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941.
[structure: see text]. Although the Hg(OTf)2.3TMU-catalyzed Friedel-Crafts-type reaction of 3-(4-pentynyl)furan afforded the exo cyclization product, the reaction of 2-(4-pentynyl)furan furnished a very low yield. We found a 10:1 mixed reagent of Hg(OAc)2 and Sc(OTf)3 showed remarkable catalytic activity for the latter transformation. The actual reacting species is presumed to be Hg(OAc)(OTf), which is efficiently generated in situ by mixing the two reagents. 相似文献
942.
The stereoselective total synthesis of (+)-vittatine 1 and (+)-haemanthamine 2 starting from d-glucose is described. The cyclohexene ring in 1 was prepared in an optically active form from d-glucose using Ferrier's carbocyclization reaction, and the critical quaternary carbon was stereoselectively generated via chirality transfer by the Claisen rearrangement of cyclohexenol 6. The hexahydroindole skeleton was effectively constructed by the intramolecular aminomercuration-demercuration of 14, followed by Chugaev reaction to provide 16. Finally, Pictet-Spengler reaction completed the first chiral synthesis of (+)-vittatine 1. On the other hand, the α-hydroxylation of the ester 5 stereoselectively proceeded to give α-hydroxy ester 19, to which was introduced an amino function to provide 4. A similar transformation of 4, as employed in the synthesis of vittatine, furnished (+)-haemanthamine 2. 相似文献
943.
Masaki Kita Eric R.O. Siwu Takahiro Takiguchi Tomoyuki Koyama Takeshi Iwashita Daisuke Uemura 《Tetrahedron letters》2007,48(19):3429-3432
Durinskiol A (1) is a long carbon-chain polyol compound with a molecular weight of 2128 mu isolated from the symbiotic dinoflagellate Durinskia sp. The relative stereochemistries of ether rings and sugar moieties in 1 were established based on 2D-NMR analysis and molecular modeling studies. Conformational analysis of the 6,5,6-bis-spiroacetal ring in 1 was also examined by using ab initio methods. 相似文献
944.
Masaki Kita Eric R.O. Siwu Takahiro Takiguchi Kaoru Yamada Takeshi Iwashita 《Tetrahedron letters》2007,48(19):3423-3427
A long carbon-chain polyol compound with a molecular weight of 2128 mu, durinskiol A (1) was isolated from the cultured symbiotic dinoflagellate Durinskia sp. Its planar structure was elucidated based on 2D-NMR and MS/MS analysis. Durinskiol A (1) caused a short body length, abnormal pigment pattern, and pericardiac and yolk-sac edema in zebrafish. 相似文献
945.
Isao Sasaki 《Polymer Degradation and Stability》2007,92(7):1408-1416
Stability of electronic parameters of conducting polymers affects the overall performance of organic electronics. We show that UV light (254 nm) treatment of polyaniline (PANI) films, containing camphorsulfonic acid (CSA) as a dopant and cast from formic acid, decreases the film resistance and keeps their improved resistance stable for at least 4 months. It has been found that due to the different origins of these electronic properties, the resistance and work function of the PANI·CSA films are affected differently by the UV treatment. The long-term stability of the resistance is governed by morphological changes of the material. On the other hand the stability of the threshold voltage of the field-effect transistor (FET) which is an indirect measure of the work function, originates from the charge density equilibration at the PANI·CSA film/insulator interface. The FT-IR, UV-vis and circular dichroism data provide the evidence that after the UV treatment the polymer molecular structure remains intact, but some secondary structural re-arrangements of the PANI·CSA take place. These re-arrangements are resulting from the strong donor-acceptor interactions between the imine and/or amine groups of the PANI chains and the CO and SO3− groups of the doping CSA-anion. These interactions enhance significantly the mechanical rigidity of the PANI matrix. The increasing broad absorption band of the “free-carrier tail” in the FT-IR spectra correlates with the conductivity increase of the UV treated PANI·CSA film. 相似文献
946.
Moore RH Spies MA Culpepper MB Murakawa T Hirota S Okajima T Tanizawa K Mure M 《Journal of the American Chemical Society》2007,129(37):11524-11534
The biogenesis of the topaquinone (TPQ) cofactor of copper amine oxidase (CAO) is self-catalyzed and requires copper and molecular oxygen. A dopaquinone intermediate has been proposed to undergo 1,4-addition of a copper-associated water molecule to form the reduced form of TPQ (TPQ(red)), followed by facile oxidation by O(2) to yield the mature TPQ (TPQ(ox)). In this study, we have incorporated a lysine residue in the active site of Arthrobacter globiformis CAO (AGAO) by site-directed mutagenesis to produce D298K-AGAO. The X-ray crystal structure of D298K-AGAO at 1.7-A resolution revealed that a covalent linkage formed between the epsilon-amino side chain of Lys298 and the C2 position of a dopaquinone derived from Tyr382, a precursor to TPQ(ox). We assigned the species as an iminoquinone tautomer (LTI) of lysine tyrosylquinone (LTQ), the organic cofactor of lysyl oxidase (LOX). The time course of the formation of LTI at pH 6.8 was followed by UV/vis and resonance Raman spectroscopies. In the early phase of the reaction, an LTQ-like intermediate was observed. This intermediate then slowly converted to LTI in an isosbestic manner. Not only is the presence of a dopaquinone intermediate in the TPQ biogenesis confirmed, but it also provides strong support for the proposed intermediacy of a dopaquinone in the biogenesis of LTQ in LOX. Further, this study indicates that the dopaquinone intermediate in AGAO is mobile and can swing from the copper site into the active-site wedge to react with Lys298. 相似文献
947.
948.
Mitsuhashi S Fukushima T Tomiya M Santa T Imai K Toyo'oka T 《Analytica chimica acta》2007,584(2):315-321
Kynurenine (KYN), a tryptophan metabolite, is a crucial compound for modulating neurotransmission because it can be metabolized in vivo into both quinolinic acid and kynurenic acid, which are the agonist and antagonist, respectively, of N-methyl-d-aspartate receptor. For the highly sensitive detection of KYN by high-performance liquid chromatography (HPLC), a fluorescence derivatization of KYN with a benzofurazan-type fluorogenic reagent, 4-N,N-dimethylaminosulfonyl-7-fluoro-2,1,3-benzoxadiazole (DBD-F) was investigated in the present study. KYN was derivatized with DBD-F (DBD-KYN) at 60 °C for 30 min, and separated on an octadecylsilica column with a gradient elution of the mobile phase, which consists of 0.1% formic acid in acetonitrile/methanol/water. DBD-KYN was detected fluorimetrically at 553 nm with an excitation wavelength of 431 nm. The limits of detection and quantification were approximately 0.30 pmol [signal-to-noise ratio (S/N) 3] and 1.0 pmol (S/N, 10) on column, respectively. Plasma KYN levels were successfully determined using 10 μL of rat plasma with satisfactory precision and accuracy. Intra- and inter-day precisions and accuracies were 1.7-6.8%, and −10 to 9.6%, respectively. KYN levels in plasma of male Sprague-Dawley rats (7 weeks old) were approximately 2.4 ± 0.32 μmol L−1 (n = 4). The proposed HPLC method was applied to determine KYN levels in the plasma of ketamine-treated rats—the animal model of schizophrenia. 相似文献
949.
To prepare sulfur-containing natural polymers effectively, several plant oils and 3,3'-thiodipropionic acid (TDP) have been used as carbon sources for the biosynthesis of copolymer poly[(3-hydroxybutyrate)-co-(3-mercaptopropionate)] [poly(3HB-co-3MP)] by a wild-type bacterium Cupriviadus necator H16. By using the plant oils, copolymer accumulation and incorporation of 3MP units are greater than those of cases using sugars. The 3MP fraction is controllable over a range of 1-39 mol-% by adjusting the cultivation conditions. Microbial degradability of the copolymers has been examined in an activated sludge supernatant. The biodegradation proceeded by two mechanisms: surface erosion and auto-catalytic hydrolysis, depending on the 3MP unit fraction, and show preferential degradation of 3HB unit sequences. 相似文献
950.
Sum frequency generation (SFG) spectra and surface pressure–molecular area (π–A) isotherms have been obtained for mixed cholesterol–DPPC
monolayers with cholesterol mole fractions, x(chol.), from 0 to 1.0, at the air–water interface, under same conditions, at 22 °C. Analysis of the spectra indicated that
incorporation of cholesterol into the monolayers at 3 mN m−1 greatly increases the conformational and orientational order of the alkyl chains of DPPC, maximizing these properties at
x(chol.)=0.4. Analysis also indicated that order in the mixed monolayers at 15 and 35 mN m−1 is not affected by incorporation of cholesterol. The π–A isotherms measured at 3 mN m−1 for the mixed monolayer with x(chol.)=0.4 have the largest negative deviation of the molecular area relative to those of ideal mixtures (the so-called “condensation
effect” of cholesterol), indicating the most thermodynamically stable state. Comparison of results from SFG spectra and π–A
isotherms explicitly proved that the condensation effect can be interpreted in terms of conformational and orientational ordering
of the alkyl chains of DPPC. 相似文献