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81.
A Pd-catalyzed asymmetric synthesis of Si-stereogenic dibenzosiloles is developed through enantioselective C-H bond functionalization of prochiral 2-(arylsilyl)aryl triflates. High chemo- and enantioselectivities are achieved by employing a Josiphos-type ligand under mild conditions. 相似文献
82.
Enantiomeric separation by capillary electrochromatography with beta-cyclodextrin-bonded negatively charged polyacrylamide gels was examined. The columns used are capillaries filled with a negatively charged polyacrylamide gel, a so-called monolithic stationary phase, to which allyl carbamoylated beta-CD (AC-beta-CD) derivatives covalently bind. The capillary wall is activated first with a bifunctional reagent to make the resulting gel bind covalently to the inner surface of the fused-silica tubing. Enantiomeric separations of 15 cationic compounds were achieved using the above-mentioned columns and mobile phases of 200 mmol l(-1) Tris-300 mmol I(-1) boric acid buffer (pH 7.0 or 9.0) or 200 mmol l(-1) Tris-300 mmol l(-1) boric acid buffer (pH 7.0) containing an achiral crown ether (18-crown-6). Enantiomeric separations of two neutral compounds were also achieved using 200 mmol l(-1) Tris-300 mmol l(-1) boric acid buffer (pH 9.0) as a mobile phase. High efficiencies of up to 150,000 plates m(-1) were obtained. Both the within- and between-run reproducibilities of retention time and separation factor were good. The reproducibilities of retention time and separation factor for three different columns prepared from a different batch of monomers were acceptable. The gel-filled capillaries were stable for at least 3 months with intermittent use, utilizing the mobile phase of 200 mmol I(-1) Tris-300 mmol I(-1) boric acid buffer (pH 9.0). 相似文献
83.
A convenient method for determination of sodium azide in beverages using ion chromatography is described. This method combines the specificity for azide with a simple sample preparation using a bubble and trap apparatus that removes any interferences. Sodium azide in a sample was acidified, and the azide was converted to the volatile hydrazoic acid, which was trapped in 2.5 mM sodium hydroxide solution. Determination was performed by isocratic ion chromatography using suppressed conductivity detection. Calibration curves were linear for 0.5 to 20 microg/mL sodium azide and the detection limit was 0.05 microg/mL. Recoveries of sodium azide from spiked samples (10.0 microg/g) were more than 82.6%. The method was then used to analyze various beverages. 相似文献
84.
Mohammed Akhter Hossain Keiko Takahashi Hisakazu Mihara Akihiko Ueno 《Journal of inclusion phenomena and macrocyclic chemistry》2002,43(3-4):271-277
-Helix peptides bearing one unit of -cyclodextrin (-CD), one unit of pyrene and one unit of nitrobenzene (NB) in their side chains have been designed and synthesized as novel molecule-responsive devices.In both the CD-peptides,
-PR17 and
-PL17, the NB unit is separated from the CD unit by two turns of the helix. Two reference peptides (PL17, and -P17,) have also been synthesized. The circular dichroism studies in the peptide absorption region (200–250 nm)of
-PR17 and
-PL17 suggestthat the CD-peptides form stable-helixstructures (83–77%), which was destabilized by accommodating guest molecules (e.g., n-pentanol) into the CD cavity. It suggests that formation of intramolecular host–guest(CD–NB) complex stabilized thehelical structure and exogenous guest molecule excluded the appending NB moiety from inside to outside of the CD cavity, thereby causing destabilization of the helical structure and increasing the random coil content. The ICD spectra of the peptides in the pyrene and nitrobenzene absorption region (250–40 nm) suggest that NB forms inclusion complex with CD. The fluorescence studies revealed that the fluorescence of the pyrene unit is quenched by the NB unit in
-PR17 and
-PL17. The fluorescence intensity increases with increasing guest concentration for the CD-peptides.This guest-responsiveenhancement in the fluorescence intensity can be explained in terms of increased distance between the pyrene and NB moieties, which is caused by exclusion of the NB moiety from the CD cavity by guest accommodation. Using the guest-responsive fluorescence quenching properties of the CD-peptides, we have obtained binding constants for various short chain alkanols.
-PL17 has higher binding affinity to the guest molecules than its isomer,
-PR17, indicating that the location of functional groups on the peptide scaffold is important in molecule detection. 相似文献
85.
Sakamoto M Ohba A Kuriyama J Maruo K Ueno S Sato K 《Colloids and surfaces. B, Biointerfaces》2004,37(1-2):27-33
We examined the crystallization of palm mid fraction (PMF) in oil-in-water (O/W) emulsion, after adding polyglycerol fatty acid esters (PGFEs). We employed ultrasonic velocity measurements and DSC techniques, with special emphases on the influences of fatty acid moiety and esterification of PGFE. Twelve types of PGFEs were examined as additives. PGFEs have a large hydrophilic moiety composed of 10 glycerol molecules to which palmitic, stearic and behenic acids were esterified as the fatty acid moiety with different degrees of esterification. Crystallization temperature (T(c)) of PMF remarkably increased with increasing concentrations of the PGFEs as the chain length of the fatty acid moiety increased, and the PGFE became more hydrophobic in accordance with increasing degree of esterification. We observed that the heterogeneous nucleation of PMF in the O/W emulsion was activated at the oil-water interface, where the template effect of very hydrophobic long saturated fatty acid chains of the PGFE might play the main role of heterogeneous nucleation. 相似文献
86.
[reaction: see text] A rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to fumaric and maleic compounds has been developed. While phosphorus-based chiral ligands fail to induce high stereoselectivity, chiral norbornadiene ligands have proved to be uniquely effective to achieve high enantioselectivity in these 1,4-addition reactions. 相似文献
87.
The molar conductivities Lambda of NaCl, KCl, and CsCl in liquid methanol were measured in the concentration range of (0.3-2.0) x 10(-3) mol dm(-3) and the temperature range of 60-240 degrees C along the liquid-vapor coexistence curve. The temperature range corresponds to the solvent density range of (2.78-1.55)rhoc, where rhoc = 0.2756 g cm(-3) is the critical density of methanol. The concentration dependence of Lambda at each temperature and density (pressure) has been analyzed by the Fuoss-Chen-Justice equation to obtain the limiting molar conductivity Lambda0 and the molar association constant KA. For all the electrolytes studied, Lambda0 increased almost linearly with decreasing density at densities above 2.0rhoc, while the opposite tendency was observed at lower densities. The relative contribution of the nonhydrodynamic effect on the translational friction coefficient zeta was estimated in terms of Deltazeta/zeta, where the residual friction coefficient Deltazeta is the difference between zeta and the Stokes friction coefficient zetaS. At densities above 2.0rhoc, Deltazeta/zeta increased with decreasing density though zeta and Deltazeta decrease, and the tendencies are common for all the ions studied. The density dependences of zeta and Deltazeta/zeta were explained well by the Hubbard-Onsager (HO) dielectric friction theory based on the sphere-in-continuum model. At densities below 2.0rhoc, however, the experimental results cannot be explained by the HO theory. 相似文献
88.
Takayuki Toyoda Hisakazu Mihara Akihiko Ueno 《Macromolecular rapid communications》2002,23(15):905-908
Peptides bearing β‐cyclodextrin and 4‐(N,N‐dimethylamino)benzoyl (DMAB) units in the peptide side chains were prepared as chemosensors for molecule detection. The DMAB unit was expected to be included into the cyclodextrin cavity intramolecularly. However, these peptides exhibited no twisted intramolecular charge transfer fluorescence and the normal fluorescence intensity decreased upon the addition of 1‐adamantanol as an exogenous guest, indicating that the DMAB units are shallowly included in the cyclodextrin cavities. 相似文献
89.
Aoyagi Y Saitoh Y Ueno T Horiguchi M Takeya K Williams RM 《The Journal of organic chemistry》2003,68(18):6899-6904
Lipase TL-mediated kinetic resolution of (+/-)-5-benzyloxy-1-tert-butyldimethylsilyloxy-2-pentanol (5) at low temperature proceeded to give the corresponding (S)-alcohol 5 and (R)-acetate 6 in quantitative yields with high enantiomeric purity. The addition of bases such as pyridine, DMAP, 2,4- and 2,6-lutidines, or triethylamine considerably enhanced the rate of kinetic resolution. The alcohol (S)-5 and the acetate (R)-6 were converted to piperazic acid derivatives (R)- and (S)-3, respectively, via the intramolecular Mitsunobu reaction as a key step. 相似文献
90.
A new efficient system for transporting saccharides through a liquid membrane has been constructed. The transport rates of saccharides were accelerated greatly by the cyclodextrin dimer 2; by contrast, the corresponding cyclodextrin monomer 1 was not effective at mediating saccharide transport. The transport rate of D-ribose through a chloroform liquid membrane was 17 times faster when the cyclodextrin dimer 2 was used as the transporter than when the cyclodextrin monomer 1 was used. Similarly the transport rate of methyl D-galactopyranoside was 16 times faster by 2 than by 1. 相似文献