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Kim, Kibong,Choi, Shin Hei,Jeon, June,Lee, Hyosun,Huh, Jung Oh,Yoo, Jaeduk,Kim, Jong Taek,Lee, Chang-Hee,Lee, Yoon Sup,Churchill, David G. American Chemical Society 2011 Inorganic Chemistry Vol.50 No.12
<P>One 8-phenyl and two 8-mesityl-substituted “scorpionate”-like BODIPY-type species of the formula [3,4,4-tris(5-<I>R</I>-(2-thienyl))-8-(2,4,6-<I>R′</I>-phenyl)-4-bora-3a,4a-diaza-<I>s</I>-indacene (R = H, R′ = H, <B>3a</B>; R, = H, R′ = Me, <B>2a</B>; R, = Me, R′ = Me, <B>2b</B>)] have been synthesized and fully characterized. Importantly, differences in their solution (MeCN) optical Cu<SUP>2+</SUP> and Hg<SUP>2+</SUP> probing capacity via <I>SSS</I>-chelation were investigated. Compounds <B>2a</B>–<B>3a</B> were prepared from the requisite 8-substituted BODIPY complexes. They were characterized first by complete <SUP>1</SUP>H, <SUP>11</SUP>B and <SUP>13</SUP>C NMR spectroscopic assignments (CD<SUB>3</SUB>Cl or CD<SUB>3</SUB>C(O)CD<SUB>3</SUB>); the molecular structures of <B>2a</B> and <B>3a</B> were determined by X-ray crystallography. Compounds <B>2a</B>–<B>3a</B> were studied by UV–vis and fluorescence spectroscopy [Φ<SUB>F</SUB> = 0.27 ± 0.013 (<B>2a</B>); 0.024 ± 0.0016 (<B>2b</B>); 0.0034 ± 0.00047 (<B>3a</B>)]. Importantly, low [Cu<SUP>2+</SUP>] with <B>3a</B> (<3.0 × 10<SUP>–5</SUP> M) gave rise to an increase of fluorescence intensity (off–on; 6.3-fold), whereas with <B>2a</B> it decreased (on–off). When [Hg<SUP>2+</SUP>] (<3.0 × 10<SUP>–5</SUP> M) was added to <B>2b</B>, the λ<SUB>em,max</SUB> value increased (off–on<I>;</I> 3.2-fold), and for <B>2a</B>, it decreased (on–off). The association constant (<I>K</I><SUB>a</SUB>) for Hg<SUP>2+</SUP>·<B>2a</B> was determined to be 3120 ± 307 M<SUP>–1</SUP>. An approximate stoichiometric 1:1 binding determined by Job plot analysis is in line with successful DFT modeling of <I>SSS</I>-Cu<SUP>2+</SUP> binding for this system type. <SUP>1</SUP>H NMR spectroscopy also revealed tentative sets of product complex peaks. These simple differences caused by formal ligand Me-group incorporation are the first for any related fluorophores, to the best of our knowledge.</P><P>Three new “scorpionate”-like BODIPY species have been isolated and characterized. They exposed interesting differences in low [Cu<SUP>2+</SUP>] and [Hg<SUP>2+</SUP>] on−off and off−on fluorescence responses through formal methyl group placement into the fluorophore skeleton.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/inocaj/2010/inocaj.2010.50.issue-12/ic101681h/production/images/medium/ic-2010-01681h_0004.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ic101681h'>ACS Electronic Supporting Info</A></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ic101681h'>ACS Electronic Supporting Info</A></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ic101681h'>ACS Electronic Supporting Info</A></P>
Effect of Skin Lipid Barrier Formation on Hataedock Treatment with Douchi
Kim, Hee-Yeon,Ahn, Sang-hyun,Yang, Injun,Kim, Kibong The Society of Korean Medicine 2017 대한한의학회지 Vol.38 No.2
Objectives: Hataedock is indigenous treatment of Korean medicine that administers herbal extracts orally to newborn infants for remove the fetal heat. The purpose of this study was to evaluate skin lipid barrier formation effect of Hataedock treatment with Douchi. Methods: We measured the Western blot to observe the expression of protein such as involucrin and loricrin. Moreover, we observed immunohistochemical changes in NC/Nga mice. The 3-week-old NC/Nga mice were divided into 3 groups: the 3-week-old control group (3w-Ctrl), 5-week-old control group (5w-Ctrl), and the Hataedock-treated group (5w-FGT). Only the 5w-FGT group was treated with Douchi at the 3rd week. We identified the changes of the lipid skin barrier and protein differentiation through immunohistochemical changes of involucrin, loricrin, filaggrin and acid sphingomyelinase (ASM) in the stratum corneum. Results: The expression of involucrin and loricrin was increased in the Western blot that was treated with concentration of Douchi extracts. In 5w-FGT group, loricrin-positive reaction was increased by 54.0%, involucrin-positive reaction was increased by 84.0%, filaggrin-positive reaction was increased by 108.0% and ASM-positive reaction was increased by 91.0% in the stratum corneum. Conclusions: These results suggest that Hataedock treatment with Douchi promoted skin lipid barrier formation by promoting differentiation of keratinocytes.
Kim, Kibong,Ha, Yonghwang,Kaufman, Lé,o,Churchill, David G. American ChemicalSociety 2012 Inorganic chemistry Vol.51 No.2
<P>Herein, molecular fluorescence 'OFF-ON' behavior with aqueous addition of biological phosphate and Zn(2+) is studied with Zn(2)(slys)(2)Cl(2) [H(2)slys = 6-amino-2-{(2-hydroxybenzylidene)amino}hexanoic acid], a fluorescent water-soluble complex, using various spectroscopic tools (e.g., (31)P NMR, UV-vis, emission, and CD spectroscopy) at the micromolar level. Adduct-dependent fluorescence intensity changes can be interpreted as a two-input (cation/anion) implication molecular logic gating system. A displacement study of PPi from the dizinc complex is also reported. Diphosphate and triphosphate addition/displacements were also studied. (31)P NMR spectroscopy shows gradual NMR peak shifts from bound ADP/GDP to free ADP/GDP with increasing [PPi]. In the emission spectrum, fluorescence quenching is shown: CD signal maxima decrease with addition of PPi. These displacement events are also tested with triphosphates (ATP, GTP), and their binding strength/displacement ability over ADP/GDP is quantified: PPi > ATP approximate to GTP (3.35 +/- 0.77 X 10(4) M(-1) for PPi, 7.73 +/- 1.79 X 10(3) M(-1) for ATP, 9.21 +/- 2.88 X 10(3) M(-1) for GTP over 1.ADP). Many anions and cations were also screened for selectivity. Tubulin polymerization was assayed in the presence of 1 and its copper analogue which reflected a slight inhibition in polymerization.</P>