• Title/Summary/Keyword: Active methylene group

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Silica Supported Ammonium Acetate: An Efficient and Recyclable Heterogeneous Catalyst for Knoevenagel Condensation between Adehydes or Ketones and Active Methylene Group in Liquid Phase

  • Gupta, Raman;Gupta, Monika;Paul, Satya;Gupta, Rajive
    • Bulletin of the Korean Chemical Society
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    • v.30 no.10
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    • pp.2419-2421
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    • 2009
  • A simple and efficient method has been developed for Knoevenagel condensation between aldehydes or ketones and active methylene group by stirring in methylene chloride at 60 ${^{\circ}C}$ under heterogeneous conditions using silica supported ammonium acetate. The products are obtained in excellent yields and are in a state of high purity. The structures of the products were confirmed by IR, $^1H$ NMR and mass spectral data and comparison with authentic samples available commercially.

Methylene Blue-stained Interstitial Cells are Electrically Active in the Myenteric Board Freshly Prepared from the Murine Small Intestine

  • Lee, Kyu-Pil;Jeon, Ju-Hong;So, In-Suk;Kim, Ki-Whan
    • The Korean Journal of Physiology and Pharmacology
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    • v.10 no.4
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    • pp.193-198
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    • 2006
  • Many gastrointestinal muscles show electrical oscillation, so-called 'slow wave', originated from interstitial cells of Cajal (ICCs). Thus, a technique to freshly isolate the cells is indispensable to explore the electrophysiological properties of the ICCs. To apply an enzyme solution on the serosal surface for cell isolation, the intestine was inverted and 0.02% trypsin solution and 0.04% collagenase solution were applied to serosal cavity. After the enzyme treatment, mucosal layer was removed and longitudinal muscle layer was gently separated from the rest of tissue. The thin layer was stretched in the recording chamber and mounted on an inverted microscope. Using ${\beta}-escine$, perforated whole cell patch clamp technique was used. Under a microscope, the tissue showed smooth muscle cells and interstitial cells around the myenteric plexus. Under voltage clamp condition, three types of membrane potential were recorded. One group of interstitial cells, which were positive to methylene blue and CD34, showed spontaneous outward current. These cells had bipolar shape and were considered as fibroblast-like cells because of their peculiar shape and arrangement. Another group, positive to c-kit and methylene blue, showed spontaneous inward current. These cells had more rounded shape and processes and were considered as ICCs. The third, positive to c-kit and had granules containing methylene blue, showed quiet membrane potentials under the voltage-clamp mode. These cells appeared to be resident macrophages. Therefore, in the freshly isolated thin tissue preparation, methylene blue could easily identify three types of cells rather than morphological properties. Using this method, we were able to study electrical properties of fibroblast and residential macrophage as well as myenteric ICCs.

Synthesis and Absorption Spectral Properties of Bis-methine Dyes Exemplified by 2,5-Bis-arylidene-1-dicyanomethylene-cyclopentanes

  • Asiri, Abdullah Mohamed
    • Bulletin of the Korean Chemical Society
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    • v.24 no.4
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    • pp.426-430
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    • 2003
  • A range of methine dyes has been synthesized by condensation of highly electronegative active methylene compound dicyanomethylenecyclopentane derived from cyclopentanone with the formyl group of substituted benzaldehydes. The electronic absorption spectroscopic properties of the dyes were investigated. In general, substituents on the aromatic aldehyde moiety have a significant effect on the visible absorption maxima of the dyes; increasing the solvent polarity also showed a pronounced effect on the absorption maxima.

Straightforward synthesis of 4'${\alpha}$-C-hydroxymethyl branched novel carbocyclic nucleosides

  • Oh, Jung-Hyo;Kim, Kwan-Woo;Hong, Joon-Hee
    • Proceedings of the PSK Conference
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    • 2002.10a
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    • pp.354.1-354.1
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    • 2002
  • Carbocyclic nucleosides are unique class in which a methylene group replaces the oxygen in the furan, which result in metabolic stability to endogenous phosphorylase. The biologically active natural carbocyclic nucleosides such as aristeromycin and neplanocin were found to possess interesting biological properties including antiviral and antitumor activity. (omitted)

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Isolation and Identification of an Unauthorized Sildenafil Analogue in a Commercial Functional Food (시판 기능성식품으로부터의 실데나필 유도체 부정첨가물질의 분리 및 구조규명)

  • Baek, Du-Jong
    • Journal of the Korean Chemical Society
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    • v.54 no.4
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    • pp.443-446
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    • 2010
  • HPLC analysis of a commercial herb drink marketed as a functional food revealed to contain an unauthorized substance similar to sildenafil, the active ingredient of the prescription drug Viagra$^{(R)}$ approved for the treatment of male erectile dysfunction. In order to identify the illegal additive, the herb drink was extracted with methylene chloride, and the extract was purified further using semipreparative HPLC. The chemical structure of the isolated substance was elucidated based on IR, LC/MS-ESI, and NMR spectroscopy, which showed the characteristics similar to sildenafil with minor modification. The only difference was the substitution of the methylpiperazine moiety of sildenafil to the hydroxyethylpiperazine group of the illegal additive.

Isolation and Identification of an Unauthorized Tadalafil Analogue in a Commercial Functional Food (시판 기능성식품으로부터의 타다라필 유도체 부정첨가물질의 분리 및 구조규명)

  • Baek, Du-Jong
    • YAKHAK HOEJI
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    • v.54 no.4
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    • pp.240-243
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    • 2010
  • High-performance liquid chromatography (HPLC) screening method revealed that a propolis product marketed as a functional food contained an undeclared substance similar to tadalafil, the active ingredient of the prescription drug Cialis$^{(R)}$ approved for the treatment of male erectile dysfunction. In order to identify the illegal additive, the propolis product was extracted with methylene chloride, and the extract was purified further using semipreparative HPLC. The chemical structure of the isolated substance was elucidated based on IR, LC/MS-ESI, and $^1H$- and $^{13}C$-NMR spectroscopy, which showed the characteristics similar to tadalafil. The only difference was the substitution of the methyl group at the piperazinedione ring of tadalafil to the amino group of the identified illegal additive.

Preparation of Dinuclear, Constrained Geometry Zirconium Complexes with Polymethylene Bridges and an Investigation of Their Polymerization Behavior

  • Noh, Seok-Kyun;Jiang, Wen-Long
    • Macromolecular Research
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    • v.12 no.1
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    • pp.100-106
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    • 2004
  • We have prepared the polymethylene-bridged, dinuciear, half-sandwich constrained geometry catalysts (CGC)[Zr(η$\^$5/:η$^1$-C$\_$9/H$\_$5/SiMe$_2$NCMe$_3$)]$_2$[(CH$_2$)$\_$n/][n=6(9), n=12(10)]by treating 2 equivalents of ZrCl$_4$with the corresponding tetralithium salts of the ligands in toluene. $^1$H and $\^$13/C NMR spectra of the synthesized complexes provide firm evidence for the anticipated dinuciear structure. In $^1$H NMR spectra, two singlets representing the methyl group protons bonded at the Si atom of the CGC are present at 0.88 and 0.64 ppm, which are considerably downfield positions relative to the shifts of 0.02 and 0.05 ppm of the corresponding ligands. To investigate the catalytic behavior of the prepared dinuciear catalysts, we conducted copolymerizations of ethylene and styrene in the presence of MMAO. The prime observation is that the two dinuclear CGCs 9 and 10 are not efficient for copo-lymerization, which definitely distinguishes them from the corresponding titanium-based dinuclear CGC. These species are active catalysts, however, for ethylene homopolymerization; the activity of catalyst 10, which contains a 12-methylene bridge, is larger than that of 9 (6-methylene bridge), which indicates that the presence of the longer bridge between the two active sites contributes more effectively to facilitate the polymerization activity of the dinuciear CGC. The activities increase as the polymerization temperature increases from 40 to 70$^{\circ}C$. On the other hand, the molecular weights of the polyethylenes are reduced when the polymerization temperature is increased. We observe that dinuciear metallocenes having different-length bridges give different polymerization results, which reconfirms the significant role that the nature of the bridging ligand has in controlling the polymerization properties of dinuclear catalysts.

Cyclohexane Oxidations by an Iron-Palladium Bicatalytic System; Soluble Catalysts and Polymer Supported Catalysts

  • Jun, Gi Won;Sim, Eun Gyeong;Park, Sang Eon;Lee, Gyu Wan
    • Bulletin of the Korean Chemical Society
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    • v.16 no.5
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    • pp.398-400
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    • 1995
  • Selective oxidation of cyclohexane in acetone solution has been studied using iron catalysts with hydrogen peroxide in-situ produced by palladium catalyst. Iron tetraphenylporphyrin chloride shows the highest activity among the tested chlorides and porphyrin complexes of some metals of the first transiton series. Iron chloride and iron tetraphenylporphyrin chloride were supported on four kinds of 4-vinylpyridine copolymer with styrene or divinyl-benzene. Nitrogen 1s photoelectron spectra give the evidence that pyridyl nitrogens of the 4-vinyl pyridine copolymer act as ligands to bind iron species. The copolymer with styrene is the most efficient support for the binding because its solubility in catalyst preparation solvent (methylene chloride) gives the pyridyl group advantage to contact with the iron catalysts. However, better catalytic activity per iron atom could be obtained with a rigid crosslinked polymer due to active site isolation.

Identification of Substrate Specificity Determinant of Achromobacter Protease I (API) and Catalytic Activity of Mutant D225E for Ornithine Substrate (Achromobacter Protease I (API)의 기질특이성 결정기의 동정과 변이체[D225E]의 Ornithine 기질에 대한 촉매활성)

  • Lim, Seong-Il;Kwon, Oh-Jin;Choi, Cheong
    • Applied Biological Chemistry
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    • v.40 no.3
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    • pp.189-195
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    • 1997
  • The structural basis of Iysine specificity of Achromobacter protease I (API) was investigated by means of site-directed mutagenesis. The precursor protein in which Glu190, one of the two candidates for determining Iysine specificity, was substituted by glutamine, aspartic acid or leucine was processed autocatalytically to attaln full pretense activity with lysine specificity. The substitution of the other candidate, Asp225, for asparagine or leucine produced no mature active forms of pro-API. The precursor protein of the mutant D225E slowly matured autocatalytically. The lysylendopeptidase activity of the mature D225E was 0.25% of that of native API, and this reduced activity is mainly due to a decrease in the affinity of the enzyme for lysine. These results suggest that Asp225 plays a critical rol in restricted substrate specificity as a lysylendopeptidase. However, D225E exhibited no measurable activity for synthetic ornithine substrate. Since the hydroxyl group of Ser194 in this mutant retained essentially the same reactivity to DFP or PMSF as that in native API, it can be noted that a methylene unit longer side chain of residue 225 is not compensated by a methylene unit shorter side chain at subsite P1 in the bound substrate.

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