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Template Synthesis and Characterization of Four- and Five-Coordinate Copper(II) Complexes with Hexaaza Macrotricyclic Ligands 1,3,6,9,11,14-Hexaazatricyclo $[12.2.1.1^{6,9}]octadecane(L_1)$ and 1,3,6,10,12,15-Hexaazatricyclo $[13.3.1.1^{6,10}]eicosane(L_1)$

  • Myunghyun Paik Suh;Shin-Geol Kang;Teak-Mo Chung
    • Bulletin of the Korean Chemical Society
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    • v.11 no.3
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    • pp.206-208
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    • 1990
  • Cu(II) hexaazamacrotricyclic complexes $[Cu(L)](ClO_4)_2$ and $[(Cu(L)Cl]ClO_4$, where L = 1,3,6,9,11,14-hexaazatricyclo$[12.2.1.1^{6,9}]octadecane(L_1)$ or 1,3,6,10,12,15-hexaazatricyclo$[13.3.1.1^{6,10}]eicosane(L_2)$, have been prepared by the simple template condensation reactions of triamines, diethylenetriamine for $L_1$, and N-(2-aminoethyl)-1,3-propanediamine for $L_2$, with formaldehyde in the presence of $Cu(OAc)_2\;or\;CuCl_2$. The Cu(II) complexes of $L_1$ contain two 1,3-diazacyclopentane ring moieties and those of $L_2$ contain two 1,3-diazacyclohexane ring moieties that are fused to the 14-membered macrocyclic framework. Spectra indicate that complexes $[Cu(L)](ClO_4)_2\;and\;[Cu(L)Cl]ClO_4$ have square-planar and square-pyramidal chromophores, respectively. square-planar $[Cu(L)](ClO_4)_2$ are remarkably stable against ligand dissociation in acidic aqueous solutions. Square-pyramidal $[Cu(L)Cl]ClO_4$ complexes dissociate their axial Cl-ligands easily in aqueous solutions to form $[Cu(L)H_2O]^{2+}$ species. Infrared and UV/vis absorption spectra of the Cu(II) complexes reveal that Cu-N interactions and the ligand field strengths are significantly weaker in the complexes of $L_2$ than in the complexes of $L_1$.

Fish length dependance of acoustic target strength for large yellow croaker (부세에 대한 음향반사강도의 체장 의존성)

  • 강희영;이대재
    • Journal of the Korean Society of Fisheries and Ocean Technology
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    • v.39 no.3
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    • pp.239-248
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    • 2003
  • This paper was conducted as an attempt in order to construct the data bank of target strength for acoustic estimation of fish length in the coastal waters of Korea. The fish length dependence of acoustic target strength for 13 large yellow croakers (Pseudosciaena crocea) at 75 kHz was investigated and the prediction of the target strength by using the Kirchhoff-Ray Mode model (KRM model) was compared with target strength measurements. The results obtained are summarized as follows; 1. In the averaged target strength pattern for 13 large yellow croakers the maximum target strength was -35.13 dB at $-13.35^{\circ}$ on a tilted angle. 2. The relationship between fork length(L, cm) and averaged target strength(TS, dB) was expressed as follows; TS=23. 76log (L) -73.45 (r=0.47) TS=20log(L) -67.35 From this result, the conversion coefficient was -73.45 dB and 6.1 dB lower than the coefficient -67.35 dB where the value of the slope of the regression equation is forced to be 20. 3. Averaged target strength and a length conversion coefficient derived from a target strength histogram for 13 large yellow croakers of mean length 25.59 cm were -41.23 dB, -69.72 dB, respectively. 4. In the range of $$2;{\ll} L (fish length /{\lambda}(wave length);{\ll}40$$, the prediction of the averaged target strength by the KRM model increased gradually with the increasing of $L/{\lambda}$ and was lower than the measured target strength.

Mass Propagation by In Vitro Culture of Bupleurum latissimum Nakai (섬시호(Bupleurum latissimum Nakai)의 조직배양을 통한 대량생산)

  • Cho, Han-Jik;Kim, Ee-Youp;Kim, Mu-Yeol;Park, Hark-Bong;Kim, Hyo-Jin
    • Korean Journal of Plant Resources
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    • v.20 no.4
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    • pp.367-374
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    • 2007
  • This study was carried out to establish the micropropagation system of Bupleurum latissimum Nakai that is a Korean native endangered species. Callus were induced from the leaf, petiole and floral bud and the percentage of callus formation was highest in the floral bud on the MS medium containing 2.0 mg ${\cdot}$ $L^{-1}$ 2,4-D. Especially, callus induced from floral bud was formed 77.8% and the percentage of shoot formation was 42.6% on the MS medium containing 2.0 mg ${\cdot}$ $L^{-1}$ 2,4-D plus 1.0 mg ${\cdot}$ $L^{-1}$ TDZ. For simultaneously callus formation and shoot regeneration, 1/2 MS medium was more effective than MS medium. The percentage callus formation, shoot regeneration and rooting were 46.3%, 13.0%, 13.0% in 1/2 MS medium, respectively. Soot regeneration from callus was good in 1/2 MS medium supplemented with 2.0 mg ${\cdot}$ $L^{-1}$ 2,4-D plus 1.0 mg ${\cdot}$ $L^{-1}$ BA where percentage of shoot regeneration was 74.1 %, and the number of shoot per explant was 2.4. The percentage of rooting was lowest (57.8%) in control while it was highest (97.8%) in 1.5 mg ${\cdot}$ $L^{-1}$ NAA. In acclimatization of regenerated plantlets, the percentage of survived plantlets was highest (86.1%), and plant height, root length and fresh weight were good in the soil for horticulture.

Preparation and Structure of $[Ni(L)]I_2$ (L:3,5,10,12-Tetramethyl-1,4,8,11-tetraazacyclotetradecane) ($[Ni(L)]I_2$ (L:3,5,10,12-Tetramethyl-1,4,8,11-tetraazacyclo-tetradecane) 합작물의 합성 및 구조)

  • 최기영;김동원
    • Korean Journal of Crystallography
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    • v.8 no.2
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    • pp.119-123
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    • 1997
  • The complex [Ni(L)]I2 (1) (L:3,5,10,12-Tetramethly-1,4,8,11-tetraazacyclotetradecane) has been prepared and characterized by X-ray diffraction methods. The complex 1 crystallized in the orthorhombic system, space group Pcab with cell parameters a=13.293(1) Å, b=28.550(7) Å, c=10.804(1) Å, z=8. Least-squares refinement of 1 led to a R(Rw) factor of 0.043 (0.046) for 1851 observed reflections of Fo>3o (Fo). The crystal structure of 1 has a slightly distorted square-planar geometry and adopts the trans-III conformation.

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Anticancer and Antimicrobial Activities of 13(E)-labd-13-ene-8α,15-diol from Brachyglottis monroi

  • Kim, Jong-Im;Choi, Hwa-Jung;Lee, Jae-Sook
    • Journal of Applied Biological Chemistry
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    • v.56 no.1
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    • pp.49-51
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    • 2013
  • In a previous study, we reported that 13(E)-labd-13-ene-$8{\alpha}$,15-diol (13E) possesses antiviral and anticancer activities. In this study, the anticancer and antimicrobial activities of 13(E) were evaluated against 4 cancer cell lines and 6 bacteria. 13(E) showed inhibitory effect on a variety of cancer cell lines. The $IC_{50}$ values was 8.3-21.3 ${\mu}g/mL$. 13(E) was the most effective growth inhibitor of murine leukaemia cell lines P388, producing approximately 8.3 ${\mu}g/mL$ of $IC_{50}$ in the cytopathic effect (CPE) method. 13(E) also inhibited the growth of the gram-positive bacteria (Staphylococcus aureus, Bacillus cereus and Listeria monocytogenes) and gram-negative bacteria (Vibrio parahaemolyticus, Escherichia coli and Salmonella enteritidis) with a range of minimum inhibitory concentration (MIC) values from 0.092 to 0.598 mg/mL and gram-negative bacteria were more sensitive to the compound (MIC, 0.092 mg/mL).

Isolation and Structure Elucidation of Radical Scavengers from Chrysanthemum boreale Makino (산국(山菊)의 자유라디칼 소거 물질 분리 및 동정)

  • Han, Wan-Soo
    • Korean Journal of Medicinal Crop Science
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    • v.11 no.1
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    • pp.1-4
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    • 2003
  • Two antioxidative compounds in Chrysanthemum boreale were isolated by a bioassay using a 2, 2-diphenyl-1-picrydrazyl(DPPH) free radical. They were identified as apigenin, linarin(acacetin-7-O-rutinoside) on the basis of $^1H\;and\;^{13}C-NMR$ and MS data. The DPPH radical scavenging activity$(RC_{50}:\;13.3{\mu}g)$ of apigenin was similar to that of ${\alpha}-tocopherol\;(12.1{\mu}g)$ and L-ascorbic acid$(13.1{\mu}g)$

Electroacupuncture therapy for the treatment of thoracolumbar disc disease in dogs (개의 흉·요추 디스크 질환에 대한 전침요법 시술 예)

  • Seo, Kang-moon
    • Korean Journal of Veterinary Research
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    • v.35 no.4
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    • pp.863-868
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    • 1995
  • Electroacupuncture therapy was performed in 2 dogs with thoracolumbar disc disease. Case was a 3-year-old female chihuahua with a calcified disc between the 13th thoracic and 1st lumbar vertebrae. Treatment was done by electroacupuncture at San sho yu, Shen yu, Huan tiao and Fu yang-San yin jiao with the current of 0.5~8 volts, 30 Hz for 30 min. She could pass feces and urine 2 days, and walk 9 days after the beginning of the therapy. Case 2 Was a 6-year-old male cocker spaniel with 4 calcified discs(T12-T13, T13-L1, L2-L3 and L6-L7) and spondylosis(lumbosacral junction). Treatment was done by electroacupuncture at Tian ping, Bai hui and Pung kung yu with the current of 2~4 volts, 30 Hz for 20 min. He could pass feces 6 days, urine 8 days, and stand 21 days, after the beginning of the therapy.

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Selective Synthesis of a New Macropolycycle Containing One N-CH2-N Linkage and Its Reaction with Cu2+ and Ni2+ Ions in Methanol

  • Kang, Shin-Geol;Kweon, Jae-Keun;Jeong, Gyeong-Rok;Lee, Uk
    • Bulletin of the Korean Chemical Society
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    • v.29 no.10
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    • pp.1905-1910
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    • 2008
  • The reaction of 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[16.4.0$0^{1.18}.0^{7.12}$]docosane ($L^1$) with formaldehyde in warm methanol yielded 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[16.4.$1^{2.6}.0^{1.18}.0^{7.12}$]tricosane ($L^7$) containing one 1,3-diazacyclohexane subunit. In methanol, $L^7$ readily reacts with $Cu^{2+}$ ion to form [$CuL^7(H_2O)$]$^{2+}$ which is extremely inert against methanolysis. In the solution containing $Ni^{2+}$ ion, however, $L^7$ reacts with methanol to yield [$NiL^3$]$^{2+}$ ($L^3$ = 2-(methoxymethyl)-5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.$0^{1.18}.0^{7.12}$]- docosane), in which one N-$CH_2OCH_3$ pendant arm is appended. The copper(II) complex [$CuL^7(H_2O)$]- $(ClO_4)_2{\cdot}3H_2O\;(I{\cdot}3H_2O)$ has a severely distorted trigonal bipyramidal coordination geometry with a 4-5- 6-5 chelate ring sequence. The crystal structure of [$NiL^3$]$(PF_6)_2{\cdot}2H_2O$ (IIb) shows that the N-$CH_2OCH_3$ pendant arm is not coordinated to the metal ion in the solid state. In various solvents (S), however, the nickel(II) complex exists as a mixture of [$NiL^3$(S)]$^{2+}$, in which the N-$CH_2OCH_3$ group as well as S is coordinated to the metal ion, and [$NiL^3$]^{2+}.

Suppressive effects of Morus alba Linne Root Bark (MRAL) on activation of MC/9 mast cells (상백피에 의한 MC/9 비만세포의 활성 억제 조절 연구)

  • Lee, Ki Jeon;Kim, Bok Kyu;Kil, Ki Jung
    • The Korea Journal of Herbology
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    • v.28 no.1
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    • pp.33-42
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    • 2013
  • Objective : Morus alba Linne Root Bark (MRAL) is a medicinal herb in Korean Medicine, known for its anti-inflammatory and anti-allergic properties. However, its mechanisms of action and the cellular targets have not yet been found and the study was developed to investigate the allergic suppressive effect of MRAL. The purpose of this study is to investigate the allergic suppressive effects of MRAL on activation of MC/9 mast cells. Methods : Cytotoxic activity of MRAL (50, 100, 200, 400 ${\mu}g/mL$) on MC/9 mast cells measured using EZ-Cytox cell viability assay kit (WST reagent). The levels of interleukin-5 (IL-5), IL-13 and IL-4, IL-5, IL-6, IL-13 mRNA expression were measured by enzyme-linked immunosorbent assay (ELISA) and real-time PCR respectively. The expression of transcription factors such as GATA-1, GATA-2, NFAT, AP-1 and NF-${\kappa}B$ p65 DNA binding activity were measured by western blot and electrophoresis mobility shift assay (EMSA). Results : Our results indicated that MRAL (50 ${\mu}g/mL$, 100 ${\mu}g/mL$) significantly inhibited PMA/Ionomycin-induced production of IL-5 and IL-13 and the expression of IL-4, IL-5, IL-6 and IL-13 mRNA in MC/9 mast cells. Moreover, MRAL (50 ${\mu}g/mL$, 100 ${\mu}g/mL$) inhibited PMA/Ionomycin-induced GATA-1, GATA-2, NFAT-1, NFAT-2, c-Fos protein expression and NF-${\kappa}B$ p65 DNA binding activity in MC/9 mast cells. Conclusions : In conclusion, we suspect the anti-allergenic activities of MRAL, may be related to the regulation of transcription factors GATA-1, GATA-2, NFAT-1, NFAT-2, c-Fos and NF-${\kappa}B$ p65 DNA binding assay causing inhibition of Th2 cytokines IL-5 and IL-13 in mast cells.

Preparationan dCrystal Structure of [Ni($L^2$)($H_2O$)]Cl$\cdot$$H_2O$ ($L^2$: 3,14-dimethyl-2,6,13,17-tetraazatricyclo [14,4,$0^{1.18}$,$0^{7.12}$]docosane-N-acetic acid) ([Ni($L^2$)($H_2O$)]Cl$\cdot$$H_2O$ ($L^2$: 3,14-dimethyl-2,6,13,17-tetraazatricyclo [14,4,$0^{1.18}$,$0^{7.12}$docosane-N-acetic acid) 착물의 합성 및 결정구조)

  • Park, Ki-Yonng;Park, Young-Soo;Kim, Jin-Gyu;Suh, Il-Hwan;Kim, Chang-Suk
    • Korean Journal of Crystallography
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    • v.10 no.1
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    • pp.33-38
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    • 1999
  • The complex [Ni(L2)(H2O)]Cl·H2O (1) (L2=3,14-dimethyl-2,6,13,17-tetraazartricyclo [14,4,01.18,07.12]docosane-N-acetic acid) has been synthesized and characterized by X-ray crystallography. 1 crystallizes in the triclinic system, space group P, with a=11.274(1), b=13.851(1), c=17.159(6) , α=90.24(2), β=101.10(2), γ=92.11(1)o V=2682.5(11) 3, Z=4, R1=0.042 and wR2=0.111 for 9432 observed reflections with [I>2σ(I)]. The central nicke(II) ion is six-coordinated octahedral geometry with bonds to the four amine nitrogen atoms the carboxylic oxygen atom of the macrocyclic ligand and to the water molecule occupying a position trans to the pendant arm.

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