• Title/Summary/Keyword: $C^{13}$-NMR

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Interaction of the Post-transition Metal Ions and New Macrocycles in Solution

  • Jung, Oh-Jin
    • Bulletin of the Korean Chemical Society
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    • 제14권6호
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    • pp.687-691
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    • 1993
  • Complexation of $Cd^{2+},\;Pb^{2+}\;and\;Hg^{2+}$ ions with four cryptands were studied by potentiometry and solution calorimetry in various weight percent methanol-aqueous solvent at 25${\circ}$C under $CO_2$free nitrogen atmosphere. The stabilities of the complexes were dependent on the cavity size of macrocycles. The $Hg^{2+}$ ion stability constants are higher than those of $Cd^{2+}\;and\;Pb^{2+}$ ion. All the cryptands formed complexes having 1 : 1 (metal to ligand) mole-ratio except for $Hg^{2+}-L_1$ (cryptand 1,2b: 3,5-benzo-9,14,17-trioxa-1,7-diazabicyclo-(8,5,5) heptadecane) and $Cd^{2+}-L_2$ (cryptand 2,2b: 3,5-benzo-10,13,18,21-tetraoxa-1,7-diazabicyclo (8,5,5) eicosane) complexes. $Hg^{2+}-L_1$ complex was a sandwitch type, and the $Cd^{2+}-L_2$ complex showed two stepwise reactions. Thermodynamic parameters of the $Cd^{2+}-L_2$ complex were $6.08(log\;K_1)$, -7.28 Kcal/mol $({\Delta}H_1)$, and $4.78\;(log\;K_2)$, -4.62 Kcal/mol $({\Delta}H_2)$, respectively, for 1 : 1 and 2: 1 mole-ratio. The sequences of the selectivity were increased in the order of $Hg^{2+}\;>Pb^{2+}\;>Cd^{2+}$ ion for $L_3\;and\;L_4$ macrocycles, and the $L_2$-macrocycle has a selectivity for $Cd^{2+}$ ion relative to $Zn^{2+},\;Ni^{2+},\;Pb^{2+}\;and\;Hg^{2+}$ ions. Thus, it is expected that the $L_2$ can be used as carrier for seperation of the post transition metals by macrocycles-mediated liquid membrane because $L_2$ is not soluble in water, and the difference of stability constants of the metal complexes with $L_2$ are large as compared with the other transition metal complexes. The $^1H\;and\;^{13}C-NMR studies indicated that the nitrogen atoms of cryptands have greater affinity to the post transition metal ions than the oxygen atoms, and that the planarities of the macrocycles were lost by complexation with the metal ions because of the perturbation of ring current of benzene molecule attached to macrocycles and counter-anions.

홀아비꽃대(Chloranthus japonicus) 뿌리로부터 분리한 shizukanol들의 생물활성 (Biological activity of shizukanols isolated from Chloranthus japonicus roots)

  • 박미란;김혜영;최경자;이선우;장경수;김진석;홍경식;박노중;조광연;김진철
    • 농약과학회지
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    • 제8권4호
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    • pp.338-346
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    • 2004
  • 홀아비꽃대(Chloranthus japonicus) 뿌리 조직의 메탄을 추출물은 벼 도열병(Magnaporthe grisea), 벼 잎집무늬마름병(Corticium sasaki), 토마토 잿빛곰팡이병(Botrytis cinerea), 토마토 역병(Phytophthora infestans) 및 밀 붉은녹병(Puccinia recondita) 등의 다양한 식물병을 효과적으로 방제하였다. 이 메탄올 추출물로부터 3개의 항균물질을 분리하였고 이들은 질량분석과 핵자기공명분석을 통하여 shizukanol B, C 및 D로 동정되었다. 이들 세 개의 물질들 중에서 shizukanol C가 실험한 식물병원균들의 균사생육 저해 활성이 가장 큰 것으로 나타났다. 즉, $12.5{\mu}g/m\ell$ 이상의 농도에서 벼 도열병균과 고추 탄저병균(Colletotrichum gloeosporioides와 C. acutatum)의 균사 생육을 완전히 억제하였고, $3.13{\mu}g/m\ell$ 이상의 농도에서는 토마토 역병균의 균사 생육이 완전히 억제되었다. 세 가지 물질은 또한 in vivo에서 벼 도열병과 밀 붉은녹병에 대하여 특히 높은 방제효과를 보였다. 다른 한편으로 세 가지 물질들은 밀과 보리 잎에 약해를 유발하였고, 또한 좀개구리밥(Lemna paucicosta)의 생장을 억제하였으며, shizukanol B, C, D의 50% 생육억제 농도는 각각 $30.0{\mu}g/m\ell$, $49.9{\mu}g/m\ell$$154{\mu}g/m\ell$였다. 그리고 shizukanol C는 시험한 5종류의 해충중에서 벼멸구(Nilaparavata lugens), 복숭아혹진딧물(Myzus persicae), 배추좀나방(Plutella xylostella) 및 담배거세미나방(Spodoptera litura)에 대해서 $1,000{\mu}g/m\ell$ 수준에서 60% 이상의 살충활성을 보였다.

1, 14-Bis(2-hydroxybenzyl)-2, 6, 9, 12-tetraazatetradecane.tetrahydro-chloride 구리착물의 합성, 안정도상수, X-ray 구조 및 전기화학적 연구 (Synthesis, Stability Constants, X-ray Structure and Electrochemical Studies of Copper (II) 1, 14-Bis (2-hydroxybenzyl)-2, 6, 9, 12-tetraazatetradecane.tetrahydrochloride Complex)

  • 김선덕;김준광;김성윤
    • 분석과학
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    • 제13권2호
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    • pp.173-178
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    • 2000
  • 두 개의 페놀기를 포함하는 열린 고리형태의 1, 14-Bis(2-hydroxybenzyl)-2, 6, 9, 12-tetraazatetradecane(bsated) 리간드를 염산염의 형태로 분리하여 원소 분석, 질량 스펙트럼 및 핵자기공명법으로 분석하였다. 합성된 리간드의 산 해리상수($logK^n{_H}$)와 $Cu^{2+}$, $Ni^{2+}$, $Co^{2+}$$Zn^{2+}$에 대한 안정도 상수($logK_{ML}$)를 전위차 적정법으로 결정하였다. 이때 온도는 $25^{\circ}C$ 및 이온강도는 0.10M($KNO_3$)로 고정시켰다. [Cu(bsated)] $(ClO_4)_2$ X-ray구조의 crystal data는 다음과 같다: Monoclinic space group $P2_1/n$, $a=17.856(4){\AA}$, $b=17.709(1){\AA}$, $c=8.539(2){\AA}$, $V=2700(2){\AA}$ with Z=4. tetrabutylammonium perchlorate 전해질의 dimethyl sulfoxide 용액속에서 [Cu(bsated)]$(ClO_4)_2$ 착물의 전기화학적 특성을 순환 전압-전류법 (CV)과 normal pulse voltammertry (NPV, 정상펄스전압전류법)으로 측정하였다.

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Studies on Biological Activity of Wood Extractives (XVII) - Components and Antioxidant activity of Alnus firma -

  • Choi, In-Ho;Choi, Tae-Ho;Park, Youngki;Lee, Oh-Kyu;Kwon, Yeong-Han;Kang, Ha-Young;Park, Il-Kwon;Choi, Don-Ha;Shin, Sang-Chul;Lee, Hak-Ju
    • Journal of the Korean Wood Science and Technology
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    • 제34권2호
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    • pp.95-100
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    • 2006
  • This study is to isolate bio-active compounds from Alnus firma and evaluate their antioxidant activity. Dried wood powder of A. firma was extracted by organic solvents and fractionated in the sequential extraction steps. The isolated compounds were characterized by EI-MS, $^{13}C-$ and $^1H-NMR$ including COSY, DEFT, HMQC, and HMBC. Antioxidant activities of the isolated compounds were evaluated by DPPH (1,1-diphenyl-2-picrylhydrazyl) free radical scavenging effect. From the wood of A. firma, three kinds of diarylheptanoids, alnusodiol (1), alnusonol (2) and alnusone (3), and gallic acid (4) were isolated. Among these four compounds, compound 1, 2, and 3 are isolated from A. firma for the first time. The antioxidant activity of gallic acid was 93.5% at the concentration of 100 ppm. This compound showed stronger antioxidant activity than those of other isolated compounds and the reference BHT (butylated hydroxytoluene).

Synthetic, Characterization, Biological, Electrical and Catalytic Studies of Some Transition Metal Complexes of Unsymmetrical Quadridentate Schiff Base Ligand

  • Maldhure, A. K.;Pethe, G. B.;Yaul, A. R.;Aswar, A. S.
    • 대한화학회지
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    • 제59권3호
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    • pp.215-224
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    • 2015
  • Unsymmetrical tetradentate Schiff base N-(2-hydroxy-5-methylacetophenone)-N'-(2-hydroxy acetophenone) ethylene diamine (H2L) and its complexes with Cr(III), Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) have been synthesized and characterized by elemental analyses, magnetic susceptibility measurements, IR, electronic spectra and thermogravimetric analyses. 1H, 13C-NMR and FAB Mass spectra of ligand clearly indicate the presence of OH and azomethine groups. Elemental analyses of the complexes indicate that the metal to ligand ratio is 1:1 in all complexes. Infrared spectra of complexes indicate a dibasic quadridentate nature of the ligand and its coordination to metal ions through phenolic oxygen and azomethine nitrogen atoms. The thermal behavior of these complexes showed the loss of lattice water in the first step followed by decomposition of the ligand in subsequent steps. The thermal data have also been analyzed for the kinetic parameters by using Horowitz-Metzger method. The dependence of the electrical conductivity on the temperature has been studied over the temperature range 313-403 K and the complexes are found to show semiconducting behavior. XRD and SEM images of some representative complexes have been recorded. The antimicrobial activity of the ligand and its complexes has been screened against various microorganisms and all of them were found to be active against the test organisms. The Fe(III) and Ni(II) complex have been tested for the catalytic oxidation of styrene.

동백(冬柏)을 위시한 차나무과(科) 식물(植物) 종실(種實)에 함유(含有)된 항산화제(抗酸化劑)에 관한 연구(硏究) (Studies on the Antioxidative Substances in the Seeds of Some Theaceae Family)

  • 김성진;최은진;임희영;김태숙;조용계
    • 한국응용과학기술학회지
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    • 제8권1호
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    • pp.35-43
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    • 1991
  • Dried seeds of Camellia japonica and Thea sinensis were investigated to determine the nature of their antioxidative activity. Activity was measured by the induction period in the coupled oxidation of a substrate lard and extracts or isolates to be tested. 70% methanol and dichloromethane extracts were found to be antioxidative abilities. Their unsaponifiables revealed weak antioxidative activity, although hexane extracts did not show antioxidative effect on lard. Column chromatography for dlchloromethane extracts gave 4 fractions(only 2 fractions were potent). HPLC was used in isolating potent antioxidative components from the column fractions and the precolumn-passed methanol extracts. They were separated into 7 and 8 components, respectively. The column fractions obtained from both seeds comprised trans-p-coumaric acid. trans-p-ferulic acid and an unknown component with minor components such as chlorogenic acid and catechin. On the other hand, the most prominent components in the methanol extracts were an unidentified component. trans-pcoumaric acid, trans-p-ferulic acid, catechin and chlorogenic acid. The unknown compound isolated from the column fractions and methanol extracts was identified as epicatechin by $^1H-and\;^{13}C-NMR$. The antioxidative activities of these components were epicatechin > catechin > chlorogenic acid > trans-p-ferulic acid > trans-p-coumaric acid.

Inhibitors of Tyrosinase and Melanogenesis from Galla rhois

  • Kim, Hyo-Jin;Jang, Dong-Il;Park, Sang-Won
    • Preventive Nutrition and Food Science
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    • 제2권4호
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    • pp.285-290
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    • 1997
  • Previously, a 50% aqueous methanol extract of Galla rhois was shown to be the most potent tyrosinase inhibition activity with an {TEX}$IC_{50}${/TEX}(the concentration causing 50% inhibition of tyrosinase activity) of 0.2mg/ml of 205 crude drug extracts. To isolate tyrosinase inhibitors, the methanol extract was evaporated to a small volume in vacuo, and then partitioned stepwise with benzene and ethyl acetate(EtOAc). the EtOAc fraction was solubilized in 10% MeOH solution, and then fractionated successively by Diaion HP-20 and Sephadex LH-20 column chromatography, and preparative HPLC. Three phenolic compounds were isolated, and characterized as gallic acid(GA), methyl gallate(MG) and 1,2,3,4,6-penta-O-galloyl-$\beta$-D-glucose(PGG) by UV, IR, {TEX}${1}^H${/TEX}-&{TEX}${13}^C${/TEX}-NMR, and FAB-MS spectroscopy, PGG({TEX}$IC_{50}${/TEX}=50$\mu\textrm{g}$/ml) showed a considerable inhibitory effect against mushroom tyrosinase, while GA({TEX}$IC_{50}${/TEX}=1.6mg/ml) and MG({TEX}$IC_{50}${/TEX}=234$\mu\textrm{g}$/ml) did not show an appreciable effect. Meanwhile, MG inhibited greatly melanogenesis in a murine melanocyte cell line, Mel-Ab. MG and PGG showed typical noncompetitive inhibition patterns against mushroom tyrosinase. These results suggest that PGG and MG may be potentially useful as either anti-browning or anti-melanogenic agents in foods and cosmetics.

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SQUID 센서 기반의 극저자장 자기공명 장치를 위한 사전자화코일 전류구동장치 개발 (Development of Prepolarization Coil Current Driver in SQUID Sensor-based Ultra Low-field Magnetic Resonance Apparatuses)

  • 황성민;김기웅;강찬석;이성주;이용호
    • Progress in Superconductivity
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    • 제13권2호
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    • pp.105-110
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    • 2011
  • SQUID sensor-based ultra low-field magnetic resonance apparatus with ${\mu}T$-level measurement field requires a strong prepolarization magnetic field ($B_p$) to magnetize its sample and obtain magnetic resonance signal with a high signal-to-noise ratio. This $B_p$ needs to be ramped down very quickly so that it does not interfere with signal acquisition which must take place before the sample magnetization relaxes off. A MOSFET switch-based $B_p$ coil driver has current ramp-down time ($t_{rd}$) that increases with $B_p$ current, which makes it unsuitable for driving high-field $B_p$ coil made of superconducting material. An energy cycling-type current driver has been developed for such a coil. This driver contains a storage capacitor inside a switch in IGBT-diode bridge configuration, which can manipulate how the capacitor is connected between the $B_p$ coil and its current source. The implemented circuit with 1.2 kV-tolerant devices was capable of driving 32 A current into a thick copper-wire solenoid $B_p$ coil with a 182 mm inner diameter, 0.23 H inductance, and 5.4 mT/A magnetic field-to-current ratio. The measured trd was 7.6 ms with a 160 ${\mu}F$ storage capacitor. trd was dependent only on the inductance of the coil and the capacitance of the driver capacitor. This driver is scalable to significantly higher current of superconducting $B_p$ coils without the $t_{rd}$ becoming unacceptably long with higher $B_p$ current.

Streptomyces hygroscopicus MJM1004가 생산하는 항진균성 항생 물질의 분리 및 구조 결정 (Isolation and Structural Determination of Antifungal Antibiotic from Streptomyces hygroscopicus MJM1004)

  • 배주윤;권형진;서주원
    • Applied Biological Chemistry
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    • 제42권4호
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    • pp.271-276
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    • 1999
  • 새로운 천연물 농약 또는 생산군주를 개발하기 위하여 Streptomyces 속의 여러 균주를 대상으로 항진균 물질을 탐색하여 항진균 물질 생산 균주 Streptomyces hygroscopicus MJM1004를 선발하였다. 항진균 물질의 생산을 위한 발효 배지를 선정하기 위하여 여러 탄소원, 질소원과 무기원을 대상으로 균체 생장 정도와 항진균 물질의 생산성을 조사하였으며, 생산 배지는 2% soybean meal, 1% glucose, 2% starch, 0.3% $CaCO_3$, 0.05% $MgSO_4{\cdot}7H_2O$, 0.05% $K_2HPO_4$를 조성으로 하였다. S. hygroscopicus MJM1004 균주의 균체에서 추출된 항진균 물질은 Candida albicans와 여러 식물 병원성 곰팡이들에 대하여 광범위한 저해 효과를 나타내었다. S. hygroscopicus MJM1004 균체로부터 분리된 항진균 물질, SH-1004를 핵자기공명법($^1H,\;^{13}C$, DQF COSY, HMQC 및 HMBC)을 통하여 분석한 결과 azalomycin F complex 임을 확인할 수 있었다. Positive FAB mass spectrum을 통하여 SH-1004는 azalomycin F4a와 F5a가 1.8 : 1의 비율로 혼합된 물질임을 확인하였다.

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Lipopolysaccharide로 유도된 Raw264.7 cell에서 Phellodendron amurense의 Jatrorrhizine에 의한 염증 억제효과 (Anti-inflammatory Effect of Jatrorrhizine from Phellodendron amurense in Lipopolysaccharide-stimulated Raw264.7 Cells)

  • 조영제
    • Journal of Applied Biological Chemistry
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    • 제54권2호
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    • pp.114-119
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    • 2011
  • 황백으로부터 n-BuOH 추출물에서 약 50%의 hyaluronidase 저해효과가 있음이 확인되었다. n-BuOH 분획 농축물을 Sephadex LH-20 및 MCI gel CHP-20 column chromatography로 정제한 결과 저해활성을 가지는 Jatrorrhizine을 분리, 동정하였다. 황백추출물과 Jatrorrhizine은 모두 농도 의존적으로 NO 발현을 억제하였고, 100 ${\mu}g/mL$의 농도에서 60% 이상의 억제 효과를 나타내었다. 황백추출물과 Jatrorrhizine의 iNOS와 COX-2의 억제력을 살펴본 결과, 100 ${\mu}g/mL$의 농도에서 45% 및 29%의 저해효과를 나타내었다. 따라서 황백추출물 및 Jatrorrhizine은 LPS로 유도되어진 대식세포주인 Raw264.7 세포에서의 염증반응의 억제효과를 기대할 수 있었다.