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81.
Synthetic studies of two components of tubulysins, tubulin polymerization inhibitors are described. The highly stereoselective synthesis of tubuvaline methyl ester (2) was accomplished by 1,3-dipolar cycloaddition of nitrone d-6 and acrylic acid derivatives 7 as a key step. The synthesis of tubuphenylalanine (3) was conducted by an aldol reaction of a boron enolate of (S)-4-isopropyl-3-propionyl-2-oxazolidinone (13) with aldehyde 14, readily prepared from phenylalanine, followed by Barton deoxygenation under radical conditions. 相似文献
82.
Zhang GJ Song KS Nakamura Y Ueno T Funatsu T Ohdomari I Kawarada H 《Langmuir : the ACS journal of surfaces and colloids》2006,22(8):3728-3734
We report a novel method of one-step direct amination on polycrystalline diamond to produce functionalized surfaces for DNA micropatterning by photolithography. Polycrystalline diamond was exposed to UV irradiation in ammonia gas to generate amine groups directly. After patterning, optical microscopy confirmed that micropatterns covered with an Au mask were regular in size and shape. The regions outside the micropatterns were passivated with fluorine termination by C3F8 plasma, and the chemical changes on the two different surfaces--the amine groups inside the patterned regions by one-step direct amination and fluorine termination outside the patterned regions--were characterized by spatially resolved X-ray photoelectron spectroscopy (XPS). The patterned areas terminated with active amine groups were then immobilized with probe DNA via a bifunctional molecule. The sequence specificity was conducted by hybridizing fluorescently labeled target DNA to both complementary and noncomplementary probe DNA attached inside the micropatterns. The fluorescence micropatterns observed by epifluorescence microscopy corresponded to those imaged by optical microscopy. DNA hybridization and denaturation experiments on a DNA-modified diamond show that the diamond surfaces reveal superior stability. The influence of a different amination time on fluorescence intensity was compared. Different terminations as passivated layers were investigated, and as a result, fluorine termination points to the greatest signal-to-noise ratio. 相似文献
83.
Kashimoto K Takata Y Matsuda T Ikeda N Matsubara H Takiue T Aratono M Tanida H Watanabe I 《Langmuir : the ACS journal of surfaces and colloids》2006,22(20):8403-8408
The total-reflection X-ray absorption fine structure (XAFS) method previously employed for the adsorption of dodecyltrimethylammonium bromide (DTAB) at the air/water interface was applied to that in the presence of NaBr. The surface concentration of the bromide ions Gamma(X)(B) of DTAB and NaBr was evaluated by using the Br K-edge absorption jump values of the total-reflection XAFS spectra and was compared to the corresponding value Gamma(H)(B) estimated from the dependence of surface tension on the bulk concentrations of DTAB m(1) and NaBr m(2). The Gamma(X)(B) values trace almost perfectly the Gamma(X)(B) versus m(1) curve up to a concentration near the critical micelle concentration (cmc) and deviate gradually above the concentration. This behavior is basically similar to that of the single DTAB system and ensures that the XAFS method is also applicable to the DTAB system, even in the presence of NaBr. In addition, this method was extended to the single nonionic amphiphile with covalently bonded bromine, and the surface concentrations of 6-bromo-1-hexanol (BrC6OH), Gamma(X)(1) and Gamma(H)(B), were evaluated and compared with each other. It was found that the Gamma(X)(1) value almost perfectly traces the Gamma(H)(1) versus m(1) curve, even at high surface concentrations. The excellent coincidence confirmed that the total-reflection XAFS method can be applied to the nonionic amphiphile system as well as a cationic surfactant with or without an added salt system. Finally, the difference between the Gamma(X)(B) and Gamma(H)(B) values observed in the DTAB with and without an added salt system is briefly described. 相似文献
84.
Aida H Mori K Yamaguchi Y Mizuta S Moriyama T Yamamoto I Fujimoto T 《Organic letters》2012,14(3):812-815
A phosphinite derivative that can be easily prepared in two steps from commercially available aminoindanol was found to be an effective catalyst for enantioselective acylation of diols. For the asymmetric desymmetrization of meso-1,2-diols, the corresponding monoester was obtained in up to 95% ee from the reaction in the presence of 5 mol % catalyst. 相似文献
85.
Iwao Soga Steve Granick 《Colloids and surfaces. A, Physicochemical and engineering aspects》2000,170(2-3):113-117
We measure, for the first time, the separate surface coverage-dependent orientations of trains and of loops/tails in the structure of an adsorbed polymer, and show that these have different average orientations. The system was PMMA (atactic polymethylmethacrylate) adsorbed onto oxidized silicon from dilute solution in carbon tetrachloride at 25.0°C. The method was FTIR-ATR (infrared spectroscopy in attenuated total reflection). With increasing surface coverage, train segments were observed to maintain constant average anisotropy with respect to the solid surface. Free segments were preferentially flattened when the surface coverage was low, but with increasing surface coverage became progressively more random in orientation. Free and bound segments were separated according to shifts of the vibrational frequencies of carbonyl segments upon hydrogen-bonding to the surface silanol groups. The dependence of segmental orientation on molecular weight of the chain is also discussed. 相似文献
86.
Kazuchika Ohta Satoru Azumane Takuya Watanabe Satoshi Tsukada Iwao Yamamoto 《应用有机金属化学》1996,10(8):623-635
Eight novel octakis(3,4-dialkoxyphenyl)- phthalocyanine derivatives, Cn-M (2, M=2H; 3, M=Ni; 4, M=Cu; a, decyloxy; b, undecyloxy; c, dodecyloxy), have been synthesized and characterized. It was found that each of the derivatives exhibits discotic liquid crystalline properties, and that each of the Cn–Cu (4) derivatives has two kinds of Drd2( P 21/ a ) mesophases. These Cn–Cu (4a,b,c) and C12–2H (2c) derivatives exhibit a unique double clearing behavior. 相似文献
87.
Time-resolved electron paramagnetic resonance (EPR), fluorescence, and phosphorescence spectra have been observed for the excited states oftrans-p-methylcinnamic acid (p-MeCA) andtrans-p-methylcinnamate anion (p-MeCA?) in rigid organic glasses at 77 K. With a stretched-polymer-film technique, we assigned the resonance fields in the time-resolved EPR spectra of the lowest excited triplet (T1) states ofp-MeCA andp-MeCA?. From the analysis of these spectra we concluded that the deviation from planar structure in the T1 state is small inp-MeCA andp-MeCA? and the direction of C=O iss-cis to the ethylenic C=C bond inp-MeCA. The deprotonation appears to have little effect on the zero-field splitting (ZFS) parameters. The ZFS parameters were calculated theoretically using semiempirical molecular orbitals. The sublevel preferentially populated by intersystem crossing (ISC) is T y in bothp-MeCA andp-MeCA?. However, following the deprotonation ofp-MeCA, (P y?P z)/(P x?P z) changes from 5.7 inp-MeCA to 2.1 inp-MeCA? (P i are relative populating rates; thex andy axes are close to the long and short in-plane molecular axes, respectively, andz-axis is perpendicular to the molecular plane). The fluorescence lifetimes indicate that the deprotonation has little effect on the sum of the three ISC rate constants for the three T1 sublevels. A decrease in acidity ofp-MeCA upon excitation has been observed. 相似文献
88.
89.
90.
A series of novel chiral bisazetidines in which two azetidine rings are either directly connected or coupled in tandem style, are synthesized in good yields by the hydroalane reduction of the corresponding bis-beta-lactame. 相似文献