• Journal of the Korean Chemical Society
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• v.30 no.4
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• pp.369-376
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• 1986

Diosgenin in an Indonesian Costus speciosus was determined by capillary gas-liquid chromatography (GLC). The experimental conditions for the hydrolysis, extraction and acetylation of the diosgenin, and the determination by GLC were investigated. 0.20g of dried sample powder was refluxed in the solution of 3N HCI and xylene at 95∼100${\circ}C$ for 4 hours and the xylene layer was separated. The residue evaporated the xylene was refluxed in 20 : 80 acetic anhydride-pyridine for 30 minutes and the diosgenin acetate was extracted with diethyl ether. Dehydrated with anhydrous $Na_2SO_4$ and evaporated the ether, the residue was dissolved in 5.00ml of n-hexane and injected into GLC. Capillary column of SE-30 25m ${\times}$ 0. 33mm was installed in GLC and the column temperature was increased from 180${\circ}$ to 270${\circ}C$ at rate of 10${\circ}C$/min. The flow rate of carrier gas $N_2$ was 2ml/min and FID was used to detect. The analytical result of the diosgenin was 0.281% and relative standard deviation of 5 measures was 1.8%.

• Archives of Pharmacal Research
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• v.21 no.4
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• pp.465-469
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• 1998

The search for platinum (II)-based compounds with improved therapeutic properties was prompted to design and synthesize a new family of water-soluble, third generation cis-diaminedichloroplatinum (II) complexes linked to uracil and uridine. Six heretofore unreported uracil and uridine-platinum (II) complexes are; [N-(uracil-5-yl-methyl)ethane-1,2-di-amine]dichloroplatinum (II) (3a), [N-(uracil-6-yl-methyl)ethane-1,2-diaminel dichloroplatinum (II) (3b), t[N-($2^1$, $3^1$,$5^1$-tri-O-acetyl)uridine-5-yl-methyl] ethane-1,2-diamineldichloroplatinum (II) (6a), {[N-($2^1$,$3^1$, $5^1$-tri-O-acetyl) uridine-6-yl-methyl]ethane-1,2-diamine)dichloroplatinum (II) (6b),[N-(uridine- 5-yl-methyl)ethane-1,2-diamine]dichloroplatinum (II) (7a), [N-(uridine-6-yl- methyl)ethane-1,2-diamine]dichloroplatinum (II) (7b). These analogues were prepared from the key starting materials, 5-chloromethyluracil (1a) and 6-chloromethyluracil (1b) which were reacted with ethylenediamine to afford the respective 5-[(2-aminoethyl)aminol methyluracil (2a) and 6-[(2-aminoethyl)amino]methyluracil (2b). The cis-platin complexes 3a and 3b were obtained through the reaction of the respective 2a and 2b with potassium tetrachloroplatinate (II). The heterocyclic nucleic acid bases 1a and 1b were efficiently introduced on the .betha.-D-ribose ring via a Vorbruggen-type nucleoside coupling procedure with hexamethyldisilazane, trimethylchlorosilane and stannic chloride under anhydrous acetonitrile to yield the stereospecific .betha.-anomeric 5-chloromethyl- $2^1$,$3^1$,$5^1$-tri-O-acetyluridine (4a) and 6-chloromethyl-$2^1$,$3^1$,$5^1$-tri-O-acetyluridine (4b), respectively. The nucleosides 4a and 4b were coupled with ethylenediamine to provide the respective 5-[(amino-ethyl)aminolmethyl-$2^1$,$3^1$,$5^1$-tri-O-acetyluridine (5a) and 6-[(aminoethyl)amino] methyl-$2^1$,$3^1$,$5^1$-tri-O-acetyluridine (5b). The diamino-uridines 5a and 5b were reacted with potassium tetrachloroplatinate (II) to give the novel nucleoside complexes, 6a and 6b, respectively which were deacetylated into the free nucleosides, 7a and 7b by the treatment with CH$_{3}$ONa. The cytotoxic activities were evaluated against three cell lines (FM-3A, P-388 and J-82) and none of the synthesized compounds showed any significant activity.

• Korean Journal of Soil Science and Fertilizer
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• v.39 no.1
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• pp.38-45
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• 2006

Movement of nitrate ($NO_3-N$) through a soil profile under no tillage (NT) or conventional tillage (CT) practices was monitored to identify the effects of tillage systems on nitrate leaching and retention in the soil profile at two commercial farms in central Illinois from 1993 through 1994. Anhydrous ammonia was applied in the 1993 growing seasons, while a mixture of urea and ammonium nitrate solution (URAN) was applied in three separate applications during the spring and early summer of the 1994 season. $NO_3-N$ of each plot through a 100 cm soil depth was found to be significantly high around $20mg\;kg^{-1}$ soil in the early 1993 season. However, downward movement of $NO_3-N$ occurred during the growing season. At the end of growing season, Flanagan and Ipava soils generally retained more $NO_3-N$ through the soil profile for both the CT plots and the NT plots than the Saybrook and Catlin soils. However, there was no significant difference between the nitrate content of the two soil types in each year. $NO_3-N$ content in NT fields were slightly higher than that observed in CT fields throughout the season before harvest. It means that NT plots may reduce the nitrate leaching to the ground water.

• Journal of the Mineralogical Society of Korea
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• v.3 no.1
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• pp.1-6
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• 1990

Clacic amphiboles along the tremolite (Tr)-tschermakite(Ts) joint were synthesized using a piston-cylinder appratus. At 750-85$0^{\circ}C$and 12-2 kb, amphibole+corundum coexist with zoisite($\pm$talc, chlorite, and Mg-staurolite), but with anorthite($\pm$cholorite, spinel, pyroxenes, and sapphirine) at lower P. At 90$0^{\circ}C$, amphibole+corundum+clinopyroxene($\pm$anorthite, forsterite, sapphirine, and garnet) are stable over the P range 12-18 kb. These amphibole-bearing assemblages are replaced at high P by clcinopyroxene+talc+chlorite+zoisite at 650-75$0^{\circ}C$, and at higher temperatures by garnet+clinopyroxene($\pm$zoisite, orthopyroxene, and Mg-staurolite). Synthetic amphiboles with Ts>~45 mol% contain as much as 0.15 excess cations per formula unit(pfu) based on 23 oxygens(anhydrous formula), whereas less tschermakitic ones are deficient in cation occupancy by up to 0.18 pfu. This trend is attributed to the 야/trioctahedral substitution in Ca-amphiboles. Compositions of synthetic amphiboles display systematic changes with P and T governed by coexisting mineral assemblages. The Ts content (=[8-Si-Na]/2) increases with increasing T( Ts/ T=~0.1 nik% K-1) in the range 750-85$0^{\circ}C$, but remains nearly constant at 850-90$0^{\circ}C$. Pressure dramatically affects the Ts content of Ca-amphiboles:it increases with P at 8-12 kb( Ts/ T=2-3 mol% K-1), but significantly decreases at 12-21 kb( Ts/ P=-2.5 mol% Kb-1). Hence, the most tschermakitic amphiboles, containing 60$\pm$5 mol % Ts, or 1.2$\pm$0.1 tetrahedral Al, occur at 12 kb and 850-90$0^{\circ}C$. Compositions of Ca-amphiboles defined by a simple reaction, 3 Tr+2 zoisite+7 corundum+H2O=5 Ts, are reversed and used to estimate thermodynamic parameters of tschermakite assuming ideal mixing of Tr-Ts solid solutions. Predicted standard molal entropy and enthalpy of tschermakite are : S$^{\circ}$of Tr-Ts solid solutions. Predicted standard molal entropy and enthalpy of tschermakite are : S$^{\circ}$=566.9$\pm$13.7 J mol-1K, -1and H$^{\circ}$=-12518.36$\pm$15.17 kJ mol.-1

• Bulletin of the Korean Chemical Society
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• v.22 no.1
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• pp.30-36
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• 2001

The crystal structures of fully dehydrated $Pd^{2+}$ - and $TI^{+}$ -exchanged zeolite X, $Pd_{18}TI_{56}Si_{100}Al_{92}O_{384}(Pd_{18}TI_{50-}X$, a = $24.935(4)\AA$ and $Pd_{21}TI_{50}Si_{100}Al_{92}O_{384}(Pd_{21}TI_{50-}X$ a = $24.914(4)\AA)$, have been determined by single-crystal X-ray diffraction methods in the cubic space group Fd3 at $21(1)^{\circ}C.$ The crystals were prepared using an exchange solution that had a $Pd(NH_3)_4Cl_2\;:TINO_3$ mole ratio of 50 : 1 and 200 : 1, respectively, with a total concentration of 0.05M for 4 days. After dehydration at $360^{\circ}C$ and 2 ${\times}$$10^{-6}$ Torr in flowing oxygen for 2 days, the crystals were evacuated at $21(1)^{\circ}C$ for 2 hours. They were refined to the final error indices $R_1$ = 0.045 and $R_2$ = 0.038 with 344 reflections for $Pd_{18}Tl_{56-}X$, and $R_1$ = 0.043 and $R_2$ = 0.045 with 280 reflections for $Pd_{21}Tl_{50-}X$; I > $3\sigma(I).$ In the structure of dehydrated $Pd_{18}Tl_{56-}X$, eighteen $Pd^{2+}$ ions and fourteen $TI^{+}$ ions are located at site I'. About twenty-seven $TI^{+}$ ions occupy site II recessed $1.74\AA$ into a supercage from the plane of three oxygens. The remaining fifteen $TI^{+}$ ions are distributed over two non-equivalent III' sites, with occupancies of 11 and 4, respectively. In the structure of $Pd_{21}Tl_{50-}X$, twenty $Pd^{2+}$ and ten $TI^{+}$ ions occupy site I', and one $Pd^{2+}$ ion is at site I. About twenty-three $TI^{+}$ ions occupy site II, and the remaining seventeen $TI^{+}$ ions are distributed over two different III' sites. $Pd^{2+}$ ions show a limit of exchange (ca. 39% and 46%), though their concentration of exchange was much higher than that of $TI^{+}$ ions. $Pd^{2+}$ ions tend to occupy site I', where they fit the double six-ring plane as nearly ideal trigonal planar. $TI^{+}$ ions fill the remaining I' sites, then occupy site II and two different III' sites. The two crystal structures show that approximately two and one-half I' sites per sodalite cage may be occupied by $Pd^{2+}$ ions. The remaining I' sites are occupied by $TI^{+}$ ions with Tl-O bond distance that is shorter than the sum of their ionic radii. The electrostatic repulsion between two large $TI^{+}$ ions and between $TI^{+}$ and $Pd^{2+}$ ions in the same $\beta-cage$ pushes each other to the charged six-ring planes. It causes the Tl-O bond to have some covalent character. However, $TI^{+}$ ions at site II form ionic bonds with three oxygens because the super-cage has the available space to obtain the reliable ionic bonds.

• Bulletin of the Korean Chemical Society
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• v.17 no.7
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• pp.631-637
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• 1996

The structures of fully dehydrated Ca2+- and Rb+-exchanged zeolite X, Ca31Rb30Si100Al92O384(Ca31Rb30-X; a=25.009(1) Å) and Ca28Rb36Si100Al92O384(Ca28Rb36-X; a=24.977(1) Å), have been determined by single-crystal X-ray diffraction methods in the cubic space group Fd&bar{3} at 21(1) ℃. Their structures were refined to the final error indices R1=0.048 and R2=0.041 with 236 reflections for Ca31Rb30-X, and R1=0.052 and R2=0.043 with 313 reflections for Ca28Rb36-X; I>3σ(I). In both structures, Ca2+ and Rb+ ions are located at six different crystallographic sites. In dehydrated Ca31Rb30-X, sixteen Ca2+ ions fill site I, at the centers of the double 6-rings (Ca-O=2.43(1) Å and O-Ca-O=93.3(3)°). Another fifteen Ca2+ ions occupy site II (Ca-O=2.29(1) Å, O-Ca-O=119.5(5)°) and fifteen Rb+ ions occupy site II opposite single six-rings in the supercage; each is 1.60 Å from the plane of three oxygens (Rb-O=2.77(1) Å and O-Rb-O=91.1(4)°). About two Rb+ ions are found at site II', 1.99 Å into sodalite cavity from their three-oxygen plane (Rb-O=2.99(1) Å and O-Rb-O=82.8(4)°). The remaining thirteen Rb+ ions are statistically distributed over site III, a 48-fold equipoint in the supercages on twofold axes (Rb-O=3.05(1) Å and Rb-O=3.38(1) Å). In dehydrated Ca28Rb36-X, sixteen Ca2+ ions fill site I (Ca-O=2.41(1) Å and O-Ca-O=93.6(3)°) and twelve Ca2+ ions occupy site II (Ca-O=2.31(1) Å, O-Ca-O=119.7(4)°). Sixteen Rb+ ions occupy site II; each is 1.60 Å from the plane of three oxygens (Rb-O=2.81(1) Å and O-Rb-O=90.6(3)°) and four Rb+ ions occupy site II'; each is 1.88 Å into sodalite cavity from their three-oxygen plane (Rb-O=2.99(1) Å and O-Rb-O=83.8(2)°). The remaining sixteen Rb+ ions are found at III site in the supercage (Rb-O=2.97(1) Å and Rb-O=3.39(1) Å). It appears that Ca2+ ions prefer sites I and II in that order, and that Rb+ ions occupy the remaining sites. Rb+ ions are too large to be stable at site I, when they are competing with other smaller cations like Ca2+ ions.

• The Journal of the Petrological Society of Korea
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• v.25 no.3
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• pp.261-281
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• 2016

Our knowledge of the lithosphere beneath the Korean Peninsula has been improved through petrologic and geochemical studies of upper mantle xenoliths hosted by Quaternary intraplate alkali basalts from Jeju Island. The xenoliths are mostly spinel lherzolites, accompanied by subordinate harzburgite and pyroxenites. The mantle xenoliths represent residual mantle material showing textural and geochemical evidence for at least a three-stage evolution, fractional partial melting, recrystallization, and metasomatism. Their composition primarily controlled by early fractional melt extraction and porphyroclastic and mylonitic fabrics formed in a shear-dominated environment, which was subsequently modified by residual slab-derived fluids (or melts). Modal metasomatic products occur as both anhydrous phase(orthopyroxene) and hydrous phase (phlogopite). Late-stage orthopyroxene is more common than phlogopite. However, chemical equilibrium is evident between the primary and secondary orthopyroxene, implying that the duration of post-metasomatic high temperatures enabled complete resetting/reequilibration of the mineral compositions. The metasomatic enrichment pre-dates the host Jeju Quaternary magmatism, and a genetic relationship with the host magmas is considered unlikely. Following enrichment in the peridotite protolith in the mantle wedge, the upper mantle beneath proto-Jeju Island was transformed from a subarc environment to an intraplate environment. The Jeju peridotites, representing old subarc fragments, were subsequently transported to the surface, incorporated into ascending Quaternary intraplate alkali basalt. The result of this study implies that long term material transfer in the transformation of geotectonic setting from a subarc to intraplate may have played a significant role in the evolution of lithospheric mantle, resulting in the enriched mantle domains, such as EM I or EM II in the lithospheric mantle beneath East Asia.

• Korean Journal of Environmental Agriculture
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• v.42 no.1
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• pp.71-81
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• 2023

An accurate and easy-to-use analytical method for determining isocycloseram and its metabolites (SYN549431 and SYN548569) residue is necessary in various food matrixes. Additionally, this method should satisfy domestic and international guidelines (Ministry of Food and Drug Safety and Codex Alimentarius Commission CAC/GL 40). Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) was used to determine the isocycloseram and its metabolites residue in foods. To determine the residue and its metabolites, a sample was extracted with 20 mL of 0.1% formic acid in acetonitrile, 4 g magnesium sulfate anhydrous and 1 g sodium chloride and centrifuged (4,700 G, 10 min, 4℃). To remove the interferences and moisture, d-SPE cartridge was performed before LC-MS/MS analysis with C₁₈ column. To verify the method, a total of five agricultural commodities (hulled rice, potato, soybean, mandarin, and red pepper) were used as a representative group. The matrix-matched calibration curves were confirmed with coefficients of determination (R²) ≥ 0.99 at a calibration range of 0.001-0.05 mg/kg. The limits of detection and quantification were 0.003 and 0.01 mg/kg, respectively. Mean average recoveries were 71.5-109.8% and precision was less than 10% for all five samples. In addition, inter-laboratory validation testing revealed that average recovery was 75.4-107.0% and the coefficient of variation (CV) was below 19.4%. The method is suitable for MFDS, CODEX, and EU guideline for residue analysis. Thus, this method can be useful for determining the residue in various food matrixes in routine analysis.

• Korean Journal of Environmental Agriculture
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• v.42 no.2
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• pp.139-151
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• 2023

Sulfonylurea herbicides are widely used in agriculture because they have a long residual period and high selectivity. An analytical method was developed using QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) technique for simultaneous determination of sulfonylurea herbicide residues in agricultural products by liquid chromatography tandem mass spectrometry and for establishment MRL (Maximum Residue Limit) of those herbicides in Korea. Extraction was performed using acetonitrile containing 0.1% formic acid with MgSO₄ (anhydrous magnesium sulfate) and NaCl (sodium chloride) and the extract was cleaned up using MgSO₄ and C₁₈ (octadecyl). The matrix-matched calibration curves were composed of 7 concentration levels from 0.001 to 0.25 mg/kg and their coefficients of determination (R²) exceeded 0.99. The recoveries of three spiking levels (LOQ, 10LOQ, 50LOQ, n=5) were in the range of 71.7-114.9% with relative standard deviations of less than 20.0% for all the five agriculture products. All validation values met criteria of the European Union SANTE/11312/2021 guidelines and Food and Drug Safety Evaluation guidelines. Therefore, the proposed analytical method was accurate, effective, and sensitive for sulfonylurea herbicide residues determination in agricultural commodities.

• Economic and Environmental Geology
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• v.47 no.4
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• pp.335-349
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• 2014

The Pocheon skarn deposit, located at the northwestern part of the Precambrian Gyeonggi massif in South Korea, occurs at the contact between the Cretaceous Myeongseongsan granite and the Precambrian carbonate rocks, and is also controlled by N-S-trending shear zone. The skarn distribution and mineralogy reflects both structural and lithological controls. Three types of skarn formations based on mineral assemblages in the Pocheon skarn exist; a sodiccalcic skarn and a magnesian skarn mainly developed in the dolostone, and a calcic skarn developed in the limestone. Iron mineralization occurs in the sodic-calcic and magnesian skarn zone, locally superimposed by copper mineralization during retrograde skarn stage. The sodic-calcic skarn is composed of acmite, diopside, albite, garnet, magnetite, maghemite, anhydrite, apatite, and sphene. Retrograde alteration consists of tremolite, phlogopite, epidote, sericite, gypum, chlorite, quartz, calcite, and sulfides. Magnesian skarn mainly consists of diopside and forsterite. Pyroxene and olivine are mainly altered to tremolite, with minor phlogopite, talc, and serpentine. The calcic skarn during prograde stage mainly consists of garnet, pyroxene and wollastonite. Retrograde alteration consists of epidote, vesuvianite, amphibole, biotite, magnetite, chlorite, quartz, calcite, and sulfides. Microprobe analyses indicate that the majority of the Pocheon skarn minerals are enriched by Na-Mg composition and have high $Fe^{3+}/Fe^{2+}$, $Mg^{2+}/Fe^{2+}$, and $Al^{3+}/Fe^{2+}$ ratios. Clinopyroxene is acmitic and diopsidic composition, whereas garnet is relatively grossular-rich. Amphiboles are largely of tremolite, pargasite, and magnesian hastingsite composition. The prograde anhydrous skarn assemblages formed at about $400^{\circ}{\sim}500^{\circ}C$ in a highly oxidized environment ($fO_2=10^{-23}{\sim}10^{-26}$) under a condition of about 0.5 kbar pressure and $X(CO_2)=0.10$. With increasing fluid/rock interaction during retrograde skarn, epidote, amphibole, sulfides and calcite formed as temperature decreased to approximately $250^{\circ}{\sim}400^{\circ}C$ at $X(CO_2)=0.10$.