• Bulletin of the Korean Chemical Society
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• v.29 no.3
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• pp.599-603
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• 2008

The complexes Pd(nbmtp)Cl2 and Pt(nbmtp)Cl2 (nbmptp = 1-nonyl-3,4-bis(methylthio)pyrrole) were prepared and their x-ray structures were determined at room temperature. The four-coordinated metal unit and the pyrrole ring formed a nearly planar geometry. The free ligand dissolved in CH2Cl2 produced two luminescence bands associated with the lone-pair electron of S (l max = 525 nm) and the pyrrole p electron (l max = 388 nm). When the two complexes were dissolved in CH2Cl2, these two luminescence bands were also observed, although the low-energy band was blueshifted. For the crystalline Pt(II) complex, only the strong charge transfer band (l max = 618 nm) from the d* orbital of Pt resulted from excitation of the lone-pair electron of S.

• Bulletin of the Korean Chemical Society
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• v.18 no.3
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• pp.324-327
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• 1997

Water soluble iridium complex, IrCl(CO)(TPPTS)2·χH2O (1) (TPPTS=m-trisulfonated triphenylphosphine) has been prepared from the reaction of a water soluble complex, IrCl(COD)(TPPTS)2·6H2O (COD=l,5-cyclooctadiene) with CO and unambiguously characterized by electronic absorption, 31P NMR, 13C NMR and IR spectral data. Complex 1 catalyzes the hydration of terminal alkynes to give ketones in aqueous solutions at room temperature. The rate of PhC≡CH hydration dramatically increases with addition of MeOH to the reaction mixture in H2O, which is understood in terms of i) the excellent miscibility between H2O and MeOH and ii) the assumed catalytic hydration pathway involving the initial formation of (alkyne)IrCl(CO)(TPPTS)2.

• Bulletin of the Korean Chemical Society
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• v.27 no.9
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• pp.1445-1449
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• 2006

Molecular tweezers based on chenodeoxycholic acid bearing different lengths of arm were synthesized andtheir anion binding affinities were evaluated by $^1H$ NMR, isothermal calorimetric titration, and ESI mass spectrometry. Molecular tweezer 6 showed a high selectivity toward $H_2PO_4\;^-$ over $Cl^-,\;Br^-,\;I^-, $ and $CH_3CO_2\;^-$ by $^1H$ NMR titration, whereas the association constant for $F^-$ revealed the largest value as determined by ITC. The selectivity of 6 towards $F^-$ was about 103 times higher than that of $Cl^-,\;H_2PO_4\;^- $, and $CH_3CO_2\;^-$. ITCexperiment of 6 with $F^-$ in a DMSO showed two binding modes; two sequential association constants $K_1\;=\;2.77\;{\times}\;10^5\;M^{-1}$ and $K_2\;=\;8.68\;{\times}\;10^6\;M^{-1}$ were found. These sequential bindings were confirmed by ESI massspectrometry. 1 : 1 and 1 : 2 complexes of 6 and $F^-$ were found at m/z 868.08 and 884.04.

• Fisheries and Aquatic Sciences
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• v.14 no.3
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• pp.179-185
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• 2011

The antioxidant activities of a methanolic extract of Eisenia bicyclis and its organic solvent fractions, including dichloromethane ($CH_2Cl_2$), ethyl acetate (EtOAc), n-butanol (n-BuOH), and water ($H_2O$) fractions, were investigated. Scavenging activities against DPPH, hydroxyl, superoxide anion, and peroxynitrite radicals were evaluated using electron spin resonance spectrometry; intracellular reactive oxygen species (ROS) were evaluated by a 2',7'-dichlorofluorescein diacetate assay using RAW264.7 mouse macrophages. The antioxidant activities of the individual fractions were: EtOAc>n-BuOH>$CH_2Cl_2$ >$H_2O$. The EtOAc fraction exhibited strong radical scavenging activity and a significantly reduced ROS level in RAW264.7 cells. Moreover, the phenolic contents of the extract and fractions followed the same order as their radical scavenging activities. Our results indicate that E. bicyclis is a valuable natural source of antioxidants that may be applicable to the functional food industry.

• Korean Journal of Crystallography
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• v.10 no.1
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• pp.1-8
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• 1999

Two conformational isomers of p-tert-butylcalix[4]arene hexanoate were prepared from the reaction of-p-tert-butylcalix[4]arene and hexanoly chloride in the presence of AlCl3 in CH2Cl2 and their structures were determined by NMR spectra and X-ray diffraction as a cone and a 1,3-alternate conformer, respectively. The crystal of cone conformer (C68H96O8·(CH3)2CO) is triclinic, P, a=15.066(1) , b=16.063(1) , c=16.365(1) , α=79.75(2)o, β=109.95(2)o, γ=80.32(0)o, V=3602.7(4) 3, Z=2. The intensity data were collected on Simens SMART diffractometer/CCD area detector. The structure was solved by direct method and refined by least-squares calculations to a final R value of 0.144 for 4638 observed reflections. The molecular conformation is distorted symmetric cone with the flattening A and D phenyl rings. The crystal of 1,3-alternate conformer (C68H96O8·2CHCl3) is orthorhombic, Pca21, a=34.586(5) , b=10.207(3) , c=20.394(4) , V=7199(3) 3, Z=4. The intensity data were collected on an Enraf-Noninus CAD-4 Diffractometer with a graphite monochromated Mo-K radiation. The structure was solved by direct method and refined by least-squares calculations to a final R value of 0.152 for 2241 observed reflections. The molecule has a pseudo mirror symmetric 1,3-alternate conformation.

• Korean Journal of Pharmacognosy
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• v.29 no.3
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• pp.209-216
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• 1998

In the course of phytochemical studies of Rumex acetosella L. (Polygonaceae), the MeOH extract of the whole plants was fractionated with $CH_2Cl_2$ and $H_2O$, and the $CH_2Cl_2$ layer was fractionated again with 90% MeOH and hexane. Whereas $H_2O$ layer was fractionated with EtOAc and then with n-BuOH again. By repeated column chromatography, compound 1 was isolated from the 90% MeOH fraction, compounds 1, 2, 3, 4 and 5 were from the ethylacetate fraction, and compound 5 was from the n--BuOH fraction. On the basis of physico-chemical, spectroscopic evidences and in comparison with authentic samples, the structures of them were confirmed to emodin, citreorosein, $chrysophanol-8-O-{\beta}-D-glucopyranoside$, luteolin and $luteolin-7-O {\beta}-D-glucopyranoside$.

• Korean Journal of Pharmacognosy
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• v.43 no.1
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• pp.6-9
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• 2012

The $CH_2Cl_2$ soluble part of the leaves of Helianthus tuberosus L. (Compositae) exhibited a potent cytotoxic activity against the cultured human tumor cell lines including A-549, SK-OV-3, SK-MEL-2, XF498 and HCT-15 in vitro. Bioassaydirected fractionation of the $CH_2Cl_2$ soluble part of this plant led to the isolation of four cytotoxic sesquiterpene lactones having ${\alpha}$-methylene-${\gamma}$-lactone ring in the molecule. On the basis of physical and spectral evidences, their structures were characterized as ${\Delta}^{4,15}$-isoatripliciolide tiglate (1), ${\Delta}^{4,15}$-isoatripliciolide methacrylate (2), budlein A isobutylate (3) and budlein A tiglate (4). The ${\Delta}^{4,15}$-isoatripliciolide tiglate (1) showed the most potent cytotoxic activity ($0.26{\mu}M<ED_{50}<2.16{\mu}M$) against all of the cell lines tested.

• Journal of the Korean Chemical Society
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• v.22 no.3
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• pp.150-157
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• 1978

The rate constants for the hydrolysis of the derivatives of N-(p-nitrophenyl)-benzohydrazonyl azide (p-$CH_3,\;p-CH_3O,\;p-NO_2$, p-Cl, p-Br) have been determined by UV spectrophotometry in 50% dioxane-water at $25^{\cicr}C$ and a rate equation which can be applied over wide pH range was obtained. Below pH 5, the rate of hydrolysis of hydrazonyl azides is accelerated by electron-donating group ($\rho$ = -0.47), whereas at the pH values greater than 7, the $\rho$-value is 0.68. The effect of salt, solvent, substituent and azide ion on the rate of hydrolysis are rationalized in terms of $S_N1$ and $S_N2$ mechanism; below pH 5, the hydrolysis proceed through $S_N1$, however, above pH 7, the hydrolysis is started by the attack of hydroxide ion and in the range of pH 5∼7, these two reactions occur competitively.

• Economic and Environmental Geology
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• v.36 no.6
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• pp.391-405
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• 2003

The Daebong gold-silver deposit consists of mesothermal massive quartz veins thar are filling the fractures along fault shear (NE, NW) Bones within banded or granitic gneiss of Precambrian Gyeonggi massif. Based on vein mineralogy, ore textures and paragenesis, ore mineralization of this deposits is composed of massive white quartz vein(stage I) which was formed in the same stage by multiple episodes of fracturing and healing, and transparent quartz vein(stage II) which is separated by a major faulting event. Stage I is divided into the 3 substages. Ore minerals of each substages are as follows: 1) early stage I=magnetite, pyrrhotite, arsenopyrite, pyrite, sphalerite, chalcopyrite, 2) middle stage I=pyrrhotite, arsenopyrite, pyrite, marcasite, sphalerite, chalcopyrite, galena, electrum and 3) late stage I=pyrite, sphalerite, chalcopyrite, galena, electrum, argentite, respectively. Ore minerals of the stage II are composed of pyrite, sphalerite, chalcopyrite, galena and electrum. Systematic studies (petrography and microthermometry) of fluid inclusions in stage I and II quartz veins show fluids from contrasting physical-chemical conditions: 1) $H_2O-CO_2-CH_4-NaCl{\pm}N-2$ fluid(early stage I=homogenization temperature: 203∼3$88^{\circ}C$, pressure: 1082∼2092 bar, salinity: 0.6∼13.4 wt.%, middle stage I=homogenization temperature: 215∼28$0^{\circ}C$, salinity: 0.2∼2.8 wt.%) related to the stage I sulfide deposition, 2) $H_2O-NaCl{\pm}CO_2$ fluid (late stage I=homogenization temperature: 205∼2$88^{\circ}C$, pressure: 670 bar, salinity: 4.5∼6.7 wt.%, stage II=homogenization temperature: 201-3$58^{\circ}C$, salinity: 0.4-4.2 wt.%) related to the late stage I and II sulfide deposition. $H_2O-CO_2-CH_4-NaCl{\pm}N_2$ fluid of early stage I is evolved to $H_2O-NaCl{\pm}CO_2$ fluid represented by the $CO_2$ unmixing due to decrease in fluid pressure and is diluted and cooled by the mixing of deep circulated meteoric waters ($H_2O$-NaCl fluid) possibly related to uplift and unloading of the mineralizing suites. $H_2O-NaCl{\pm}CO_2$ fluid of stage II was hotter than that of late stage I and occurred partly unmixing, mainly dilution and cooling for sulfide deposition. Calculated sulfur isotope compositions ({\gamma}^{34}S_{H2S}$) of hydrothermal fluids (3.5∼7.9%o) indicate that ore sulfur was derived from mainly an igneous source and partly sulfur of host rock. Measured and calculated oxygen and hydrogen isotope compositions ({\gamma}^{18}O_{H_2O}$, {\gamma}$D) of ore fluids (stage I: 1.1∼9.0$\textperthousand$, -92∼-86{\textperthansand}$, stage II: 0.3{\textperthansand}$, -93{\textperthansand}$) and ribbon-banded structure (graphitic lamination) indicate that mesothermal auriferous fluids of Daebong deposit were two different origin and their evolution. 1) Fluids of this deposit were likely mixtures of $H_2O$-rich, isotopically less evolved meteoric water and magmatic fluids and 2) were likely mixtures of $H_2O$-rich. isotopically heavier $\delta$D meteoric water and magmaticmetamorphic fluids.

• Archives of Pharmacal Research
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• v.20 no.3
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• pp.259-263
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• 1997

In the preparation of acyclic thymidine nucleoside analogues, $K_2CO_3$(or NaH) treated thymine in DMSO was alkylated with .omega.-chloroalkyl nitrite (Cl-(CH_2)n-CN; n=1, 2, 3, 4) to provide an isomeric mixture of 1-(${\omega}$-cyanoalkyl)thymine (2a-d) and 1,3-bis(${\omega}$-cyanoalkyl)thymine in approximately 5:1 ratios. Reduction of the cyano function 2a-d with $NaBH_{4}/CoCl_{2}$ center dot$ 6H_{2}O$gave the corresponding 1-(${\omega}$aminoalkyl)thymine (3a-d). The newly formed primary amino function in 3a-d was directly reacted with 2-chloroethylisocyanate to afford the 1-[.omega.($N^{I}$-2-chloroethylureido) alkyl]thymine (4a-d) in good yields. Nitrosation of 1-[5-($ N^{I}-2$-chloroethylureido)pentyl] thymine (4d) with glacial acetic acid and dry $NaNO_{2}$-powder in anhydrous $CH_{2}Cl_{2}$gave two types of regioisomeric nitrosoureas, 1-[5-($N^{I}$--chloroethyl-$N^{I}$--nitrosoureido)pentylithymine (5d) and 1-[5-($N^{I}-2$-chloroethyl-N-nitrosoureido)pentyllthymine in approximately 5 :1 ratios. The in vitro cytotoxicity of the synthesized compounds (2a-d, 3a-d, 4a-d and 5a-d) against three cell lines (K-562, P-388 and FM-3A) are measured as $IC^{50}$ values. Compounds 3b and 4c showed moderate activities against all three cell lines, and all other compounds were found to be not active.