers conference.

1. 大鼠眶额叶与吗啡成瘾关系的研究2.在自由活动的猕猴大脑上进行神经元单位记录方法的建立

本论文的实验研究内容包括"大鼠眶额叶与吗啡成瘾关系的研究"及"在自由活动的称猴大脑上进行神经元单位放电记录方法的建立"两部分。第一部分在第一部分，着重探讨了眶额叶在吗啡诱导的心理成瘾中的作用。大量的研究证据表明，人类的眶额叶参与了强迫性的药物渴求行为。然而，我们不知道眶额叶在其中是起抑制作用还是促进作用？在人类，眶额叶的功能失调通常会打断动机化行为、不能预测后果以至不能进行正确地判断或者产生难以妙制的重复性行为，那么眶额叶的损伤对吗啡的奖赏效应以及吗啡诱导的药物依赖有什么影响呢？此外，DAD2受体的活动在吗啡成瘾中有十分重要的作用，那么眶额叶中DAD2受体的活动对吗啡诱导的心理成瘾的影响如何呢？另外，给动物或者人系统注射巴氯芬一GAB标受体的激动剂能缓解吗啡诱导的心理成瘾，那么眶额叶GAB绳受体的激活对吗啡诱导的心理成瘾是否具有抑制作用呢？因此，在第一部分我们以大鼠作为吗啡渴求的动物模型围绕上述三个问题开展实验工作。在第一部分的研究中，运用条件化位置偏好的模型，分别研究了大鼠眶额叶电损伤、大鼠眶额叶微量注射DAD2激动剂和拮抗剂以及GABAB受体激动剂一巴氯芬对吗啡诱导的药物依赖的影响；结果表明：（1）大鼠眶额叶在吗啡一环境刺激这个特殊的条件化学习过程中的作用是十分有限的；（2）如果条件化建立之后眶额叶的功能受损，可能导致眶额叶抑制功能的障碍，表现出抑制功能的减弱，因而不能抑制原来在一定的条件下引导的行为反应，所以，表现出对药物渴求的增加；长期滥用药物所导致眶额叶的功能受损势必会增加对药物的依赖。（3）眶额叶的DADZ受体可能对药物心理渴求起着抑制作用，当DAD2受体受到抑制时，眶额叶对吗啡渴求行为的抑制被削弱，导致动物渴求行为明显增加。同时，本研究也证实了眶额叶的GABAB受体活动没有涉及到对心理渴求的调节； 第二部分在第二部分，着重介绍了"在自由活动的称猴大脑上进行神经元单位放电记录方法的建立"。单个神经元活动的胞外记录是现代神经生物学研究的重要手段之一，是在细胞水平上研究大脑的感觉、运动、认知功能等常用而又极其重要的方法，它在研究动物脑与行为的关系上发挥着越来越重要的作用。然而，在传统的记录系统里记录设施通常限制着动物的活动，也影响了动物行为的自然展示，因而对动物脑功能与某些行为关系的研究具有很大的局限性。在传统技术的基础上，我们对神经元胞外记录方法进行了一系列的改进，建立起一套轻便的记录系统和适合在户外自由活动的琳猴大脑上进行神经元单位放电的胞外记录及追踪动物行为的方法。利用这种方法，就可以在室外自由活动称猴的大脑上记录到信噪比高且能稳定数小时的放电神经元；在单位放电的记录过程中，动物是处于室外自由活动状态不会因为实验操作引起动物的紧张；伴随着神经元单位放电的记录，同时进行着动物相关行为信息的记录；其中下列几个因素在方法的建立上起着至关重要的作用：（1）特殊设计的可移动的微电极；（2）小而轻的放大器；（3）信号的无线传输方式；它的建立为我们研究细胞活动和动物行为关系以及研究非人灵长类社会行为的细胞学基础提供了一种全新的方法。

Validation of a method for the analysis of volatile organic compounds in water

Dissertação de mestrado, Qualidade em Análises, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2015

Synthesis, spectroscopic characterization and X-ray structures of five-coordinate diorganotin(IV) complexes containing 5-hydroxypyrazoline derivatives as ligands

Four new diorganotin(IV) complexes have been prepared from R(2)SnCl(2) (R = Me, Ph) with the ligands 5-hydroxy-3-metyl-5-phenyl-1-(S-benzildithiocarbazate)-pyrazoline (H(2)L(1)) and 5-hydroxy-3-methyl-5-phenyl-1-(2-thiophenecarboxylic)-pyrazoline (H(2)L(2)). The complexes were characterized by elemental analysis, IR. (1)H (13)C, (119)Sn NMR and Mossbauer spectroscopes The complexes [Me(2)SnL(1)], [Ph(2)SnL(1)] and [Me(2)SnL(2)] were also studied by single crystal X-ray diffraction and the results showed that the Sn(IV) central atom of the complexes adopts a distorted trigonal bipyramidal (TBP) geometry with the N atom of the ONX-tridentate (X = O and S) ligand and two organic groups occupying equatorial sites. The C-Sn-C angles for [Me(2)Sn(L(1))] and [Ph(2)Sn(L(1))] were calculated using a correlation between (119)Sn Mossbauer and X-ray crystallographic data based on the point-charge model Theoretical calculations were performed with the B3LYP density functional employing 3-21G(*) and DZVP all electron basis sets showing good agreement with experimental findings General and Sn(IV) specific IR harmonic frequency scale factors for both basis sets were obtained from comparison with selected experimental frequencies (C) 2010 Elsevier B V All rights reserved