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21.
We report on the effect on performance of varying the length of the capillary during throughout in-capillary derivatization (TICD) capillary electrophoresis (CE). Performance was evaluated by on-line coupling with a sample and CE runbuffer loading device that was newly introduced for this study. The device was assembled with a low cost using two 5 mm inner diameter (ID) disposable polyethylene syringes. First, a sequence was manually formed consisting of a 200 microL run buffer solution plug, a 100 microL sample plug and another 200 microL run buffer solution plug. Each plug was separated from its neighbor by a 100 microL air plug. When each plug reached the injection point where both a platinum-wire anode and the end of the separation capillary tube were located, 340 V/cm separation voltage (electrophoresis voltage) and 34 V/cm injection voltage were applied to the capillary for 3 s. Then the analytes were derivatized during migration in 50 microm ID capillaries filled with 2 mM o-phthalaldehyde (OPA)/N-acetylcysteine (NAC) in a 20 mM phosphate-borate buffer (pH 10), followed by separating and detecting of OPA derivatives by absorbance of 340 nm. Derivatization, separation, and detection were performed systematically using capillaries which varied in length from 5 to 80 cm. In the case of TICD-CE of a mixture containing 1 mM aspartic acid (Asp) and 20 mM m-nitorophenol (MNP) as a test solution, it was determined that peak area and peak width ratios of Asp to MNP did not depend on capillary length. Enantiomeric separations of DL-alanine (Ala) and Asp were examined using a run buffer consisting of a 45 microM beta-cyclodextrin (CD)-2 mM OPA/NAC-20 mM phosphate-borate buffer (pH 10). Even though the resolution of these enantiomeric pairs decreased with decreasing capillary length, as expected, the peaks corresponding to both enantiomeric amino acids were identified even when a 5 cm capillary was used. An 8-component amino acid mixture was also tested with 5 cm and 10 cm capillaries. 相似文献
22.
Matsuura K Hibino M Ikeda T Yamada Y Kobayashi K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(2):352-359
We describe herein the relationship between the spatial arrangement of self-organized galactose clusters and lectin recognition. beta-Galactose-modified deoxyuridine phosphoramidite was synthesized and applied to solid-phase synthesis to provide 18-, 20-, and 22-mers of site-specifically galactosylated oligodeoxynucleotides (Gal-ODNs). These Gal-ODNs were self-organized through hybridization with the corresponding 18-, 20-, and 22-mers of half-sliding complementary ODNs (hsc-ODNs) to give periodic galactoside clusters. The self-organization of ODNs was confirmed by size exclusion chromatography and gel electrophoresis. The binding of the Gal-clusters to the FITC-labeled RCA(120) lectin was analyzed by monitoring the change in fluorescence intensity. The assembly of 20-mer Gal-ODN with the 20-mer hsc-ODN was strongly and cooperatively recognized by the lectin. The 18-mer assembly was bound more weakly and less cooperatively, and the 22-mer assembly was minimally bound to the lectin. RCA(120) lectin recognized not only the density of galactoside residues, but also the spatial arrangement. The size of the Gal cluster was estimated from the association constant of Gal-ODN with hsc-ODN. The relationship between lectin-recognition and Gal-cluster size is also discussed. 相似文献
23.
Takehiko Nishio Kyoko Iseki Norihito Araki Takenori Miyazaki 《Helvetica chimica acta》2005,88(1):35-41
The radical reactions of N‐(2‐halogenoalkanoyl)‐substituted anilines (anilides) of type 1 have been investigated under various conditions. Treatment of compounds 1a – 1o with Bu3SnH in the presence of (2,2′‐azobis(isobutyronitrile) (AIBN) afforded a mixture of the indolones (oxindoles) 2a – 2o and the reduction products 5a – 5o (Table 1). In contrast, the N‐unsubstituted anilides 1p – 1s, 1u , and 1v gave the corresponding reduction products exclusively (Table 1). Similar results were obtained by treatment of 1 with Ni powder (Table 2) or wth Et3B (Table 3). Anilides with longer N‐(phenylalkyl) chains such as 6 and 7 were inert towards radical cyclization, with the exception of N‐benzyl‐2‐bromo‐N,2‐dimethylpropanamide ( 6b ), which, upon treatment with Ni powder in i‐PrOH, afforded the cyclized product 9b in low yield (Table 4). Upon irradiation, the extended anilides 6, 7, 10 , and 11 yielded the corresponding dehydrobromination products exclusively (Table 5). 相似文献
24.
The asymmetric hydroformylation of 2‐ and 3‐vinylfurans ( 2a and 2b , resp.) was investigated by using [Rh{(R,S)‐binaphos}] complexes as catalysts ((R,S)‐binaphos = (11bS)‐4‐{[1R)‐2′‐phosphino[1,1′‐binaphthalen]‐2‐yl]oxy}dinaphtho[2,1‐d:1′,2′‐f][1,3,2]dioxaphosphepin; 1 ). Hydroformylation of 2 gave isoaldehydes 3 in high regio‐ and enantioselectivities (Scheme 2 and Table). Reduction of the aldehydes 3 with NaBH4 successfully afforded the corresponding alcohols 5 without loss of enantiomeric purity (Scheme 3). 相似文献
25.
26.
Wenjie Tao Xiaoming Wang Shingo Ito Kyoko Nozaki 《Journal of polymer science. Part A, Polymer chemistry》2019,57(3):474-477
Herein, we report the synthesis of palladium complexes bearing an N‐heterocyclic carbene (NHC)‐sulfonamide bidentate ligand and their application in ethylene oligomerization and ethylene/polar monomer cooligomerization. These catalysts could smoothly catalyze ethylene oligomerization and ethylene/methyl acrylate cooligomerization albeit the performance was lower compared to that of a NHC–phenoxide catalyst. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 474–477 相似文献
27.
A one-pot approach to indolo[2,1-b]quinazolines from indole-3-carbaldehydes through the Dakin oxidation was developed. It was shown that the reaction proceeded through the condensation of indole-3-carbaldehydes with isatoic anhydrides, derived in situ from indole-3-carbaldehydes by the Dakin oxidation, and further oxidation/cyclization steps. 相似文献
28.
Atsutoshi Yamada Yuki Watanabe Kyoko Noda Sumitaka Itoh Koji Ishihara Masahiko Inamo Refat Moustafa Hassan Hideo D. Takagi 《Journal of solution chemistry》2014,43(9-10):1479-1486
The reduction reaction of the Cu(II)–pitn complex (pitn = 1,3-di(pyridine-2-carboxaldimino)propane) by decamethylferrocene [Fe(Cp*)2] was examined in acetonitrile. The observed pseudo-first-order rate constants exhibited saturation kinetics with increasing excess amount of [Fe(Cp*)2]. Detailed analyses revealed that the reaction is controlled by a structural change prior to the electron transfer step, rather than a conventional bimolecular electron transfer process preceded by ion pair (encounter complex) formation. The rate constant for the structural change was estimated to be 275 ± 13 s?1 at 298 K (?H* = 33.3 ± 1.0 kJ·mol?1, ?S* = 86 ± 5 J·mol?1·K?1), which is the fastest among gated reactions involving CuN4 complexes. It was confirmed by EPR measurement and Conflex calculations that the dihedral angle between the two N–N planes is significantly large (40°) in solution whereas it is merely 17.14° in the crystal. 相似文献
29.
Yohei Saito Atsushi Mizokami Kouji Izumi Renato Naito Masuo Goto Kyoko Nakagawa-Goto 《Molecules (Basel, Switzerland)》2021,26(9)
α-Trifluoromethyl chalcones were prepared and evaluated for their antiproliferative activities against androgen-independent prostate cancer cell lines as well as five additional types of human tumor cell lines. The most potent chalcone 5 showed superior antitumor activity in vivo with both oral and intraperitoneal administration at 3 mg/kg. Cell-based mechanism of action studies demonstrated that 5 induced cell accumulation at sub-G1 and G2/M phases without interfering with microtubule polymerization. Furthermore, several cancer cell growth-related proteins were identified by using chalcone 5 as a bait for the affinity purification of binding proteins. 相似文献
30.
Kumar Samir Taneichi Taiga Fukuoka Takao Namura Kyoko Suzuki Motofumi 《Cellulose (London, England)》2021,28(17):10803-10813
Cellulose - Surface-enhanced Raman spectroscopy (SERS)-based biosensors have recently been extensively developed because of their high sensitivity and nondestructive nature. Conventional SERS... 相似文献