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51.
We have successfully developed a novel environmentally friendly electrolytic system using recyclable solid-supported bases for in situ generation of a supporting electrolyte from methanol as a solvent. It was found that solid-supported bases are electrochemically inactive at an electrode surface. It was also found that solid-supported bases dissociate methanol into methoxide anions and protons. Therefore, in the presence of solid-supported bases, it was clarified that methanol serves as both a solvent and a supporting electrolyte generated in situ. Anodic methoxylation of various compounds with solid-supported bases was carried out to provide the corresponding methoxylated products in good to excellent yields with a few exceptions. The methoxylated products and the solid-supported bases were easily separated by only filtration, and the desired pure methoxylated products were readily isolated simply by concentration of the filtrates. The separated and recovered solid-supported bases were recyclable for several times. 相似文献
52.
The effects of ultrasonication on the chemical polymerization of aniline leading to the formation of conducting polyaniline colloids were examined. The formation rate of the colloids was significantly increased under ultrasonication. Furthermore, it was also observed that the morphological structure of the colloids thus prepared was greatly affected by the sonication. The polyaniline colloids were further characterized by a range of techniques including electric resistance meter, gel permeation chromatography, FT-IR and cyclic voltammetry. It is noteworthy that the application of ultrasound to the polymerization resulted in a marked increase in the doping level, which reflected to the high electroconductivity of polyaniline colloids. 相似文献
53.
Antioxidant and prooxidant effects of nitric oxide (NO) on lipid peroxidation in aqueous and non-aqueous media were examined. In an aqueous solution, NO did not induce peroxidation of unoxidized methyl linoleate (ML) and suppressed the radical initiator-induced oxidation of ML. NO suppressed the Fe(II) ion-induced oxidation of mouse liver microsomes. NO reduced the O2 consumption during the radical initiator-induced oxidation of linoleic acid in an aqueous medium. NO conversion into NO2- in an aqueous medium was not affected by unoxidized ML and was slightly reduced by peroxidizing ML. On the other hand, as well as pure NO2, NO induced peroxidation of unoxidized ML in n-hexane in a dose-dependent fashion. NO did not suppress the radical initiator-induced oxidation of ML in n-hexane. Nitrogen oxide species (NO2 or N2O3) formed by autoxidation was dramatically lost in n-hexane in the presence of unoxidized ML. The results indicated that NO terminated lipid peroxidation in an aqueous medium, whereas NO induced lipid peroxidatiton in a non-aqueous medium. Hence, NO showed both antioxidant and prooxidant effects on lipid peroxidation depending on the solvents. 相似文献
54.
Electropolymerization of an immiscible monomer in aqueous electrolytes using acoustic emulsification
This paper reports on the novel electropolymerization of an immiscible monomer, such as 3,4-ethylenedioxythiophene (EDOT), in aqueous electrolytes using acoustic emulsification. This new methodology has many practical advantages and characteristics: (a) the formation of stable monomer droplets in aqueous electrolytes without added surfactants using ultrasonic treatment; (b) very smooth electropolymerization in aqueous electrolytes via the direct electron transfer between the electrode and the immiscible monomer droplets; (c) good conductivity after doping of the polymer film formed. 相似文献
55.
Baba D Ishii H Higashiya S Fujisawa K Fuchigami T 《The Journal of organic chemistry》2001,66(21):7020-7024
Anodic fluorination of N-benzoyl, N-acethyl-, and N-formylthiazolidine derived from L-cysteine was carried out in dimethoxyethane (DME) and acetonitrile containing various supporting fluoride salts using an undivided cell. Highly regioselective fluorination proceeded to provide the corresponding 5-monofluorinated thiazolidine derivatives in good yields in DME, and the diastereoselectivitiy was moderate to high regardless of the supporting fluoride salts. The diastereoselectivitiy of the fluorination was greatly affected by the bulkyness of the subsitituent on the nitrogen atom, and N-benzoylthiazolidine gave much higher diastereoselectivity compared with N-formyl derivative. The fluorination of the thiazolidines was not achieved by commercially available fluorinating reagents such as N-fluoropyridinium salts. 相似文献
56.
Anodic fluorination of (E)-3-benzylidene-2,3-dihydrothiochroman-4-one and 3-benzyl-1-thiochromone derivatives under a variety of electrolytic conditions was found to provide selectively or exclusively the same fluorinated products: (E)-3-benzylidene-2,3-dihydro-2-fluorothiochroman-4-ones. In addition, di- and trifluorinated derivatives were also obtained depending on the starting heterocycles and electrolytic conditions. The factors affecting the product selectivity were also examined. 相似文献
57.
Ronaldo Alves Garcia Dirce Kiyomi Hayashida Mochida Maria del Carmen Romero Fuster Maria Aparecida Soares Ruas 《Transactions of the American Mathematical Society》2000,352(7):3029-3043
We consider asymptotic line fields on generic surfaces in 4-space and show that they are globally defined on locally convex surfaces, and their singularities are the inflection points of the surface. As a consequence of the generalized Poincaré-Hopf formula, we obtain some relations between the number of inflection points in a generic surface and its Euler number. In particular, it follows that any 2-sphere, generically embedded as a locally convex surface in 4-space, has at least 4 inflection points.
58.
Yasuo Sasaki Ryo SugiuraYasuhiro Nishiyama Hiroki TanimotoTsumoru Morimoto Kiyomi Kakiuchi 《Tetrahedron》2014
A new caged firefly luciferin (luciferin) with a thiochromone S,S-dioxide (TSSDO) as a photolabile protecting group was synthesized. Photodeprotection of the caged compound proceeded smoothly under photoirradiation at 365 nm in aqueous solution. The bioluminescence of the regenerated luciferin after uncaging was detected using a typical luciferin–luciferase reaction. These results indicated that TSSDO could be an attractive chemical tool for regulating biological phenomena. 相似文献
59.
The anodic substitution reaction proceeded smoothly without affecting the oxidation of the nucleophile in a one-step electrochemical operation using acoustic emulsification. 相似文献
60.
Torigoe H Rahman SM Takuma H Sato N Imanishi T Obika S Sasaki K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(9):2742-2751
Due to the instability of pyrimidine motif triplex DNA at physiological pH, triplex stabilization at physiological pH is crucial in improving its potential in various triplex-formation-based strategies in vivo, such as gene expression regulation, genomic DNA mapping, and gene-targeted mutagenesis. To this end, we investigated the thermodynamic and kinetic effects of our previously reported chemical modification, 2'-O,4'-C-aminomethylene-bridged nucleic acid (2',4'-BNA(NC)) modification of triplex-forming oligonucleotide (TFO), on triplex formation at physiological pH. The thermodynamic analyses indicated that the 2',4'-BNA(NC) modification of TFO increased the binding constant of the triplex formation at physiological pH by more than 10-fold. The number and position of the 2',4'-BNA(NC) modification in TFO did not significantly affect the magnitude of the increase in the binding constant. The consideration of the observed thermodynamic parameters suggested that the increased rigidity and the increased degree of hydration of the 2',4'-BNA(NC)-modified TFO in the free state relative to the unmodified TFO may enable the significant increase in the binding constant. Kinetic data demonstrated that the observed increase in the binding constant by the 2',4'-BNA(NC) modification resulted mainly from the considerable decrease in the dissociation rate constant. The TFO stability in human serum showed that the 2',4'-BNA(NC) modification significantly increased the nuclease resistance of TFO. Our results support the idea that the 2',4'-BNA(NC) modification of TFO could be a key chemical modification to achieve higher binding affinity and higher nuclease resistance in the triplex formation under physiological conditions, and may lead to progress in various triplex-formation-based strategies in vivo. 相似文献