反式和顺式-1，2-二氰-（4-乙基苯）乙烯结构的谱学分析

合成了2种新型的可溶性四氮杂卟啉中间体：反式-1，2二氰-（4-乙基苯）乙烯和顺式-1，2-二氰（4-乙基苯）乙烯。通过UV-Vis，FFIR，GC／MS，^1H NMR等方法对这2种化合物的结构进行了表征，给出了它们完整的结构信息。分析比较了顺、反异构体结构上的差异，分析两者的紫外-可见光谱（UV-Vis）、红外光谱（FTIR）和核磁共振光谱（^1H NMR）谱图的差异及其产生原因。

假根羽藻细胞色素b6f蛋白复合体中α-胡萝卜素的结构与功能

细胞色素b6f蛋白复合体（Cyt b6f）是光合链中连接两个光系统（PSII 和PSI）的中间电子载体蛋白复合物，其主要的生理功能是催化电子传递和质子跨膜转移，形成跨膜质子电化学梯度，为ATP的合成提供能量，在光合作用光能转化过程中占有很重要的地位。细菌和莱茵衣藻Cyt b6f的晶体结构已于2003年底获得了近原子水平的解析，但有关该复合物中两种色素（Chl a和β-Car）的生理功能及其机理尚无明确的解释。预计它们将成为今后几年的研究热点,因为揭示Cyt b6f蛋白复合体中Chl a和β-Car分子的生理功能对于进一步阐明光合作用高效转能及其调控的分子机理具十分重要的意义。鉴于目前尚未见到海洋绿藻Cyt b6f的报道，本文以海洋绿藻—假根羽藻（Bryopsis corticulans）类囊体膜上的Cyt b6f蛋白复合体为对象，对其中的类胡萝卜素的分子结构与生理功能进行了比较系统地研究。 首先，我们改进了原用于菠菜类囊体膜Cyt b6f的分离、纯化流程，在原流程的基础上增加了一次2 mol/L NaBr洗膜，彻底地去除了膜表面的杂蛋白;还调整了第二次硫酸铵分级沉淀时的饱和度，并将38-45%饱和度下的沉淀物确定为需要收集的Cyt b6f制剂。采用此改进的流程，我们首次从假根羽藻类囊体膜中分离纯化了高活性、高纯度的Cyt b6f制剂。SDS-PAGE分析的结果显示该制剂的4个多肽亚基 （Cytf 、Cyt b6 、Rieske[Fe-s]及亚基IV）的表观分子量分别为34.8、24.0、18.7和16.7 kD;Cyt b6 / f 比值接近2.0， 其纯度值为9.9 nmol cyt f/mg;其催化电子传递的活性 （C10-PQH2→PC）为73 e/s。HPLC 和共振拉曼光谱分析表明，假根羽藻Cyt b6f中的类胡萝卜素为α-胡萝卜素分子，它是一种在Cyt b6f中尚未报道过的类胡萝卜素。定量分析表明，每个假根羽藻Cyt b6f单体中全反式(all-trans)和9顺式（9-cis）α-胡萝卜素的含量分别为0.2和0.7个分子，另外还含有1.2分子的Chl a。CD光谱分析表明该9-cis-α-胡萝卜素处在一个不对称的蛋白环境中。TLC分析表明该制剂是一种缺脂的Cyt b6f蛋白复合体。 采用稳态荧光激发光谱，时间分辨吸收光谱及Chl a的光破坏实验对假根羽藻Cyt b6f中α-胡萝卜素的功能进行了研究。结果表明，Cyt b6f中α-胡萝卜素可以将它吸收的光能传递给Chl a，其能量传递效率为62.4%，提出α-胡萝卜素分子与Chl a分子之间的单线态能量传递是遵从Föster 机制进行的;α-胡萝卜素分子对Chl a分子有一定的光保护作用，这种保护作用是通过清除单线态氧来实现的。另外还发现Cyt b6f中的Chl a分子可能与其周围的氨基酸残基存在相互作用，认为这是其进行自我光保护的一种方式。 此外，还采用HPLC研究了光和暗交替对假根羽藻Cyt b6f中α-胡萝卜素构型的影响，并对假根羽藻Cyt b6f选择结合α-胡萝卜素的原因进行了初步的分析。

Mutation analysis of a large Chinese pedigree with congenital preaxial polydactyly

Mutations in the long-range limb-specific cis-regulator (ZRS) could cause ectopic shh gene expression and are responsible for preaxial polydactyly (PPD). In this study, we analyzed a large Chinese isolated autosomal dominant PPD pedigree. By fine mapping

Deep RNA sequencing at single base-pair resolution reveals high complexity of the rice transcriptome

Understanding the dynamics of eukaryotic transcriptome is essential for studying the complexity of transcriptional regulation and its impact on phenotype. However, comprehensive studies of transcriptomes at single base resolution are rare, even for modern organisms, and lacking for rice. Here, we present the first transcriptome atlas for eight organs of cultivated rice. Using high-throughput paired-end RNA-seq, we unambiguously detected transcripts expressing at an extremely low level, as well as a substantial number of novel transcripts, exons, and untranslated regions. An analysis of alternative splicing in the rice transcriptome revealed that alternative cis-splicing occurred in similar to 33% of all rice genes. This is far more than previously reported. In addition, we also identified 234 putative chimeric transcripts that seem to be produced by trans-splicing, indicating that transcript fusion events are more common than expected. In-depth analysis revealed a multitude of fusion transcripts that might be by-products of alternative splicing. Validation and chimeric transcript structural analysis provided evidence that some of these transcripts are likely to be functional in the cell. Taken together, our data provide extensive evidence that transcriptional regulation in rice is vastly more complex than previously believed.

Anti-human Immunodeficiency Virus-1 Constituents of the Bark of Poncirus trifoliata

A total of 36 compounds (1-36) were obtained from the stem bark of Poncirus trifoliata including three new prenylated flavonoids, (-)-5,4'-dihydroxy-7,8-[(3 '',4 ''-cis-dihydroxy-3 '',4 ''-dihydro)-2 '',2 ''-dimethylpyrano]-flavone (1), (-)-5,4'-dihydroxy-7,8-[(3 ''-hydroxy-4 ''-one)-2 '',2 ''-dimethylpyrano]-flavone (2), and (-)-5,4'-dihydroxy-7,8-[(cis-3 ''-hydroxy-4 ''-ethoxy-3 '',4 ''-dihydro)-2 '',2 ''-dimethylpyrano]-flavone (3). The new structures were elucidated by means of spectroscopic methods. Compounds 1-20 were evaluated for their anti-human immunodeficiency virus-1 (HIV-1) activity, in which 2 showed significant anti-HIV-1 activity with high therapeutic index (T1) of 143.65.

CHARACTERISTICS OF FATTY ACID METHYL ESTERS (FAMEs) AND ENZYMATIC ACTIVITIES IN SEDIMENTS OF TWO EUTROPHIC LAKES

Enzymatic activities and fatty acid methyl esters (FAMEs) in the sediments of two eutrophic lakes in Wuhan city were investigated. The results showed phosphatase and dehydrogenase activities in the lotus zone and plant floating bed zone were significantly lower than those in other sites, and urease activity was the highest where microorganism agents were put in. Fatty acid group compositions indicated the predominance of aerobic bacteria in the surface sediments in shallow lakes. The ratios of FAMEs specific for bacteria and Gram-positive bacteria exibited significant differences between the two lakes. The results of trans to cis indicated that the microorganisms in Lake Yuehu could adapt themselves to environmental stress better. The enzymatic activities and FAMEs showed differences in different sites, indicating that ecological restoration measures and environmental conditions could affect lake sediment to some extent. But the monitoring, work would be done in series to exactly evaluate the effect of the remediation measures.

Expression pattern, cellular localization and promoter activity analysis of ovarian aromatase (Cyp19a1a) in protogynous hermaphrodite red-spotted grouper

Aromatase plays a key role in sex differentiation of gonads. In this study, we cloned the full-length cDNA of ovarian aromatase from protogynous hermaphrodite red-spotted grouper (Epinephelus akaara), and prepared the corresponding anti-EaCyp19a1a antiserum. Western blot and immunofluorescence studies revealed ovary-specific expression pattern of EaCyp19a1a in adults and its dynamic expression change during artificial sex reversal. EaCyp19a1a was expressed by follicular cells of follicular layer around oocytes because strong EaCyp19a1a immunofluorescence was observed in the cells of ovaries. During artificial sex reversal, EaCyp19a1a expression dropped significantly from female to male, and almost no any positive EaCyp19a1a signal was observed in testicular tissues. Then, we cloned and sequenced a total of 1967 bp T-flanking sequence of EaCyp19a1a promoter, and showed a number of potential binding sites for some transcriptional factors, such as SOX5, GATA gene family, CREB, AP1, FOXL1, C/EBP, ARE and SF-1. Moreover, we prepared a series of 5' deletion promoter constructs and performed in vitro luciferase assays of EaCyp19a1a promoter activities. The data indicated that the CREB regulation region from -1010 to -898 might be a major cis-acting element to EaCyp19a1a promoter, whereas the elements GATA and SOX5 in the region from -1216 to -1010 might be suppression elements. Significantly, we found a common conserved sequence region in the fish ovary-type aromatase promoters with identities from 93% to 34%. And, the motifs of TATA box, SF-1, SOX5, and CREB existed in the region and were conserved among the most of fish species. (C) 2009 Elsevier Ireland Ltd. All rights reserved.

Antimicrobial activity-specific to Gram-negative bacteria and immune modulation-mediated NF-kappa B and Sp1 of a medaka beta-defensin

Defensins are a group of cationic antimicrobial peptides which play an important role in the innate immune system by exerting their antimicrobial activity against pathogens. In this study, we cloned a novel beta-defensin cDNA from medaka (Oryzias latipes) by rapid amplification of cDNA ends (RACE) technique. The full-length cDNA consists of 480 bp, and the open reading frame (CRF) of 189 bp encodes a polypeptide of 63 amino acids (aa) with a predicted molecular weight of 7.44 kDa. Its genomic organization was analyzed, and Southern blot detection confirmed that only one copy of beta-defensin exists in the medaka HNI strain. RT-PCR, Western blot and immunohistochemistry detections showed that the beta-defensin transcript and protein could be detected in eyes, liver, kidney, blood, spleen and gill, and obviously prevalent expression was found in eyes. Antimicrobial activity of the medaka beta-defensin was evaluated, and the antibacterial activity-specific to Gram-negative bacteria was revealed. Furthermore, the lipopolysaccharide (LPS), a major component of the outer membrane of Gram-negative bacteria, was demonstrated to be able to induce about 13-fol up-regulation of the beta-defensin within first 12 h. In addition, promoter and promoter mutagenesis analysis were performed in the medaka beta-defensin. A proximal 100 base pair(bp) sequence (+26 to -73)and the next 1700 bp sequence (-73 to -1755) were demonstrated to be responsible for the basal promoter activity and for the transcription regulation. Three nuclear factor kappa B (NF-kappa B) cis-elements and a Sp1 cis-element were revealed by mutagenesis analysis to exist in the 5' flanking sequence, and they were confirmed to be responsible for the up-regulation of medaka beta-defensin stimulated by LPS. And, the Sp1 cis-element was further revealed to be related to the basal promoter activity, and transcriptional factor II D (TFIID) was found to be in charge of the gene transcription initiation. All the obtained data suggested that the novel medaka beta-defensin should have antimicrobial activity-specific to Gram-negative bacteria, and the antibacterial immune function should be modulated by NF-kappa B and Sp1. (C) 2008 Elsevier Ltd. All rights reserved.

Transient Reorientation of a Doped Liquid Crystal System under a Short Laser Pulse

The transient optical nonlinearity of a nematic liquid crystal doped with azo-dye DR19 is examined. The optical reorientation threshold of a 25-mu m-thick planar-aligned sample of 5CB using a 50 ns pulse duration 532 nm YAG laser pulse is observed to decrease from 800 mJ/mm(2) to 0.6 mJ/mm(2) after the addition of 1 vol% azo dopant, a reduction of three orders of magnitude. When using a laser pulse duration of 10 ns, no such effect is observed. Experimental results indicate that the azo dopant molecules undergo photoisomerization from trans-isomer to cis-isomer under exposure to light, and this conformation change reorients the 5CB molecules via intermolecular coupling between guest and host. This guest-host coupling also affects the azo photoisomerization process.

Investigation on acceleration response of fiber optic mandrel hydrophone

The acceleration response of fiber optic mandrel hydrophone is studied based on the theory of elastic dynamics in this paper. For the first time the influence of the optical fiber on the acceleration response is taken into consideration. And the derivation of the radial deformation of the mandrel is presented in details. The acceleration response is evaluated both theoretically and experimentally and the results are in good agreement.

Design and path planning for a remote-brained service robot

This article introduced an effective design method of robot called remote-brain, which is made the brain and body separated. It leaves the brain in the mother environment, by which we mean the environment in which the brain's software is developed, and talks with its body by wireless links. It also presents a real robot TUT06-B based on this method which has human-machine interaction, vision systems, manipulator etc. Then it discussed the path planning method for the robot based on ant colony algorithm in details, especially the Ant-cycle model. And it also analyzed the parameter of the algorithm which can affect the convergence. Finally, it gives the program flow chat of this algorithm.

拉米呋淀及其衍生物的合成和药效评估

（1）研究了专利中报道的以2-苯甲酰氧甲基5-乙氧基-1，3氧硫杂环戊烷为中间体，在不同的Lewis酸催化下与乙酰化的胞嘧啶的C-N键偶联反应。研究结果发现，反应的最终产物为苯甲酸2-乙氧基-2-（N_4'-乙酰基胞嘧啶-1'-基）-乙酯。依据实验结果，我们提出了硅甲基化的乙酰基胞嘧啶首先进攻氧硫杂环中间体时，烷硫基比乙氧基基团更易离去，从而进攻氧硫杂环中间体的C-2位而非C-5位的反应机理。（2）研究了不同的Lewis酸催化剂对以2-苯甲酰氧甲基-5-乙酰氧基-1，3-氧硫杂环戊烷中间体与乙酰化胞嘧啶的C-N键形成反庆的影响。结果显示，由于催化剂SnCl_4与氧硫环的硫原子螯合，从而导致胞嘧啶的氮原子从氧硫环的β面进攻，产生顺反产物的比值为3：1，是合成顺式产物的最好催化剂。（3）设计了四步反应合成2-羟甲基-5-（胞嘧啶-1'-基）-1，3-氧硫杂环戊烷（cis-BCH-189）的路线：通过苯甲酰氧基乙醛与2，5-二羟基-1，4-二噻烷的羟醛缩合反应构筑1，3-氧硫杂环戊烷，经乙酰化反应及SnCl_4催化下的C-N键形成反应接上乙酰化胞嘧啶，最后在K_2CO_3/MeOH体系中脱去保护基，得到主产物cis-BCH-189。利用该方法合成外消旋的cis-BCH-189，未见文献报道。其优点在于原料便宜易得，产品收率高，操作简单，是大量合成cis-BCH-189的有效方法。（4）设计了如下合成2-羟甲基-4-（胞嘧啶-1'-基）-1，3-氧硫杂环戊烷的路线：以苯甲酰氧基乙醛和巯基乙醇为原料，在甲苯溶剂中和p-TsOH催化下，经羟醛缩和反应合成得到2-苯甲酰氧基-1，3-氧硫杂环戊烷，然后经间氯过苯甲酸（m-CPBA）氧化为亚砜，在NaOAc/Ac_2O中回流发生普梅雷尔重排反应，得到2-苯甲酰氧甲基-4-乙酰氧基-1，3-氧硫杂环戊烷中间体，以Lewis酸SnCl_4为催化剂，获得顺反比值为2：1的产物。将顺式产物在K_2CO_3/MeOH体系中脱去保护基，得到外消旋的顺式-2-羟甲基-4-（胞嘧啶-1'-基）-1，3-氧硫杂环戊烷。反应共五步，总产率为11%，合成路线未见文献报道。此合成路线原料使宜易得，操作简单，是合成大量产品的有效途径。（5）分另研究了以（-）-樟脑酰氯和（+）-（艹孟）氧基甲酰氯为手性拆分试剂时cis-BCH-189的拆分效果，结果显示前者几乎对其没有拆分能力，而后者却是非常好的拆分试剂。拆分过程为（+）-（艹孟）氧基甲酰氯与顺式-2-羟甲基-5-（N_4'-乙酰基胞嘧啶-1'-基）-1，3-氧硫杂环戊烷经化学反应成酯后，于0 ℃在甲醇溶剂中重结晶，得到左旋光异构体，经K_2CO_3/MeOH体系酯解脱保护基后，得以拉米呋啶纯品，旋光度为[α]_D~(20) = -137°(c0.01, MeOH)；母液浓缩析出的固体经脱保护基后可得到右旋光的对映体，旋光度为[α]_D~(20) = +34.03°(c0.01, MeOH)。（6）探索了以Hg(CN)_2、HgBr_2银盐及TMSOTf等为催化剂的反应条件下，溴代半乳糖四乙酸酯及β-D-半乳糖五乙酸酯分别与顺式-2-羟甲基-5-（N_4'-乙酰基胞嘧啶-1'-基）-1，3-氧硫杂环戊烷的糖苷键形成反应。结果发现以Lewis酸TMSOTf为催化剂时，以β-D-半乳糖五乙酸酯为反应原料获得的BCH-189的糖苷衍生物的产率最高；而在汞催化下，以溴代半乳糖四乙酸酯为反应原料获得的BCH-189的糖苷衍生物的产率仅为10～ 20%。以TMSOTf为催化剂，将拉米呋定、顺反BCH-189及顺式2-羟甲基-4-（胞嘧啶-1'-基）-1，3-氧硫杂环戊烷与β-D-半乳糖五乙酸酯反应合成了系列苷类似物的半乳糖衍生物。（7）将系列核苷类似物的乙酰化半乳糖糖苷及脱保护基的核苷类似物的半乳糖糖苷和拉米呋定纯品于2.2.15细胞株中进行抗病毒性能的药效研究，药效结果显示核苷类似物的乙酰化半乳糖糖苷均优于其完全脱保护基的半乳糖糖苷，也优于未与半乳糖偶联的母体核苷体化合物及抗乙肝病毒的药物拉米呋定。

由二酐的异构体合成的聚酰亚胺

聚酰亚胺是一类综合性能优异的重要耐热高分子材料，它在航空，航天工业，微电子工业等诸多领域获得了广泛的应用。异构的聚酰亚胺是近几年新兴起的结构材料之一，与传统结构的聚酰亚胺比较，具有更高的玻璃化温度，良好的溶解性能，低的熔融粘度，宽的加工窗口，和相当的机械性能和热稳定性，是一种较有发展前景的结构材料；同时异构的二酐单体又可以用来合成芳香环状聚酰亚胺，对这些十分稳定又具有很好溶解性能的环状齐聚体的研究还刚刚开始。为此，本论文主要就以下方面开展研究工作：1，以环己烯为原料，经六步，高收率地合成了PMDA的异构体，MPDA。发现MPDA在室温下同甲醇和苯胺的开环选择反应分别得到了不对称的酷化产物和对称的酞化产物，这种开环选择的差别可归结于在酞化反应过程中形成了环状氢键中间体。通过MPDA和苯胺的亚胺化反应研究，发现在DMAc中热环化得到单亚胺化合物和双亚胺化合物的混合物，而在对氯酚中热环化或者在DMAc中化学环化均只得到唯一双亚胺化合物。单晶X-Ray衍射证实了单亚胺化合物的结构。发现在DMAc中热环化时单亚胺化合物和双亚胺化合物可以相互转化，而在氮气或者真空高温条件下单亚胺化合物不能转化成双亚胺化合物，从而提出了反应机制，即少量DMAc中的水分可以影响生成单亚胺化合物。发现MPDA和ODA或者MDA聚合时有很大的生成环状聚酰亚胺的倾向，它们的环状性质由IR，MALDI-TOF-MS，和NMR所证实。发现环状聚酰胺酸放置时，不同的环之间可以发生转换，从而可以提高受热力学控制的环的收率。用溶剂萃取和重结晶的方法分离得到了环状聚酰亚胺二聚体，用单晶X-Ray衍射的方法表征了二聚体包容不同溶剂时的分子结构，从分子水平的角度研究了环状聚酞亚胺的结构和性能的关系。除了MPDA得到的聚酞亚胺有较高的g值外，异构体聚酰亚胺的其它性能如力学性能、热稳定性能、溶解度性能、形态结构性能等差别不大。2．以2，3-二甲基苯胺为原料，经四步，高收率地得到了3,3'-BTDA。发现螺双内酚在乙酸配中回流可以直接有效地转化成二配3,3'-BTDA，并提出了转化机制。单晶X-Ray衍射表明3,3'-BTDA和3,4'-BTDA都有非共平面的分子结构。通过研究异构的BTDA得到的聚酞亚胺，发现并表征了3,3'-BTDA和ODA聚合时有很大的生成环状聚酞亚胺的倾向。异构化BTDA得到的聚酞亚胺的Tg值规律：3,3'-BTDA＞3,4'-BTDA＞4,4'-BTDA；溶解性能规律：3,3'-BTDA＞3,4'-BTDA＞4,4'-BTDAA；融体粘度规律：3,3'-BTDA＞4,4'-BTDAA3,4'-BTDA；热机械性能规律：4,4'-BTDA澎3,4'-BTDA＞3,3'-BTDA。可以看出3,4'-BTDAA得到的聚酰亚胺既有良好的加工性能，又能保持材料的热机械性能。由DSC测得的异构模型化合物的Tm，△Hm，和△Sm数据可以有效地解释异构聚酰亚胺的Tg规律。3．合成了cis-1,2,3,4-CHDA，发现在一定条件下可以转化成它的异构体trans-1,2,3,4-CHDA，1HNMR直接跟踪热异构化反应的进程，并提出了转化机制。单晶X-Ray衍射确定了两个二配异构体的绝对构型。发现在用trans-1,2,3,4-CHDA制备聚酞亚胺时无论用两步法或者一步法，均能很容易地得到高分子量的聚合物。而它的异构体cig-1,2,3,4-CHDA在制备聚酞亚胺时，由于形成环状聚酞亚胺，用传统的方法得不到高分子量的聚合物，增加单体的浓度可以有效制得高分子量的聚合物。发现顺式聚合物的溶解性能比反式异构体的好，Tg值比相应反式异构体的高，其它如热氧化稳定性，机械性能，光学性能，异构体间没有明显的差别。但是，两个异构体都可以制得坚韧的透明薄膜。

环糊精衍生物的设计、合成及其对环辛烯光异构化研究

环糊精(Cyclodextrins, CDs)经化学修饰后可以得到各种类型的衍生物，不仅可以扩展其原有的键合能力，而且还可以改变其选择性，是当代超分子化学的一个研究热点。环糊精第二面的仲羟基比第一面的伯羟基有着更好的催化性能，第二面的选择性修饰将产生更多有价值的衍生物，可用于催化、酶模拟、手性识别等方面。 取代苯甲酰基修饰环糊精对顺式环辛烯(cis-cyclooctene)光异构化反应有非常重要的影响作用，苯环上取代基的性质和取代位置与产物的%ee值和对映体构型之间存在某种内在联系。有目的地选择适宜取代基，设计、合成新型环糊精光增感剂, 有可能按预定目的得到更高%ee值的反式环辛烯；同时，取代苯甲酰基修饰环糊精对cis-cyclooctene光异构化的增感机理有待于进一步阐明。 本论文工作对环糊精的化学修饰以及超分子体系对cis-cyclooctene不对称光异构化反应方面的进展进行了调研。合成了一系列单-6-位取代苯甲酰基修饰环糊精，用于cis-cyclooctene光异构化增感反应，并用圆二色光谱滴定法研究这些环糊精衍生物与cis-cyclooctene的相互作用，以探索光增感反应机理。在此基础上，探讨了环糊精第二面的选择性修饰方法。内容主要包括： 1. 简要介绍了超分子化学的概况，并对环糊精的选择性修饰方法和超分子体系对cis-cyclooctene不对称光异构化反应的主要成果和最新进展进行了评述。 2. 合成了12种单-6-O-(取代苯甲酰基)-β-环糊精，其中10种为新化合物。采用紫外光谱、红外光谱、核磁共振波谱以及质谱等手段对化合物的结构进行了表征。 3. 探索了直接选择性修饰环糊精第二面的便捷新方法。用取代苯甲酰咪唑酯为酰化试剂，0.2M碳酸盐缓冲溶液(pH=9.9)作催化剂，能够有效地活化2-位仲羟基，对环糊精第二面进行选择性修饰，此方法既简便又经济；同时，发现取代苯甲酰基能够在β-CD第二面的2-位、3-位羟基间相互迁移。 4. 用单-6-O-(取代苯甲酰基)-β-环糊精作光增感剂，对cis-cyclooctene光异构化反应进行研究。实验结果证明：取代苯甲酰基上的取代基性质、位置、长度对反应的对映选择性有很大影响；此外，反应体系溶剂极性对产物的%ee值和对映体构型也有重大影响。用单-6-O-(3-甲氧苯甲酰基)-β-CD作增感剂，cis-cyclooctene光异构化反应产物(R)-trans-cyclooctene的对映选择性为45.8%ee，是到目前为止取得的最好对映选择性。 5. 采用圆二色光谱滴定法研究环糊精衍生物与cis-cyclooctene的相互作用，计算包结物的平衡常数，研究包结物的相对稳定性，为探索光增感反应机理提供基础。我们猜测：电子效应对cis-cyclooctene光异构化反应的影响，可能比取代基位置对反应的影响更大，借助电子效应有希望获得更高的%ee值。 Cyclodextrins can be subjected to diverse modifications to give a wide variety of cyclodextrin derivatives, which could not only extend their original molecular binding ability, but also alter their molecular selectivity. Therefore, cyclodextrin chemistry is currently a significant topic in supramolecular chemistry. The more open secondary hydroxyl side of CDs is stated to be catalytically very important, modifications of this face are believed to produce valuable derivatives for catalysis, enzyme mimic, chiral discrimination, etc. Mono-6-O-(substituted benzoyl)-β-CDs as novel supramolecular photosensitizing hosts have recently excited considerable attention in photochirogenesis. The supramolecular photosenstization of cis-cyclooctene mediated by them gave chiral trans-cyclooctene, enantiomeric excess of which was critically affected by the substituent introduced to the sensitizer moiety. In order to enhance the photoenantiodifferentiating ability, and elucidate the origin mechanisms of substituent-dependent enantioselectivity, in this work a series of mono-6-O-(substituted benzoyl)-β-CDs have been synthesized, and applied for enantiodifferentiating photoisomerization of cis-cyclooctene. The major contents are as follows: 1. The general aspects of supramolecular chemistry were descibed briefly. The new progress and important achievements on methods of selective modification of cyclodextrin and supramolecular enantiodifferentiating photoisomerization of cis-cyclooctene were reviewed. 2. Twelve mono-6-O-(substituted benzoyl)-β-CDs including ten novel compounds have been synthesized. Their structures have been characterized by using UV-vis, IR, NMR and MS methods. 3. A new convenient strategy for direct acylation of β-cyclodextrin on the secondary hydroxyl face was achieved by using the combination of N-benzoylimidazole and carbonate buffer in DMF, and the acyl migration between the C-2 and C-3 hydroxyl groups of β-cyclodextrin was found. 4. Experiments using mono-6-O-(substituted benzoyl)-β-CDs as chiral sensitizing hosts for mediating the enantiodifferentiating photoisomerization of cis-cyclooctene, were carried out. The results indicate that enantiomeric excess was critically affected, or even switched in sign, by the substituent introduced to the sensitizer moiety, and polarity of solvent. Using mono-6-O-(3-methoxybenzoyl)-β-CD as chiral sensitizing host, (R)-trans-cyclooctene was obtained in up to 45.8% enantiomeric excess, which is the highest value ever reported for supramolecular photochirogenesis with analogous hosts. 5. The conformational variation of these modified CDs and their complexation behaviors with cis-cyclooctene were examined by circular dichroism spectroscopy in water-methanol mixed solvents, which reveal that the orientation of chromophore was highly sensitive to the type, position and length of the introduced substituents. In the end, the complex stability constants(Ks) were calculated, and the mechanisms of reaction were discussed. Maybe, electronic effects are more important than positions of substituents for mediating the enantiodifferentiating photoisomerization of cis-cyclooctene.

Rotamers of m-aminophenol cation studied by mass analyzed threshold ionization spectroscopy and theoretical calculations

The vibrationally resolved spectra of selected rotamers of m-aminophenol have been recorded by mass analyzed threshold ionization spectroscopy in connection with two-color resonant two-photon excitation scheme. The adiabatic ionization energies of the cis and trans rotamers are 61460 +/- 5 and 61734 +/- 5 cm(-1), respectively. The frequencies of modes 1 (breathing) and 18a (in-plane CH bending) are measured to be 744 and 1097 cm(-1) for the cis, and 736 and 1104 cm(-1) for the trans rotamer, respectively. This indicates that different orientation of the OH with respect to the NH2 substituent only slightly influences these two modes. (C) 2004 Elsevier B.V. All rights reserved.