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191.
[reaction: see text] Two new unsymmetrical 1,2,4,5-tetrazines, 3-methylsulfinyl-6-methylthio-1,2,4,5-tetrazine (4) and 3-(benzyloxycarbonyl)amino-6-methylsulfinyl-1,2,4,5-tetrazine (5), were prepared, and the scope of their participation in intermolecular inverse electron demand Diels-Alder reactions was defined. As anticipated, sulfoxides 4 and 5 (4 > 5) display a reactivity that is substantially greater than that of their corresponding sulfides (2 and 3), being derived from their enhanced electron-deficient character and resulting in a wider range of potential dienophile choices or the use of milder reaction conditions. The cycloaddition reactions were expectedly regioselective, typically producing a single cycloadduct, ensuring their synthetic utility, but both were found to proceed with a regioselectivity opposite what would be anticipated and complementary to that observed with 2 and 3. 相似文献
192.
Ohyama K Fujimoto E Wada M Kishikawa N Ohba Y Akiyama S Nakashima K Kuroda N 《Journal of separation science》2005,28(8):767-773
Capillary electrochromatography (CEC) with a novel stationary phase, 3-(4-sulfo-1,8-naphthalimido)propyl-modified silyl silica gel (SNAIP), proved useful for the separation of nucleosides and nucleic acid bases. The application scope of SNAIP, which is a relatively polar reversed-phase (RP)-type stationary phase, was successfully expanded to include the CEC separation of polar compounds although the combination of non-polar RP phase with highly aqueous mobile phase is often inadequate. Due to the permanently charged sulfonic acid groups and the naphthalimidopropyl moiety, the retention of charged and relatively polar nucleosides as well as bases on the SNAIP stationary phase was effected by electrostatic and hydrophobic interactions. This yielded a unique selectivity on SNAIP toward nucleosides and bases. The characteristic EOF on SNAIP, which was stronger at higher aqueous content in the mobile phase, proved suitable for the separation of polar compounds in reversed-phase mode with highly aqueous mobile phase. In addition, when a double stepwise gradient was employed to accelerate the latest peak (adenine), the elution time was shortened to less than half its original duration. 相似文献
193.
Chihara K Kishikawa N Ohyama K Nakashima K Kuroda N 《Analytical and bioanalytical chemistry》2012,403(9):2765-2770
The Petasis reaction is the multi-component reaction of a carbonyl compound, amine, and arylboronic acid to form an α-amino acid or a β-aminoalcohol. In this work, as the first analytical application of the Petasis reaction, a high-performance liquid chromatographic (HPLC) method with fluorescence detection was developed for determination of glyoxylic acid. The glyoxylic acid was derivatized with 1-pyreneboronic acid, as fluorescent arylboronic acid, in the presence of N-methylbutylamine, as amine, to give a fluorescent α-amino acid. HPLC separation of the fluorescent derivative was performed within 30 min on an octyl column eluted with a gradient prepared from acetonitrile and 50 mmol L(-1) acetate buffer (pH 4.0). The detection limit (S/N=3) for glyoxylic acid was 5.0 nmol L(-1) (20 fmol/injection). The method can be used to determine the concentration of glyoxylic acid in human urine without interference from biological components. 相似文献
194.
Takeshi Yagi Naofumi Kuboki Yoshihisa Suzuki Naotaka Uchino Kazunori Nakamura Kazuaki Yoshida 《Optical Review》1997,4(5):596-600
A new fiber-optic ammonia sensor utilizing rectangular-cladding eccentric-core fiber and a sensitive film containing an indicator dye is demonstrated. The sensitive film is a SiO2-GeO2 gel film including an indicator dye of bromocresol purple or bromocresol green, which is dip-coated by a sol-gel technique. The attenuation of this sensor changes depending on the concentration of ammonia at the wavelength range of 500–700 nm. This sensor can detect several ppm of gaseous ammonia. Various factors determining the sensitivity to detect the ammonia gas and time response of the sensor are also studied. 相似文献
195.
From the dried roots of Neonauclea sessilifolia (Rubiaceae), two new triterpenoid saponins, 3-O-beta-D-glucopyranosyl-(1-->2)-beta-D-quinovopyranosyl quinovic acid (1) and 3-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-quinovopyranosyl pyrocincholic acid 28-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester (2), were isolated, together with five known saponins. The structures of the new saponins were determined by spectroscopic and chemical means. 相似文献
196.
Sameh Ahmed Naoya Kishikawa Kaname Ohyama Toshihide Maki Hiromasa Kurosaki Kenichiro Nakashima Naotaka Kuroda 《Journal of chromatography. A》2009,1216(18):3977-3984
Quinones are a class of compounds of substantial toxicological and pharmacological interest. An ultrasensitive and highly selective chemiluminescence (CL) method was newly developed for the determination of quinones based on the utility of photochemically initiated luminol CL. The method involved ultraviolet (UV) irradiation of quinones to generate reactive oxygen species (ROS) through the unique photosensitization reaction accompanied with the photolytical generation of 3,6-dihydroxyphthalic acid (DHPA) from quinones. The photoproducts were detected by luminol CL reaction. Interestingly, it was noticed that DHPA had enhancement effect for the luminol CL. The generation of the enhancer (DHPA) in association with the oxidant (ROS) in the photochemical reaction greatly increases the sensitivity and selectivity of the proposed luminol CL method. In order to elucidate the type of ROS produced by the photosensitizaion reaction in relation to the proposed CL reaction, we investigated the quenching effect of selective ROS scavengers in the luminol CL. Although several ROS were generated, superoxide anion was the most effective ROS for the generated CL. Moreover, the enhancement mechanism of DHPA for luminol CL was confirmed. The enhancement was found to be through the formation of stabilized semiquinone anion radical that provided long-lived CL. The generation of the semiquinone radical was confirmed by electron spin resonance technique. Furthermore, we developed an HPLC method with on-line photochemical reaction followed by the proposed CL detection for the determination of four quinones. A luminol analogue, L-012, was used for its high sensitivity. The detection limits for quinones obtained with the proposed method (S/N = 3) were in the range 1.5–24 fmol that were 10–1000 times more sensitive compared with the previous methods. Finally, the developed HPLC-CL system was successfully applied for the determination of quinones in airborne particulate samples collected at Nagasaki city. 相似文献
197.
Dewi Yana Tomoko Shimizu Keita Hamasaki Hisakazu Mihara Akihiko Ueno 《Macromolecular rapid communications》2002,23(1):11-15
A cyclodextrin‐peptide hybrid (17NNβ) bearing two naphthalene units in the peptide side chain has been designed and synthesized as a novel chemosensor molecule. Circular dichroism study of the compound revealed that the peptide has α‐helix structure with a helix content of 41%. The peptide revealed both monomer and excimer emission and the intensity of the excimer emission increased while that of the monomer emission decreased upon addition of the guest compound. This behavior was observed for various guest molecules, suggesting that the system can be used for detecting molecules in aqueous solution. 相似文献