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71.
Stereoblock poly(lactic acid) consisting of D- and L-lactate stereosequences can be successfully synthesized by solid-state polycondensation of a 1:1 mixture of poly(L-lactic acid) and poly(D-lactic acid). In the first step, melt-polycondensation of L- and D-lactic acids is conducted to synthesize poly(L-lactic acid) and poly(D-lactic acid) with a medium-molecular-weight, respectively. In the next step, these poly(L-lactic acid) and poly(D-lactic acid) are melt-blended in 1:1 ratio to allow formation of their stereocomplex. In the last step, this melt-blend is subjected to solid-state polycondensation at temperature where the dehydrative condensation is allowed to promote chain extension in the amorphous phase with the stereocomplex crystals preserved. Finally, stereoblock poly(lactic acid) having high-molecular-weight is obtained. The stereoblock poly(lactic acid) synthesized by this way shows a higher melting temperature in consequence of the controlled block lengths and the resulting higher-molecular-weight. The product characterization as well as the optimization of the polymerization conditions is described. Changes in M(w) of stereoblock poly(lactic acid) (sb-PLA) as a function of the reaction time. 相似文献
72.
Chetsumon Aparat Umeda Fusako Maeda Isamu Yagi Kiyohito Mizoguchi Tadashi Miura Yoshiharu 《Applied biochemistry and biotechnology》1998,(1):249-256
A photobioreactor was constructed using anchored polyurethane foam strips (1 x 1 x 40 cm) fixed onto a stainless-steel ring
to prevent flotation, as a biomass support material (BSM). This type of reactor was named a seaweed-type bioreactor. A filamentous
cyanobacterium, Scytonema sp. TISTR 8208, which produces a novel cyclic dodecapeptide antibiotic, was immobilized in seaweed-type
photobioreactor and cultivated with air containing 5% CO2 sparged at a gas flow rate of 250 mL/min under illumination at a light intensity of 200 μmol photon m-2s-1. The antibiotic produced in the seaweed-type photobioreactor was purified by HPLC and examined regarding its spectrum and
mode of action. The antibiotic effectively inhibited the growth of Gram-positive bacteria, pathogenic yeasts, and filamentous
fungi, but it had only a weak effect on Gram-negative bacteria. Scanning electron micrograph analysis showed that the most
characteristic change was swelling of the cells after exposure to the antibiotic. The antibiotic seems to alter the conformation
of the microbial cell membrane, thereby changing its permeability, leading to osmotic shock. 相似文献
73.
Alkenyl, aryl or allylic selenides smoothly couple with Grignard reagents in the presence of Ni(II)-phosphine complexes as catalysts to afford the corresponding unsaturated compounds in good yields. The reactivity order of coupling reaction with BuMgBr catalyzed by NiCl2 [Ph2PCH2CH2CH2PPh2] was found to be PhSeMe « PhCl > PhSMe by the competitive reactions. 相似文献
74.
Chiral polythiophenes (PTs), in sharp contrast to other optically active polymers, exhibit optical activity in the pi-pi* transition region which is derived from the chirality of the main chain when they self-assemble to form a supramolecular pi-stacked aggregate with intermolecular interactions in a poor solvent or in a film. We now report that the regioregular, optically active PT poly[(R)-3-[4-(4-ethyl-2-oxazolin-2-yl)phenyl]thiophene] (poly-1) exhibits unique split-type induced circular dichroism (ICD) in the pi-pi* transition region of the main chain upon complexation with various metal salts such as trifluoromethanesulfonates of copper(I), copper(II), silver(I), and zinc(II), and iron(II) perchlorate in chloroform, which is a good solvent for poly-1. The appearance of ICD and slight changes in the UV/Vis spectra (no color change), except for the zinc salts, indicated that the chirality may not be induced by chiral pi-stacked aggregates of poly-1, but by the chirality of the main chain, for example, a predominantly one-handed helical structure induced by intermolecular coordination of the oxazoline groups to metal ions. The sign of the Cotton effect depends on the metal salt; most metal salts induced ICDs with similar Cotton-effect patterns, while zinc salts caused an inversion of the signs of the Cotton effect of poly-1 accompanied by a gradual red shift in the absorption of up to 125 nm. The changes in the conformation and the size of the poly-1 aggregates induced by different metal salts were also investigated by (1)H NMR titrations, static light scattering (SLS), atomic force microscopy (AFM), and membrane filtration. On the basis of these results, we propose a possible model for the chiral supramolecular aggregates of poly-1 with metal salts. 相似文献
75.
A novel carbonyl alkynylation has been accomplished based on utilization of the Meerwein-Ponndorf-Verley (MPV) reaction system. The success of the MPV alkynylation crucially depends on the discovery of the remarkable ligand acceleration effect of 2,2'-biphenol. For example, the alkynylation of chloral (2c) with the aluminium alkoxide 6(R = Ph), prepared in situ from Me(3)Al, 2,2'-biphenol and 2-methyl-4-phenyl-3-butyn-2-ol (1a) as an alkynyl source, proceeded smoothly in CH(2)Cl(2) at room temperature to give the desired propargyl alcohol 3ca in almost quantitative yield after 5 h stirring. The characteristic feature of this new transformation involving no metal alkynides can be visualized by the fact that the alkynyl group bearing keto carbonyl was transferred successfully to aldehyde carbonyl without any side reactions on keto carbonyl. Although the use of (S)-1,1[prime or minute]-bi-2-naphthol and its simple analogues was found to be unsuitable for inducing asymmetry in this reaction, design of new chiral biphenols bearing a certain flexibility of the biphenyl axis led to satisfactory results in terms of enantioselectivity as well as reactivity. 相似文献
76.
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79.
Kenshu Fujiwara Masanori Kobayashi Fuyuki Yamamoto Yu-ichi Aki Mariko Kawamura Daisuke Awakura Seiji Amano Azusa Okano Akio Murai Hidetoshi Kawai Takanori Suzuki 《Tetrahedron letters》2005,46(30):5067-5069
The common left-half [C31-C33(OC1-C7)-C40] part of pectenotoxins has been synthesized convergently from the C31-C35, C36-C40, and C1-C7 parts. The C31-C35 part, prepared via a new route shorter than our previous route, was coupled with the C36-C40 part through reductive lithiation and addition reactions to give an adduct stereoselectively, which was converted to a cyclic acetal corresponding to the C31-C40 part. The left-half was synthesized by a three-step process including esterification of the C31-C40 part with the C1-C7 part. 相似文献
80.
[reaction: see text] Indium-mediated allenylation of alpha,beta-unsaturated ketones in the presence of tert-butyldimethylsilyl triflate and dimethyl sulfide gives 6-siloxy-1,2,5-trienes, which undergo W(CO)(5)(L)-catalyzed 5-endo cyclization to give the corresponding cyclopentene derivatives in good yield. Furthermore, this novel W(CO)(5)(L)-catalyzed cyclization of allenyl silyl enol ethers proceeds in a 6-endo manner when 5-siloxy-1,2,5-trienes are employed as a substrate. In these reactions, effective electrophilic activation of allenyl compounds for attack by silyl enol ethers is achieved using a catalytic amount of W(CO)(6). 相似文献