• Title/Summary/Keyword: michael addition

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Platinum-Catalyzed Reductive Aldol and Michael Reactions

  • Lee, Ha-Rim;Jang, Min-Soo;Song, Young-Jin;Jang, Hye-Young
    • Bulletin of the Korean Chemical Society
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    • v.30 no.2
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    • pp.327-333
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    • 2009
  • For the Pt-catalyzed nucleophilic addition of enones, Pt complexes were employed in the presence of various phosphine ligands and $H_2\;(or\;Et_3SiH),$ affording inter- and intra-molecular coupling products in good to modest yield. Depending on reaction protocols, different phosphine ligands were required to optimize the conditions. In the aldol reaction, the Pt catalyst involving $P(2,4,6-(OMe)_3C_6H_2)3\;or\;P(p-OMeC_6H_4)_3$ was chosen. Michael reaction proceeds in good yields in the presence of $P(p-CF_3C_6H_4)_3$. Regarding the activity of the reductants, $H_2$ exhibited superior activity to $Et_3SiH$, resulting in a shorter reaction time and higher yield in the aldol and Michael reaction. In light of the deuterium labeling studies, the catalytic cycle including the hydrometalation of the enones by the platinum hydride species was proposed.

Preparation of Amine-Containing Poly(amide-sulfone)s Using Vinylsulfone Reactive Monomers and Their Properties

  • Jeon, Young-Min;Lim, Tai-Ho;Kim, Soo-Han;Kim, Jong-Gyu;Gong, Myoung-Seon
    • Macromolecular Research
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    • v.15 no.1
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    • pp.17-21
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    • 2007
  • A series of new, vinyl sulfone-containing monomers was prepared by p-aminophenyl vinyl sulfone (1) with various acid chlorides such as adipoly chloride, terephthaloyl chloride and isophthaloyl chloride. Finally, tertiary amine-containing poly(amide-sulfone)s were prepared by the Michael-type addition polymerization using N,N-dimethylethylenediamine (DMEDA), p-phenylenediamine and piperazin. To evaluate the relevant properties for permselective membranes and enzyme substrate, various physical properties such as molecular weight, solubility, quaternization behavior and thermal properties were examined.

Acrolein with an α,β-unsaturated Carbonyl Group Inhibits LPS-induced Homodimerization of Toll-like Receptor 4

  • Lee, Jeon-Soo;Lee, Joo Young;Lee, Mi Young;Hwang, Daniel H.;Youn, Hyung Sun
    • Molecules and Cells
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    • v.25 no.2
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    • pp.253-257
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    • 2008
  • Acrolein is a highly electrophilic ${\alpha},{\beta}$-unsaturated aldehyde present in a number of environmental sources, especially cigarette smoke. It reacts strongly with the thiol groups of cysteine residues by Michael addition and has been reported to inhibit nuclear $factor-{\kappa}B$ ($NF-{\kappa}B$) activation by lipopolysaccharide (LPS). The mechanism by which it inhibits $NF-{\kappa}B$ is not clear. Toll-like receptors (TLRs) play a key role in sensing microbial components and inducing innate immune responses, and LPS-induced dimerization of TLR4 is required for activation of downstream signaling pathways. Thus, dimerization of TLR4 may be one of the first events involved in activating TLR4-mediated signaling pathways. Stimulation of TLR4 by LPS activates both myeloid differential factor 88 (MyD88)- and TIR domain-containing adapter inducing $IFN{\beta}$ (TRIF)-dependent signaling pathways leading to activation of $NF-{\kappa}B$ and IFN-regulatory factor 3 (IRF3). Acrolein inhibited $NF-{\kappa}B$ and IRF3 activation by LPS, but it did not inhibit $NF-{\kappa}B$ or IRF3 activation by MyD88, inhibitor ${\kappa}B$ kinase $(IKK){\beta}$, TRIF, or TNF-receptor-associated factor family member-associated $NF-{\kappa}B$ activator (TANK)-binding kinase 1 (TBK1). Acrolein inhibited LPS-induced dimerization of TLR4, which resulted in the down-regulation of $NF-{\kappa}B$ and IRF3 activation. These results suggest that activation of TLRs and subsequent immune/inflammatory responses induced by endogenous molecules or chronic infection can be modulated by certain chemicals with a structural motif that enables Michael addition.

Synthesis and Properties of Self-photocuring Polyurethane Acrylate Oligomer for Color Pre-coated metal (선도장 컬러강판용 도료에 적용하기 위한 자가 광경화형 폴리우레탄 아크릴레이트 올리고머 합성 및 물성)

  • Park, So-Young;Cheon, Jungmi;Jeong, Boo Young;Lee, Do Hyeok;Chun, Jae Hwan
    • Journal of Adhesion and Interface
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    • v.21 no.1
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    • pp.14-19
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    • 2020
  • In this study, we synthesized a self-photocuring intermediate(SPI) by Michael addition reaction and synthesized polyurethane acrylate oligomer. Analysis and physical properties of the synthesized SPI and polyurethane acrylate oligomer were confirmed by FT-IR, NMR and UTM. As the content of the SPI increased, the tensile strength increased and the elongation decreased. In addition, since the film was hydrophobic, the surface energy tended to decrease. When the content of the SPI was 40 wt%, adhesion, processability, and pencil hardness were excellent, and solvent resistance was excellent overall.

Involvement of Mrs3/4 in Mitochondrial Iron Transport and Metabolism in Cryptococcus neoformans

  • Choi, Yoojeong;Do, Eunsoo;Hu, Guanggan;Caza, Melissa;Horianopoulos, Linda C.;Kronstad, James W.;Jung, Won Hee
    • Journal of Microbiology and Biotechnology
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    • v.30 no.8
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    • pp.1142-1148
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    • 2020
  • Mitochondria play a vital role in iron uptake and metabolism in pathogenic fungi, and also influence virulence and drug tolerance. However, the regulation of iron transport within the mitochondria of Cryptococcus neoformans, a causative agent of fungal meningoencephalitis in immunocompromised individuals, remains largely uncharacterized. In this study, we identified and functionally characterized Mrs3/4, a homolog of the Saccharomyces cerevisiae mitochondrial iron transporter, in C. neoformans var. grubii. A strain expressing an Mrs3/4-GFP fusion protein was generated, and the mitochondrial localization of the fusion protein was confirmed. Moreover, a mutant lacking the MRS3/4 gene was constructed; this mutant displayed significantly reduced mitochondrial iron and cellular heme accumulation. In addition, impaired mitochondrial iron-sulfur cluster metabolism and altered expression of genes required for iron uptake at the plasma membrane were observed in the mrs3/4 mutant, suggesting that Mrs3/4 is involved in iron import and metabolism in the mitochondria of C. neoformans. Using a murine model of cryptococcosis, we demonstrated that an mrs3/4 mutant is defective in survival and virulence. Taken together, our study suggests that Mrs3/4 is responsible for iron import in mitochondria and reveals a link between mitochondrial iron metabolism and the virulence of C. neoformans.