• Title/Summary/Keyword: NMR

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Copolymerization of Ethylene and Norbornene via Polymethylene Bridged Dinuclear Constrained Geometry Catalysts

  • Zhu, Yin-Bang;Jeong, Eung-Yeong;Lee, Bae-Wook;Kim, Bong-Shik;Noh, Seok-Kyun;Lyoo, Won-Seok;Lee, Dong-Ho;Kim, Yong-Man
    • Macromolecular Research
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    • v.15 no.5
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    • pp.430-436
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    • 2007
  • The dinuclear half-sandwich CGCs (constrained geometry catalyst) with a polymethylene bridge, $[Ti({\eta}^5 : {\eta}^1-indenyl)SiMe_2NCMe_3]_2(CH_2)_n]$[n = 6 (1) and 12 (2)], have been employed in the copolymerization of ethylene and norbornene (NBE). To compare the mononuclear metallocene catalysts; $Ti({\eta}^5 : {\eta}^1-2-hexylindenyl)SiMe_2NCMe_3$ (3), $(Cp^* SiMe_2NCMe_3)$Ti (Dow CGC) (4) and ansa-$Et(Ind)_2ZrCI_2$ (5), were also studied for the copolymerization of ethylene and NBE. It was found that the activity increased in the order: 1 < 2 < 3 < 5 < 4, indicating that the presence of the bridge between two the CGC units contributed to depressing the polymerization activity of the CGCs. This result strongly suggests that the implication of steric disturbance due to the presence of the bridge may playa significant role in slowing the activity. Dinuclear CGCs have been found to be very efficient for the incorporation of NBE onto the polyethylene backbone. The NBE contents in the copolymers formed ranged from 10 to 42%, depending on the polymerization conditions. Strong chemical shifts were observed at ${\delta}$42.0 and 47.8 of the isotactic alternating NBE sequences, NENEN, in the copolymers with high NBE contents. In addition, a resonance at 47.1 ppm for the sequences of the isolated NBE, EENEE, was observed in the $^{13}C-NMR$ spectra of the copolymers with low NBE contents. The absence of signals for isotactic dyad at 48.1 and 49.1 ppm illustrated there were no isotactic or microblock (NBE-NBE) sequences in the copolymers. This result indicated that the dinuclear CGCs were effective for making randomly distributed ethylene-NBE copolymers.

Antifungal Activity of Benzoic Acid from Bacillus subtilis GDYA-1 against Fungal Phytopathogens (Bacillus subtilis GDYA-1로부터 분리한 benzoic acid의 식물병원성 곰팡이에 대한 항균활성)

  • Yoon, Mi-Young;Seo, Kook-Hwa;Lee, Sang-Heon;Choi, Gyung-Ja;Jang, Kyoung-Soo;Choi, Yong-Ho;Cha, Byeong-Jin;Kim, Jin-Cheol
    • Research in Plant Disease
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    • v.18 no.2
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    • pp.109-116
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    • 2012
  • A bacterial strain antagonistic to some fungal phytopathogens was isolated from the stem of a Persimmon tree in Yeongam, Korea. This bacterium was identified as Bacillus subtilis by 16S rRNA gene sequencing and designated as B. subtilis GDYA-1. In in vivo experiment, the fermentation broth exhibited antifungal activities against Magnaporthe oryzae on rice plants, Phytophthora infestans on tomato plants, and Puccinia recondita on wheat plants. We isolated one antifungal compound and its chemical structure was determined by mass and $^1H$-NMR spectral data. The antifungal substance was identified as benzoic acid. It inhibited mycelial growth of M. oryzae, Rhizoctonia solani, Sclerotinia sclerotiorum, and P. capsici with minimum inhibition concentration (MIC) values, ranging from 62.5 to 125 ${\mu}g/ml$. Moreover, the substance effectively suppressed Phytophthora blight of red pepper caused by P. capsici in a pot experiment. To the author's knowledge, this is the first report on the antifungal activity of benzoic acid against phytopathogenic fungi. Benzoic acid and B. subtilis GDYA-1 may contribute to environmental-friendly protect crops from phytopathogenic fungi.

Structural Analysis of Natural Indigo Colorants Extracted from Polygonum tinctorium (천연인디고 색소의 구조분석)

  • Chung, In-Mo;Lee, Kwang-Gill;Sung, Gyou-Byung;Kim, Hyun-Bok;Nam, Sung-Hee;Hong, In-Pyo
    • Journal of Sericultural and Entomological Science
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    • v.49 no.1
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    • pp.8-13
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    • 2007
  • Natural indigo colorants were prepared by extraction of Polygonum tinctorium which was harvested just in the blooming season(in the late of July). The components were analyzed by TLC and HPLC, and its structures were analyzed by FT-IR, EI-mass. The results obtained are summarized as follows; The natural indigo powder was dissolved in DMSO and developed in eluent, $CHCI_3/CH_3CN$(8.5:1.5 v/v) by means of TLC for its quality analysis. It was segregated into indirubin as a red colour and indigo as a blue colour. In case of HPLC analysis,. FT-IR spectrum of indirubin showed a peak for NH residue between 3200 and $3300cm^{-1}$. $^1H-NMR$ spectrum for indigo displayed AA'BB' spin system caused by indole structure between 6.5 and 7.7ppm of H4, 5, 6 and 7, and -NH proton for indirubin showed an singlet between 10.88 and 11.0ppm. EI-mass spectrum of indigo and indirubin both disclosed their molecular size as 262 and it implies that these two substances are isomer.

Role of a Phytotoxin Produced by Fusarium oxysporum f. sp. raphani on Pathogenesis of and Resistance to the Fungus (무 시들음병균이 생산하는 Phytotoxin의 병원성 및 저항성에서 역할)

  • Shim, Sun-Ah;Kim, Jin-Cheol;Jang, Kyoung Soo;Choi, Yong Ho;Kim, Heung Tae;Choi, Gyung Ja
    • Horticultural Science & Technology
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    • v.31 no.5
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    • pp.626-632
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    • 2013
  • In the course of a developing screening method for resistant radish to Fusarium oxysporum f. sp. raphani, we found that the fungus produces phytotoxic compound against Raphanus sativus. The culture filtrate of F. oxysporum f. sp. raphani KR1 represented the strongest phytotoxicity when the fungus was incubated in the malt extract broth with 150 rpm at $25^{\circ}C$ for 14 days. Under bioassay-guided purification, we isolated a substance from liquid culture of F. oxysporum f. sp. raphani KR1, with phytotoxic effect against R. sativus. The compound was identified as fusaric acid by mass and nuclear magnetic resonance spectral analyses. Phytotoxicity of the compound against cruciferous vegetable crops, including radish, cabbage, and broccoli, was investigated. Fusaric acid represented phytotoxicity on radish seedlings by concentration dependant manner. And the phytotoxin demonstrated strong phytotoxicity on the resistant cultivars as well as susceptible cultivars of radish to F. oxysporum f. sp. raphani. In addition, fusaric acid isolated from the fungus also showed a potent phytotoxic efficacy against non-host Brassicaceae crops of the fungus such as cabbage and broccoli. The results demonstrate that fusaric acid produced by F. oxysporum f. sp. raphani is non-host-specific toxin and for screening of resistant radish to the fungal pathogen, spore suspension of the fungus without the phytotoxin has to be used.

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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    • v.14 no.6
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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.

Efficient Synthesis of hypho-2,5-$S_2B_7H_{11}$ and Preparation of New nido-, arachno-, and hypho-Metalladithiaborane Clusters Derived from Its Anion hypho-$S_2B_7H_{10}{^-}$

  • 강창환;김성준;고재정;강상욱
    • Bulletin of the Korean Chemical Society
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    • v.16 no.11
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    • pp.1067-1074
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    • 1995
  • Reaction of arachno-S2B7H8- with either THF or 1,2-dimethoxyethane upon refluxing condition results in the formation of the previously known compound hypho-S2B7H10-. Protonation of hypho-S2B7H10- with HCl/Et2O generates hypho-2,5-S2B7H11 in good yield. This hypho-S2B7H10- anion has been employed to generate a series of new nido-, arachno-, and hypho-metalladithiaborane clusters. Reaction of the anion with Cp(CO)2FeCl results in direct metal insertion and the formation of a complex containing the general formula (η5-C5H5)FeS2B7H8. Spectroscopic studies of nido-6-CpFe-7,9-S2B7H8 Ⅰ demonstrated that compound Ⅰ was shown to have an nido-type cage geometry derived from an octadecahedron missing one vertex, with the iron atom occupying the three-coordinate 6-position in the cage and the two sulfurs occupying positions on the open face of the cage. Reaction of hypho-S2B7H10- with CoCl2/Li+[C5H5]- gave the previously known complex arachno-7-CpCo-6,8-S2B6H8 Ⅱ. Also, the reaction of the anion with [Cp*RhCl2]2 gave the complex arachno-7-Cp*Rh-6,8-S2B6H8 Ⅲ, the structure of which was shown to be that of complex Ⅱ. The similarity of the NMR spectra of Ⅱ and Ⅲ suggest that Ⅲ adopts cage structure similar to that previously confirmed for Ⅱ. A series of 9-vertex hypho clusters in which the sulfur atoms are bridged by different species isoelectronic with a BH3 unit, such as HMn(CO)4 or SiR2 have been prepared. Compounds Ⅳ,Ⅴ and Ⅵ are each 2n+4 skeletal electron systems and would be expected according to skeletal electron counting theory to adopt hypho-type polyhedral structures derived from an icosahedron missing three vertices. The complex hypho-1-(CO)4Mn-2,5-S2B6H9 Ⅳ was obtained by the reaction of the anion with (CO)5MnBr and has been shown from spectroscopic data to consist of a (CO)4Mn fragment bound to the two sulfur atoms S2 and S5 of hypho-S2B7H10-. Also, similar hypho-type complexes hypho-1-R2Si-2,5-S2B6H8 (R=CH3 Ⅴ, R=C6H5 Ⅵ) have been prepared from the reaction of hypho-S2B7H10- with R2SiHCl.

Proliferative Effects of Flavan-3-ols and Propelargonidins from Rhizomes of Drynaria fortunei on MCF-7 and Osteoblastic Cells

  • Chang, Eun-Ju;Lee, Won-Jung;Cho, Sung-Hee;Choi, Sang-Won
    • Archives of Pharmacal Research
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    • v.26 no.8
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    • pp.620-630
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    • 2003
  • The proliferative effects of thirty Oriental medicinal herbs on MCF-7 (estrogen-sensitive breast cancer cell line) and ROS 17/2.8 osteoblast-like cells were determined using the MTT assay. Methanol extracts from several herbs was found to show proliferative activity on the above two cell lines in the range of 5 to 100 $\mu$g/mL. Among these active herbs, the methanol extract from the rhizomes of Drynaria fortunei showed the most potent proliferative activity, and the cell proliferations were significantly increase by 136 and 158% in the MCF-7 and ROS 17/2.8 cells, respectively, when treated with 100 $\mu$ g/mL. Through a bioassay-guided separation, eight flavonoids, including four new flavan-3-ols and two propelargonidins, together with the known (-)-epiafzelechin and naringin, were isolated. Their chemical structures were characterized as (-)-epiafzelechin (1), (-)-epiafzelechin-3-O-$\beta$-D-allopyranoside (2), (-)-epiafzelechin-3-O-(6"-O-acetyl)-$\beta$-D-allopyranoside (3), 4$\beta$-carboxymethyl-(-)-epiafzelechin methyl ester (4), 4$\beta$-car-boxymethyl-(-)-epiafzelechin sodium salt (5), naringin (6), (-)-epiafzelechin-(4$\beta$\rightarrow8)-4$\beta$-car-boxymethylepiafzelechin methyl ester (7) and (-)-epiafzelechin-($4\beta\rightarrow8, 2\beta\rightarrowΟ\rightarrow7)-epiafzelechin-(4\beta\righarrow8)-epiafzelechin (8) by extensive 1D and 2D NMR spectroscopy. Most of these flavonoids, in the range of $10^{-15}∼10^{-6}$ M, accelerated the proliferation of MCF-7 cell, with compounds 7 and 8, in the range of $10^{-15}∼10^{-12}$ M, showing especially potent proliferation effects. Meanwhile, seven flavonoids, with the exception of compound 4, stimulated the proliferation of ROS 17/2.8 cells in the range of $10^{-15}∼10^{-6}$ M, with compounds 5-8 especially accelerating the proliferation, in dose-dependent manners ($10^{-15}∼10^{-9}$ M), and their proliferative effect was much stronger than that of $E_2$ and genistein. These results suggest that propelargonidin dimers and trimers isolated from the rhizomes of Drynaria fortunei may be useful as potential phytoestrogens, which play important physiological roles in the prevention of postmenopausal osteoporosis.

Synthesis of Dendritic Polystyrene-block-Linear Poly(t-butyl acrylate) Copolymers by an Amide Coupling (아미드 커플링을 통한 덴드리틱 Polystyrene-Block-Linear Poly(t-butyl acrylate) 공중합체의 합성)

  • Song, Jie;Cho, Byoung-Ki
    • Polymer(Korea)
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    • v.33 no.2
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    • pp.158-163
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    • 2009
  • In this study, we synthesized a series of dendritic polystyrene-b-linear poly (t-butyl acrylate) copolymers with well-defined molecular architectures. The hydroxyl group located at the focal point of the second generation dendron bearing polystyrene ($M_n$ = 1000 g/mol) peripheries was converted into amine group via the following stepwise reactions: 1) tosylatoin, 2) azidation, and 3) reduction. On the other hand, the linear poly (t-butyl acrylate)s were prepared by an atom transfer radical polymerization (ATRP) of t-butyl acrylate where benzyl 2-bromopropanoate and Cu(I)Br/PMDETA were used as initiator and catalyst, respectively. To convert the end group of prepared poly (t-butyl acrylate) s into carboxylic acid, a debenzylation was performed using Pd/C catalyst under $H_2$ atmosphere. In the final step, dendritic-linear block copolymers were obtained through a simple amide coupling reaction mediated by 4-(dimethylamino) pyridine(DMAP) and N,N'-diisopropylcarbodiimide(DIPC). The resulting diblock copolymers were shown to have well-defined molecular weights and narrow molecular weight distributions as supported by $^1H$-NMR spectroscopy and gel permeation chromatography(GPC).

Pancreatic Lipase Inhibitors Isolated from the Leaves of Cultivated Mountain Ginseng (Panax ginseng) (산양삼 잎으로부터 Pancreatic lipase 저해 활성물질의 분리)

  • Hong, Ju-Yeon;Shin, Seung-Ryeul;Bae, Man-Jong;Bae, Jong-Sup;Lee, In-Chul;Kwon, O-Jun;Jung, Ji-Wook;Kim, Yong-Han;Kim, Tae-Hoon
    • Food Science and Preservation
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    • v.17 no.5
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    • pp.727-732
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    • 2010
  • Activity-guided fractionation of an ethyl acetate (EtOAc)-soluble portion of an ethanolic extract from the leaves of cultivated mountain ginseng, using pancreatic lipase inhibition assay, led to the isolation and identification of three flavonoids of a previously described structure, kaempferol-3-O-sophoroside (I), kaempferol-3-O-${\beta}$-Dglucopyranoside (astragalin, II) and kaempferol (III). All compounds (I.III) showed pancreatic lipase inhibitory activities, with $IC_{50}$ values ranging from $20.3{\pm}2.2$ to $9.1{\pm}1.5$ ${\mu}M$, kaempferol (III) showed the most potent inhibitory activity with an $IC_{50}$ of $9.1{\pm}1.5$ ${\mu}M$. The level of activity may depend on the number of C-3 glucosyl group(s) linked to the kaempferol backbone, and the isolated compounds may have promise as pancreatic lipase inhibitors.

Synthesis and Characterization of Polymers with Azobenzene and Hexamethylene Groups in Main Chain (주사슬에 아조벤젠기와 헥사메틸렌기를 갖는 고분자의 합성 및 특성)

  • Gu, Su-Jin;Lee, Eung-Jae;Bang, Moon-Soo
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.20 no.4
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    • pp.86-92
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    • 2019
  • Polymers with various compositions of azobenzene and hexamethylene groups in the main chain were synthesized by a Schotten-Baumann reaction and their properties were investigated. The chemical structures and physical properties of the synthesized polymers were investigated by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, differential scanning calorimetry, thermogravimetric analysis, polarized optical microscopy, and x-ray diffraction. The polymers showed an inherent viscosity of 1.28-1.36 dl/g and were relatively insoluble in most organic solvents. The melt transition temperature increased rapidly with increasing number of azobenzene groups in the polymer. When the azobenzene monomer content was more than 50 mol%, no melting transition occurred below the decomposition temperature. Among the polymers with a melt transition temperature, the MP-A3C7 and MP-A5C5 polymers were liquid crystalline materials and exhibited a nematic phase with weak liquid crystallinity over a wide liquid crystal temperature range. This difference in the properties of the synthesized polymers is likely due to the changes in intermolecular forces resulting from the linearity and polarity of the trans-form of azobenzene.