Dynamics in dye-doped LC systems in presence of trans-cis isomerism

The excitation as well as relaxation dynamics of dye-doped nematic liquid crystal cells has been explored both experimentally and theoretically. Overshoots in the build up of the probe signal diffracted from gratings written onto dye-doped liquid crystal systems have often been observed. The overshoot behaviour makes the accurate measurement of nonlinear optical (NLO) response magnitude difficult and ambiguous. Moreover, it complicates the understanding of the dynamics and the physics of the NLO processes. On the basis of the system with trans-cis isomerisation as a mechanism of the NLO effect the quantitative model has been built to describe the experimental results which we observe. The two unknown material parameters: diffusion coefficient and cis species lifetime are calculated from the relaxation data. A quantitative model of the signal build-up uses these parameters. The calculated dynamic behaviour based on this model correlates very well with the experimental data. The model is used to predict the performance of the system with various dopant diffusion properties.

A novel proline rich bombesin-related peptide (PR-bombesin) from toad Bombina maxima

A novel bombesin-related peptide was isolated from skin secretions of Chinese red belly toad Bombina maxima. Its primary structure was established as pGlu-Lys-Lys-Pro-Pro-Arg-Pro-Pro-Gln-Trp-Ala-Val-Gly-His-Phe-Met-NH2. The amino-terminal (N-terminal) 8-residue segment comprising four prolines and three basic residues is extensively different from bombesins from other Bombina species. The peptide was thus named proline rich bombesin (PR-bombesin). PR-bumbesin was found to elicit concentration-dependent contractile effects in the rat stomach strip, with both increased potency and intrinsic activity as compared with those of [Leu(13)]bombesin. Analysis of different bombesin cDNA structures revealed that an 8 to 14- nucleotide fragment replacement in the peptide coding region (TGGGGAAT in the cDNAs of multiple bombesin forms from Bombina orientalis and CACCCCGGCCACCC in the cDNA of PR-bombesin) resulted in an unusual Pro-Pro-Arg-Pro-Pro motif in the N-terminal part of PR-bombesin. (C) 2002 Elsevier Science Inc. All rights reserved.

聚乙二醇模拟干旱对甜高粱幼苗丙二醛、脯氨酸含量的影响；Effects of Drought Stress Simulated by PEG on Malonaldehyde and Proline Contents of Sweet Sorghum Seedlings

以甜高粱品种KFJT-CK及经过碳离子辐照选育出的早熟突变株KFJT-1为材料,用浓度分别为5%,10%和15%的聚乙二醇(PEG)6000模拟干旱对其进行胁迫处理,测定丙二醛(MDA)及脯氨酸(Pro)的含量。随着胁迫时间的延长和胁迫程度的增加,MDA含量持续升高;Pro含量在5%和10%PEG胁迫下持续升高,在15%PEG胁迫下先升高后降低。表明碳离子辐照可能使甜高粱膜脂过氧化特性发生改变,影响Pro的表达。为进一步研究碳离子束辐照对甜高粱的耐旱生理提供一定的基础,并为下一步的育种工作提供有用的参考。

Highly cis-1,4 selective polymerization of dienes with homogeneous Ziegler-Natta catalysts based on NCN-pincer rare earth metal dichioride precursors

The first aryldiimine NCN-pincer ligated rare earth metal dichlorides (2,6-(2,6-C6H3R2N=CH)(2)C6H3)LnCl(2)(THF)(2) (Ln = Y, R = Me (1), Et (2), Pr (3); R = Et, Ln = La (4), Nd (5), Gd (6), Sm (7), Eu (8), Tb (9), Dy (10), Ho (11), Yb (12), Lu (13)) were successfully synthesized via transmetalation between 2,6-(2,6-C2H3-R2N=CH)(2)-C6H3Li and LnCl(3)(THF)(1 similar to 3.5). These complexes are isostructural monomers with two coordinating THF molecules, where the pincer ligand coordinates to the central metal ion in a kappa C:kappa N: kappa N' tridentate mode, adopting a meridional geometry.

Metal dependent control of cis-/trans-1,4 regioselectivity in 1,3-butadiene polymerization catalyzed by transition metal complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine

Fe(III), Cr(III), Fe(II), Co(II) and Ni(II) chloride complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine have been synthesized and characterized along with single crystal X-ray diffraction. These complexes, in combination with MAO, have been examined in butadiene polymerization. The catalytic activity and regioselectivity are strongly controlled by metal center and cocatalyst (MAO/Co ratio dependent in the case of Co(II) complex). The activity decreases in the order of Fe(III) > Co(II) > Cr(III) approximate to Ni (II) complexes, in consistent with the space around the metal center. Polybutadiene with different microstructure content, from high trans-1,4 units (88-95% for iron(III) and Cr(III)), medium trans-1,4 and cis-1,4 units (55% and 35%, respectively, for iron(II)) to high cis-1,4 units 79% for Co(II) and 97% for Ni(II) call be easily achieved by varying of the metal center.

Synthesis and properties of polyimides derived from cis- and trans-1,2,3,4-cyclohexanetetracarboxylic dianhydrides

Cis-1,2,3,4-cyclohexanetetracarboxylic dianhydride (cis-1,2,3,4-CHDA) was synthesized. It was found that under such conditions as heating or boiling in acetic anhydride, cis-1,2,3,4-CHDA could be converted to its trans-isomer. The process of thermal isomerization was monitored by H-1 NMR spectra and the mechanism of conversion was proposed. Their absolute structures of cis- and trans-1,2,3,4-CHDAs were elucidated by single crystal X-ray diffraction. The polycondensations of cis- and trans-1,2,3,4-CHDAs with aromatic diamines such as 4,4'-oxydianiline (ODA), 4,4'-methylenedianiline (MDA), 4,4'-diamino-3,3'-dimethyldiphenylmethane (DMMDA), 4,4'-bis(4-aminophenoxy)benzene (TPEQ), 2,2-bis[4-(4-aminophenoxy)phenyl] propane (BAPP) were studied. It is easy to obtain higher molecular weight polyimides from trans-1,2,3,4-CHDA using conventional one-step or two-step methods. However, higher molecular weight polyimides derived from cis-1,2,3,4-CHDA could not be prepared by the usual methods (solid content ca. 10%) owing to the trend of forming cyclic oligomers.

The chemical resolution of racemic cis-2-hydroxymethyl-5(cytosine-1 '-yl)-1,3-oxathiolane (BCH-189)-one direct method to obtain lamivudine as anti-HIV and anti-HBV agent

Racemic cis-BCH-189 can be resolved to (-)-enantiomer (lamivudine) and (+)-enantiomer by esterification of cis-2-hydroxymethyl-5-(N-4(')-acetylcytosine-1'-yl)-1,3-oxathiolane and (+)-menthyl chloroformate in CH3CN with pyridine as base. The two diastereomers of ester were seperated by recrystallization in methanol at 0degreesC. Lamivudine was obtained by deprotection of (-)-diastereomer with high yield.

Study on the cyclization of cis-1,4 polybutadiene in various solvents and its mechanism

The cyclization of cis-1,4 polybutadiene in various solvents (mesitylene,xylene, toluene,benzene and cyclohexane) with the catalyst composed of CH2=CHCH2Cl-AlEt2Cl was studied. The infrared spectra of the cyclized products were investigated. It was shown that the products produced in cyclohexane and mesitylene have infrared spectra identical with those of the original cis-1,4-polybutadiene and the products obtained in other aromatics have infrared spectra different from each other and distinguishing with those of the parent cis-1,4 polybutadiene. The analyses of infrared spectra came to the conclusion that the molecules of aromatic solvent participate in cyclization of cis-1,4 polybutadiene at the given condition. A possible reaction scheme involving an electrophilic substitution of carbonium ions for Ar-H of aromatic solvents was proposed. Some experimental facts were explained with great satisfaction on the basis of the above mechanism.

Hydrogen-deuterium exchange reactions of cis- and trans-cyclopropane derivatives with D2O and CD3OD in the gas phase

Gas-phase hydrogen-deuterium (H/D) exchange reactions involving four isomeric cyclopropane derivatives were investigated under chemical ionization (CI) conditions, using D2O and CD3OD as reagent gases. There are abundant ions at [M + 1](+), [M + 2](+) and [M + 3](+) in the D2O and CD3OD positive-ion CI mass spectra of the two isomer pairs 1, 2 and 3, 4, Their CI mass spectra are identical with each pair, and so are the collision-induced dissociation (CID) spectra of ions [M + 1](+), [M + 2](+) and [M + 3](+) of each of the two isomer pairs. The CID spectra of [M + 1](+) ions indicate that they have common D/H exchange reactions within each pair, which take place between molecular ions and deuterium-labeling reagents to form the [M - H + D](+) ions. Those of their [M + 2](+) ions show that they have common D/H exchange reactions within each pair, which form the [M-d1 + H](+) ions. Those of their [M + 3](+) ions show that they have common D/H exchange reactions within each pair, which take place between the [M-d1] and deuterium-labeling reagents to produce [Md-2 + H](+) for the isomer pair 1, 2 and [M-d1 + D](+) for the Isomer pair 3, 4. The number and position, and active order of the active hydrogen atoms of the isomer pairs 1, 2 and 3, 4 were determined. Copyright (C) 2000 John Wiley & Sons, Ltd.

Synthesis of cis-(+/-)-2-hydroxymethyl-5-(cytosine-1 '-yl)-1,3-oxathiolane (BCH-189)

The target compound BCH-189 was synthesized with high yield via four steps from benzoyloxy acetylaldehyde and p-dithiane-2,5-diol as starting materials. The synthetic route is preferable to what literature reported.