Electropolymeric generation of optically active polypyrrole

The facile synthesis of optically active polypyrrole has been achieved via the enantioselective electropolymerization of pyrrole on indium-tin-oxide-coated glass electrodes in aqueous solution containing D-(+) or L-(-) tartaric acid, (1S)-(+)-10-camphorsulfonic acid and L-lactic acid. The dark films of conducting polypyrroles salt formed under electrostatic conditions (+0.65V vs. Ag/AgCl) exhibited strong circular dichroism (CD) spectra typical of polymers possessing helical chirality. The quantitative reversal of the CD spectrum of the salt grown in (+)-tartaric acid as opposed to (-)-tartaric acid suggests that electropolymerization is highly enantioselective, with one helical screw of the polymer chain being preferentially produced depending on the hand of the tartaric anion incorporated. (C) 1997 Elsevier Science Ltd.

Asymmetric polymerization of the mixture of TrMA and MMA initiated by chiral complexes

A mixture of triphenylmethyl methacrylate (TrMA) and methyl methacrylate (MMA) was polymerized with chiral anionic initiator, such as fluorenyl lithium-(-)-sparteine [FlLi-(-)-Sp] and fluorenyl lithium-(+)-2S,3S-dimethoxy-1,4-bis(dimethylamino) butane [FlLi-(+)-DDB] in toluene at -78 degrees C. The results show that after the stable helix formed, when FlLi-(+)-DDB was used as the initiator, TrMA and MMA could be copolymerized, whereas when FlLi-(-)-Sp was used, the two monomers tended to be selectively polymerized into two polymers. This phenomenon has been explained by the existence of helix-selective polymerization. (C) 1997 John Wiley & Sons, Inc.

SYNTHESIS AND PROPELLER-PROPELLER TRANSITION OF OPTICALLY-ACTIVE POLY(DIPHENYL-O-TOLYLMETHYL METHACRYLATE)

Diphenyl-o-tolylmethyl methacrylate (DPTMA) was synthesized and polymerized using initiators of organolithium complexes with (+) - (2S,3S) -dimethoxy-1,4-bis(dimethylamino) butane (DDB) and (-) -sparteine (Sp) as the chiral ligands. DDB was suitable for its complex effective to prepare optically active poly(diphenyl-o-tolylmethyl methacrylate) (PDPTMA) with one-handed helical conformation, whereas only low-molecular weight polymer was formed when Sp was used as ligand due to the repulsive hindrance between the triarylmethyl group and the ligand. A new mutarotation, propeller-propeller transition, was observed for PDPTMA from the optical rotation curves and CD spectra in THF solution. The equivalent period of PDPTMA was estimated to be 14 angstrom based on the x-ray diffraction. (C) 1993 John Wiley & Sons, Inc.

INTERACTIONS OF THIAMINE WITH ANIONS - STRUCTURE OF THIAMINE DITHIOCYANATE

The crystal structure analysis of {3-[(4-amino-2-methyl-5-pyrimidinyl)methyl]-5-(2-hydroxyethyl)-4-methylthiazol}ium dithiocyanate reveals that there are two types of anion bridges between the two aromatic rings of the same thiamine which adopts the usual F conformation, one of which involves a contact between H(C2) on the thiazolium ring and the hydroxy O atom from a neighbouring molecule. The crystal packing shows a novel triple helical structure formed by strongly hydrogen-bonded thiamine-SCN- molecular chains.

STRUCTURE OF MESOMORPHIC FORM OF ISOTACTIC POLYPROPYLENE

The structure of quenched isotactic polypropylene (iPP) films, including samples etched with fuming nitric acid (FNA), has been studied by infrared (IR) spectra, wide-angle x-ray diffraction (WAXD), small-angle x-ray scattering (SAXS), and differential scanning calorimetry (DSC) measurements. The changes of IR, SAXS, DSC, and WAXD results induced by annealing for etched samples have been compared with those for unetched ones. The IR absorbance spectrum of the quenched iPP etched by FNA did not change. In addition, the SAXS intensity did not increase when these samples were annealed, indicating that the total (IR) crystallinity (i.e., the content of chain segments in the helical conformations) of the etched samples does not increase. However, WAXD patterns of the samples changed in a manner similar to those of the unetched one, from the original two blurred diffraction peaks to the sharp crystal patterns of alpha-form iPP, suggesting that the mesomorphic (or liquid crystal-like) phase has reorganized to alpha-form crystals. It is concluded that the change of WAXD of quenched iPP films during annealing results mainly from transformation of order in the mesomorphic phase, rather than only from an increase of crystal size. In other words, mesomorphic-form iPP is not constituted by any known crystals (such as alpha or beta crystals) in small sizes; its WAXD pattern reflects truly the degree of order in the mesomorphic phase.

HELIX-INDUCED ASYMMETRIC POLYMERIZATION

Asymmetric polymerization could be induced by an already formed optically active living prepolymer with one-handed screw sense helix conformation. The usually formed anionic active centre on the prepolymer could be changed to cationic, radical and even of Ziegler-Natta type. These living prepolymers with various kinds of active centre were all effective to induce a consequent asymmetric polymerization of a monomer which may be other than that in the prepolymer, to afford an optically active helical chain with the same screw sense as that of the prepolymer. Eight monomers have been used in the work. Optical rotation, circular dichroism and gelpermeation chromatography have been taken to prove the helix-induced asymmetric polymerization.

STUDY ON OPTICAL-ROTATORY OF HELIX POLYMER POLY(TRIPHENYLMETHYL METHACRYLATE)

The optical rotatory of helix polymer poly(triphenylmethyl methacrylate) (PTrMA) has been studied. The specific rotation of PTrMA is related with the length of helical chain linearly, while P(n)BAR<6 and P(n)BAR greater-than-or-equal-to 15. When P(n)BAR greater-than-or-equal-to 15, [alpha]D/20 = 1.6 P(n)BAR + 290-degrees. The contribution of each repeating unit to [alpha]D/20 is 1.6-degrees. In the 300-600 nm region, the ORD of PTrMA obeys both the Drude equation and Moffitt equation. The relationship between the [alpha]D of PTrMA and the solvent, concentration and temperature has also been investigated.

CRYSTALLINITY OF UNIFORM OLIGO(OXYETHYLENE) MONO-N-ALKYL ETHERS STUDIED BY X-RAY-DIFFRACTION AND DIFFERENTIAL SCANNING CALORIMETRY

The crystallinity of two series of uniform oligo(oxyethylene) mono-n-alkyl ethers has been investigated: alpha-alkyl,omega-hydroxyoligo(oxyethylene)s, H(CH2)n(OCH2CH2)mOH, and alpha-alkyl,omega-methoxyoligo(oxyethylene)s, H(CH2)n(OCH2CH2)mOCH3. The hydroxy-ended oligomers formed bilayer crystals, and the methoxy-ended oligomers formed monolayer crystals. The helical oxyethylene blocks were oriented normal to the layer-crystal end-group plane, whilst the trans-planar alkyl blocks were generally tilted at an angle delta = 60-degrees. The melting temperature and enthalpy of fusion were higher for hydroxy-ended oligomers than for corresponding methoxy-ended oligomers.

In vitro selected peptides bind with thymidylate synthase mRNA and inhibit its translation

Thymidylate synthase (TS), an essential enzyme for catalyzing the biosynthesis of thymidylate, is a critical therapeutic target in cancer therapy. Recent studies have shown that TS functions as an RNA-binding protein by interacting with two different sequences on its own mRNA, thus, repressing translational efficiency. In this study, peptides binding TS RNA with high affinity were isolated using mRNA display from a large peptide library (>10(13) different sequences). The randomized library was subjected up to twelve rounds of in vitro selection and amplification. Comparing the amino acid composition of the selected peptides (12th round, R12) with those from the initial random library (round zero, R0), the basic and aromatic residues in the selected peptides were enriched significantly, suggesting that these peptide regions might be important in the peptide-TS mRNA interaction. Categorizing the amino acids at each random position based on their physicochemical properties and comparing the distributions with those of the initial random pool, an obvious basic charge characteristic was found at positions 1, 12, 17 and 18, suggesting that basic side chains participate in RNA binding. Secondary structure prediction showed that the selected peptides of R12 pool represented a helical propensity compared with R0 pool, and the regions were rich in basic residues. The electrophoretic gel mobility shift and in vitro translation assays showed that the peptides selected using mRNA display could bind TS RNA specifically and inhibit the translation of TS mRNA. Our results suggested that the identified peptides could be used as new TS inhibitors and developed to a novel class of anticancer agents.

Evolutionary analysis of phycobiliproteins: Implications for their structural and functional relationships

Phycobiliproteins, together with linker polypeptides and various chromophores, are basic building blocks of phycobilisomes, a supramolecular complex with a light-harvesting function in cyanobacteria and red algae. Previous studies suggest that the different types of phycobiliproteins and the linker polypeptides originated from the same ancestor. Here we retrieve the phycobilisome-related genes from the well-annotated and even unfinished cyanobacteria genomes and find that many sites with elevated d(N)/d(S) ratios in different phycobiliprotein lineages are located in the chromophore-binding domain and the helical hairpin domains (X and Y). Covariation analyses also reveal that these sites are significantly correlated, showing strong evidence of the functional-structural importance of interactions among these residues. The potential selective pressure driving the diversification of phycobiliproteins may be related to the phycobiliprotein-chromophore microenvironment formation and the subunits interaction. Sites and genes identified here would provide targets for further research on the structural-functional role of these residues and energy transfer through the chromophores.

刺参急性口围肿胀病和皱纹盘鲍肌肉萎缩症的病理学研究

本论文以大连沿海养殖刺参劾皱纹盘鲍为研究对象，利用组织学、超微病理学、病理生理学的方法，开展了患病病理学研究，并对可能诱发刺参和皱纹盘鲍病害的原因，以及病变过程进行了初步探讨。 中国北方养殖刺参[Apostichopus japonicus (Selenka)]幼参和成参的急性口围肿胀病。急性口围肿胀病是爆发于中国北方辽宁省和山东省沿岸养殖刺参群体中的一种新发现的疾病，并且从2004年开始已经引起刺参的大面积死亡现象，经济损失重大。 本文报道在养殖患病刺参的肠上皮细胞内发现大量的病毒样颗粒。这是首次报道病毒样粒子感染刺参。组织学检查表明该病毒具有包涵体结构，寄生于肠上皮细胞中。电镜检查的结果表明，该病毒粒子呈球形，直径80-100纳米，螺旋状核衣壳，具有囊膜结构且囊膜表面具有纤突结构。 进一步的形态学和病理学分析发现该病毒具有许多报道的关于冠状病毒的特征。细胞质内的 病毒颗粒大部分以团聚方式存在于一个完整的包膜内，形成典型的病毒包涵体结构。最明显的细胞病理学特征是细胞质内大面积的粒状物质的存在，该区域相对缺少相应的细胞器。在病毒包涵体内的管状结构，核衣壳包涵体以及双层膜囊泡也在病变细胞内发现。 在病参体内未发现立克次氏体，衣原体，细菌以及其他寄生生物。 中国北方养殖皱纹盘鲍(Haliotis discus hannai)的肌肉萎缩症病理研究 。 在2004年和2005年的中国北方海区，养殖皱纹盘鲍幼体和成体群体中爆发了严重的肌肉萎缩症。肌电图监测显示病鲍的肌肉萎缩是肌源性的而不是神经源性的。 与正常对照组对比结果显示，病鲍的肌纤维数量和肌纤维直径都显著降低。 肌酶谱测定结果显示，病鲍血清中的肌酸激酶水平，肌酸激酶—肌同工酶水平和乳酸脱氢酶水平，与正常血清对比，呈显著升高状态，说明病鲍体内发生了肌细胞损伤。超薄切片电镜检测结果显示在发生病变的肌细胞内存在双螺旋丝状结构的包涵体（Paired helical filaments, PHFs）, 该结构是人类患包涵体肌炎的主要的病理特征。 本文首次报道在无脊椎动物中发现双螺旋丝包涵体结构。 对损伤的肌纤维的进一步研究发现了异常增生的小圆柱体结构（Small Cylinder Structure, SCS）和致密小体(Dense colored particles, DCP),同时观察到这两种异常结构与肌纤维的损伤直接相关。本文还对该病的感染机制作了探讨。 中国北方皱纹盘鲍(Haliotis discus hannai)肌肉萎缩的病理生理研究。严重的足肌肉萎缩症是鲍的一种慢性致死性疾病。在中国北方的养殖皱纹盘鲍群体中第一次发现是在2000年，随后在各养殖海区，自然海区及实验室养殖过程中都发现了该病的暴发。 超微结构电镜检测显示肌肉纤维损伤严重，其内的大部分肌原纤维断裂或消失。 大量的花瓣状的糖原颗粒聚集在断裂的肌原纤维中，还有一些被包裹在包膜内。 这说明在病鲍体内的糖原代谢处于被抑制状态（或停止状态），随后的血清学检测表明病鲍血清中的葡萄糖含量与正常对照的含量显著降低，也证明了糖代谢途径的终止。病鲍血清中胆固醇和甘油三酯的量显著降低，伴随着高密度脂蛋白的水平显著升高，说明脂肪代谢途径的亢进状态。病鲍血清中的二氧化碳水平的显著降低说明出现了酸碱平衡紊乱，通过病因学分析可知该酸碱平衡紊乱应属于代谢性酸中毒。病鲍血清中的钠离子和钾离子浓度显著升高，无机磷和镁离子浓度显著降低说明出现了患病皱纹盘鲍体内出现了电解质紊乱。病鲍血清中蛋白质含量的检测表明患病皱纹盘鲍已出现低蛋白血症，说明病鲍出现了严重的营养不良。病鲍血清中的尿酸含量，胆碱酯酶水平和γ-转肽酶水平与正常对照组相比显著降低。各项指标检测的结果说明糖代谢途径的终止造成了病鲍一系列的调节体系的不平衡和各种生理功能的紊乱，甚至造成了鲍的最终死亡。

Isolation and characterization of a marine magnetotactic spirillum axenic culture QH-2 from an intertidal zone of the China Sea

Magnetotactic bacteria (MTB) are ubiquitous in aquatic habitats. Because of their fastidious requirements for growth conditions, only very few axenic MTB cultures have been obtained worldwide. In this study, we report a novel marine magnetotactic spirillum axenic culture, designated as QH-2, isolated from the China Sea. It was able to grow in semi-solid or liquid chemically defined medium. The cells were amphitrichously flagellated and contained one single magnetosome chain with an average number of 16 magnetosomes per cell. Phosphate and lipid granules were also observed in the cells. Both rock magnetism and energy-dispersive X-ray spectroscopy characterizations indicated that the magnetosomes in QH-2 were single-domain magnetites (Fe3O4). QH-2 cells swam mostly in a straight line at a velocity of 20-50 mu m/s and occasionally changed to a helical motion. Unlike other magnetotactic spirilla. QH-2 cells responded to light illumination. As a consequence of illumination, the cells changed the direction in which they swam from parallel to the magnetic field to antiparallel. This response appears to be similar to the effect of an increase in [O-2]. Analysis of the QH-2 16S rRNA sequence showed that it had greater than 11% sequence divergence from freshwater magnetotactic spirilla. Thus, the marine QH-2 strain seems to be both phylogenetically and magnetotactically distinct from the freshwater Magnetospirillum spp. studied previously. (C) 2010 Elsevier Masson SAS. All rights reserved.

Acute peristome edema disease in juvenile and adult sea cucumbers Apostichopus japonicus (Selenka) reared in North China

Acute peristome edema disease (APED) is a new disease that broke out in cultured sea cucumber along the Shangdong and Liaoning province coasts in China, PR, and has caused a great deal of death in Apostichopus japonicus (Selenka) since 2004. Here we report virus-like particles found in intestine epithelium of sea cucumbers reared in North China. It is the first time that sea cucumbers are reported to be infected by virus. Histological examinations showed that the viral inclusion bodies existed in intestine epithelium cells. Electron microscopic examinations show that the virions were spherical, 80-100 nm in diameter, and composed of a helical nucleocapsid within an envelope with surface projections. Detailed studies on the morphogenesis of these viruses found many characteristics previously described for coronaviruses. Virus particles always congregated, and formed a virus vesicle with an encircling membrane. The most obvious cellular pathologic feature is large granular areas of cytoplasm, relatively devoid of organelles. Tubular structures within virus-containing vesicles, nucleocapsid inclusions, and double-membrane vesicles are also found in the cytopathic cells. No rickettsia, chlamydia, bacteria, or other parasitic organisms were found. (c) 2007 Elsevier Inc. All rights reserved.

Floral Organogenesis and Development of two Taxa in Tribe Hyoscyameae (Solanaceae)-Przewalskia tanguitca and Hyoscyamus niger

Floral organogenesis and development of Przeivalskia langutica Maxim, endemic to China and Hyoscyamus niger L. , which belong to the tribe Hyoscyameae (Solanaceae), were studied using scanning electron microscope. They have three common characters of floral organ initiation and development: 1) initia-tion of the floral organs in the two species follows Hofmeister's rule; 2) the mode of corolla tube development belongs to the "late sympetaly" type; 3) primordia of the floral appendages initiated in a pentameroua pattern and acropetal order. But initiation of the calyx-lobe primordia showed different modes in these two species. The calyx-lobe primordia of H, niger have simultaneously whorled initiation, while those of P, tangulica have helical initiation, but the five calyx-lobe primordia form a ring after all five calyx-lobe primordia occur. The systematic significance of the present results in the genera Hyoscyamus and Przeivalskia is discussed in this paper.

促肾上腺皮质激素释放激素及去甲肾上腺素对高原鼠兔体液免疫的抑制作用

采用第三脑室注入CRF 及N E 的方法观察对高原鼠兔(Ochotona curzoniae) 体液免疫的影响。结果表明: 第三脑室注入CRF 1 μg 可抑制抗体生成, 比对照下降29.2% (P < 0.01) , 而在第三脑室注入CRF 受体阻断剂α-helical CRF- (9241) 50μg 后再注入CRF 1μg 则可取消CRF 对抗体生成的抑制作用; 第三脑室注入5 nM N E, 与对照相比, 抗体水平下降38.85%(P < 0.01) , 而使用6-OHDA 损毁脑内交感神经系统则使抗体水平升高24.31% (P < 0.01)。这些结果表明, 高原鼠兔中枢CRF 升高对体液免疫有抑制作用, 中枢交感神经系统对体液免疫也具有紧张性抑制作用。