• Journal of the Korean Chemical Society
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• v.45 no.3
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• pp.242-246
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• 2001

The quaternary thiophosphates, $A_2NiP_2S_6$ (A=Rb, Cs), have been synthesized with halide fluxes and structurally characterized by single-crystal X-ray diffraction technique. These compounds crystallize in the space group $C_{2h}^5-P2_1/n$ of the monoclinic system with two formula units in a cell of dimensions a=5.960(2), b=12.323(4), $c=7.491(3)\AA$, $\beta=97.05(3)^{\circ}$, and $V=546.0(3)\AA^3$ for Rb2NiP2S6 and a=5.957(4), b=12.696(7), $c=7.679(4)\AA$, $b=93.60(5)^{\circ}$, and $V=579.7(5)\AA^3$ for $Cs_2NiP_2S_6.$ These compounds are isostructural. The structure of $Cs_2NiP_2S_6$ is made up of one-dimensional $_\infty^1[NiP_2S_6^{2-}]$ chains along the a axis and these chains are isolated by $Cs^+$ ions. The Ni atom is octahedrally coordinated by six S atoms. These Ni$S_6$ octahedral units are linked by sharing three m-S atoms of the $[P_2S_6^{4-}]$ anions to form the infinite one-dimensional $_\infty^1[NiP_2S_6^{2-}]$ chain. For $Cs_2NiP_2S_6$, the magnetic susceptibility reveals an antiferromagnetic exchange interaction below 8K,which corresponds to the Neel temperature ($T_N$). Above $T_N$, this compound obeys Curie-Weiss law. The magnetic moment, C, and ${\theta}forCs_2NiP_2S_6$ are 2.77 B.M., 0.9593 K, and -19.02 K, respectively. The effective magnetic moment obtained from the magnetic data is agreed with the spin-only value of $Ni^{2+}d^8$(2.83 B.M.) system.

• Journal of the Korean Chemical Society
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• v.44 no.5
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• pp.403-409
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• 2000

The formation and dissociation rates of $Zn^{2+}$ Complexes with l,4,7,10-tetraaza-13,16-diox-acyclooctadecane-N,N',N",N'"-tetraacetic acid (1), 1,4,7,10-tetraaza-13,16- dioxacyclooctadecane-N,N',N",N'"-tetramethylacetic acid (2), and 1,4,7,10-tetraaza-13,16- dioxacyclooctadecane-N,N',N",N'"-tetrapropionic acid(3) have been measured by stopped-flow and conventional spectrophotometry. Observations were made at 25.0$\pm$0.1 $^{\circ}C$ and at an ionic strength of 0.10 M NaClO$_4$. The formation reactions of $Zn^{2+}$ ion with 1 and 2 took place by the rapid formation of an intermediate complex (ZnH$_3L^+$) in which the $Zn^{2+}$ ion is incompletely coor-dinated. This might then lead to be a final product in the rate-determining step.ln the pH range 4.76-5.76, the diprotonated (H2L2-) form is the kinetically active species despite of its low concentration. The stability con-stants (log$K_{(ZnH$_3$3$L^+$)}$) and specific water-assisted rate constants (koH) of intermediate complexes have been deter-mined from the kinetic data. The dissociation reactions of $Zn^{2+}$ complexes of 1,2, and 3 were investigated with $Cu^{2+}$ ions as a scavenger in acetate buffer. All complexes exhibit acid-independent and acid-catalyzed con-tributions. The effect of buffer and $Cu^{2+}$ concentration on the dissociation rate has also been investigated. The ligand effect on t dissociation rate of $Zn^{2+}$ complexes is discussed in terms of the side-pendant armsand the chelate ring sizes of the ligands.

• Journal of the Mineralogical Society of Korea
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• v.26 no.2
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• pp.101-110
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• 2013

Due to the large specific surface area and great reactivity toward environmental contaminants, nanocrystalline mackinawite (FeS) has been widely applied for the remediation of contaminated groundwater and soil. Furthermore, nanocrystalline FeS is rather thermodynamically stable against anoxic corrosion, and its reactivity can be regenerated continuously by the activity of sulfate-reducing bacteria. However, nanocrystalline mackinawite is prone to either spread out along the groundwater flow or cause pore clogging in aquifers by particle aggregation. Accordingly, this mineral should be modified for the application of permeable reactive barriers (PRBs). In this study, coating methods were investigated by which mackinawite nanoparticles were deposited on the surface of alumina or activated alumina. The amount of FeS coating was found to significantly vary with pH, with the highest amount occurring at pH ~6.9 for both minerals. At this pH, the surfaces of mackinawite and alumina (or activated alumina) were oppositely charged, with the resultant electrostatic attraction making the coating highly effective. At this pH, the coating amounts by alumina and activated alumina were 0.038 and 0.114 $mmol{\cdot}FeS/g$, respectively. Under anoxic conditions, arsenite sorption experiments were conducted with uncoated alumina, uncoated activated alumina, and both minerals coated with FeS at the optimal pH for comparison of their reactivity. Uncoated activated alumina showed the higher arsenite removal compared to uncoated alumina. Notably, the arsenite sorption capacity of activated alumina was little changed by the coating with FeS. This might be attributed to the abundance of highly reactive hydroxyl functional groups (${\equiv}$AlOH) on the surface of activated alumina, making the arsenite sorption by the coated FeS unnoticeable. In contrast, the arsenite sorption capacity of alumina was found to increase substantially by the FeS coating. This was due to the consumption of the surface hydroxyl functional groups on the alumina surface and the subsequent occurrence of As(III) sorption by the coated FeS. Alumina, on the surface area basis, has about 8 times higher FeS coating amount and higher As(III) sorption capacity than silica. This study indicates that alumina is a better candidate than silica for the coating of nanocrystalline mackinawite.

• Korean Journal of Food Science and Technology
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• v.30 no.3
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• pp.709-716
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• 1998

Three kinds of anti-complementary system and macrophage activating polysaccharides, AB-20-Ia, AB-20-IIa-2a and AB-20-IVa-2 were isolated from the fruit body of Agaricus bisporus and their structures were characterized. The proteoglycan, AB-20-IVa-2 showing the most potent anti-complementary and macrophage activity was composed of glucose, galactose, mannose, xylose, fucose and arabinose in a molar ratio of 3.48:1.83:1.00:0.79:0.74:0.11 and its main component amino acids were phenylalanine (34.72%) and valine (27.84%). The neutral polysaccharides, AB-20-Ia and AB-20-IIa-2a showing lower activity than AB-20-IVa-2, consisted of xylose, glucose, mannose, fucose and arabinose in molar ratios of <0.05:<0.05:2.07:1.00:2.72 and 2.16:1.58:1.00:0.20:0.14, respectively. The molecular weights of AB-20-Ia, AB-20-IIa-2a and AB-20-IVa-2 were 840,000, 750,000 and 650,000 respectively. In the $^1H-\;and\;^{13}C-NMR$ spectra of AB-20-Ia and AB-20-IIa-2a, AB-20-Ia showed only ${\beta}-configuration\;(^1H:\;4.8\;ppm,\;^{13}C:\;107.0\;ppm)$ in the anomerization of the glycosidic linkages, while AB-20-IIa-2a had both ${\alpha}-anomer\;(^1H:\;5.4\;ppm,\;^{13}C:\;102.0\;ppm)\;and\;{\beta}-anomer$. Especially, AB-20-Ia and AB-20-IIa-2a showed acetyl signals $(^1H:\;2.5\;ppm,\;^{13}C:\;21.0\;ppm)$. In the methylation analysis of the three polysaccharides, high proportion of 1,6-linked glucofuranosyl residues were detected in AB-20-Ia, whereas 1,6-linked glucopyranosyl residues and branches linked at position 4 of those mainly contained in AB-20-IIa-2a. AB-20-IVa-2 consisted mainly of 1,2-linked xylofuranosyl residues and 1,6-linked glucopyranosyl residues and branches linked at position 3 of those.

• Journal of the Korean Chemical Society
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• v.33 no.1
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• pp.55-64
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• 1989

Reduction and equilibrium of vanadium-DTPA (DTPA = diethylenetriaminepentaacetic acid, $H_5A$) complexes at mercury electrodes are studied in 0.5M $NaClO_4$ aqueous solution at 3.2 < pH < 10.5 and 25$^{\circ}$C. At 3.2 < pH < 5.9, the reduction reaction is $V{\cdot}A^{2-}+H^-+e^-=V{\cdot}HA^{2-}$, while at 5.9 < pH < 10.5 it is $V{\cdot}A^{2-}+H^-+e^-=V{\cdot}A^{3-}$. The stability constants of $V{\cdot}HA^{2-}$ and $V{\cdot}A^{3-}$ are found to be $6.46{\times}10^{9}$ and $3.09{\times}10^{14}$, respectively. V(IV)-DTPA undergoes stepwise complexation as $VO^{2+}+H_2A^{3-}=VO{\cdot}HA^{2+}H^{+}$ and $VO{\cdot}HA^{2-}=VO{\cdot}A^{3+}+H$, where acidity constant of $VO{\cdot}HA^{2-}$- is pKa = 7.15. Stability constants of $VO{\cdot}HA^{2-}$ and $VO{\cdot}A^{3-}$ are found to be $1.41{\times}10^{14}$ and $3.80{\times}10^{17}$, respectively. It is detected that $VO^{2+}-DATA$ is reduced irreversibly to $VO^{2-}$ with the transfer coefficient of $\alpha$ = 0.43. At more cathodic overpotential, the reduction is stepwise as V(IV)${\to}$V(III)${\to}$V(II). The first one corresponds to $VO{\cdot}HA^{2-}+e^{-}{\to}VO{\cdot}HA{3+}$ at 3.2 < pH < 7.2 and $VO{\cdot}A^{3-}+e^{-}{\to}VO{\cdot}A^{4-}$ at 7.2 < pH < 10.5. The second is identical to that of V(III). Diffusion coefficients of $VO{\cdot}HA^{2-}$ and $VO{\cdot}A^{3-}$ are found to be $(9.0{\pm}0.3){\times}10^{-6}cm^2/s$ and $(5.9{\pm}0.4){\times}10^{-6}cm^2/ses$, respectively.

• Journal of Korean Society of Environmental Engineers
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• v.31 no.3
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• pp.179-185
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• 2009

In this research, the removal capacity of Cr(VI) by the reused powdered wastes (RPW) containing aluminium oxides was studied. As a pre-treatment process for the preparation of calcined wastes, calcination was conducted at $550^{\circ}C$ to remove organic fraction in the raw wastes. In order to study the adsorption trend of Cr(VI) ions from aqueous solutions, the pH-edge adsorption, adsorption kinetic and adsorption isotherm were investigated using a batch reactor in the presence of four different background electrolytes($NO_3\;^-,\;CO_3\;^{2-},\;SO_4\;^{2-},\;PO_4\;^{3-}$). Cr(VI) adsorption was greatly reduced in the presence of $SO_4\;^{2-}$ and $PO_4\;^{3-}$ over the entire pH range. Meanwhile the inhibition effect by $NO_3\;^-$ and $CO_3\;^{2-}$ was relatively lower than that by $SO_4\;^{2-}$ and $PO_4\;^{3-}$. Cr(VI) adsorption was maximum around pH 4.5 in the presence of $NO_3\;^-$ and $CO_3\;^{2-}$. As the concentration of background electrolytes increased, Cr(VI) adsorption decreased. This result mightly suggests that adsorption between the surface of RPW and Cr(VI) occurs through outer-sphere complex. Cr(VI) adsorption onto the RPW was well described by second-order kinetics. From the Langmuir isotherm at initial pH 3, the maximum adsorbed amount of Cr(VI) onto the RPW was 11.1, 10, 3.3, 5 mg/g in the presence of $NO_3\;^-,\;CO_3\;^{2-},\;SO_4\;^{2-}$, and $PO_4\;^{3-}$, respectively.

• Journal of the Mineralogical Society of Korea
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• v.4 no.1
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• pp.22-31
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• 1991

Three crystal structures of dehydrated $Ag^+$-and $Ca^{2+}$- exchanged zeolite $A(Ag_4Ca_4-A,\;Ag_^Ca_3-A,\;and\;Ag_8Ca_2-A)$ treated at 250${\circ}C$ with 0.1 Torr of Rb vapor have been determined by single-crystal x-ray diffraction techniques in the cubic space group Pm3m at 21(1)${\circ}C$ (a=12,271(1)${\AA}$, 12.255(1)${\AA}$, and 12.339(1)${\AA}$, respectively). Their structures were refined to the final error indices. R(weighted) of 0.072 with 130 reflections, 0.050 with 110 reflections, and 0.083 with 86 reflections, respectively, for which $I>3{\rho}(I)$. In each structure, Rb species are found at three different crystallographic sites:3$Rb^+$+ions per unit cell are located at 8-ring centers, ca. 5.6 to 6.4 $Rb^+$ ions are found opposite 6-rings on threefold axes in the large cavity, and ca. 2.5 to 3.0 $Rb^+$ ions are found on threefold axes in the sodalite unit. Also, Ag species are found at two different crystallographic stites: ca. 0.7 to 2.1 $Ag^+$ lie opposite 4-rings and ca. 2.2 to 4.8 Ag atoms are located near the center of the large cavity. In these structures, the numbers of Ag atoms per unit cell are 2.2, 2.4, and 4.8, respectively, and these may form hexasilver clusters at the centers of the large cavities. The $Rb^+$ ions, by blocking 8-rings, may have prevented silver from migrating out of the structure. Each hexasilver cluster is stabilized by coordination to up to 13 $Rb^+$ions. An excess absorption of about 0.8 Rb atom per unit cell indicates that the presence of a triangular symmetric $(Rb_3)2^{+}$ cation in sodalite cavity. At least one large-cavity six-ring $Rb^+$ ion must necessarily approach this cluster and may be viewed as a member of it to give $(Rb)_4^{3+}$, $(Rb)_5^{4+}$ or $(Rb)_6^{5+}$.

• Investigative Magnetic Resonance Imaging
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• v.8 no.1
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• pp.32-41
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• 2004

Purpose : To measure the NMR relaxation properties of MnPC, to observe the characteristics of liver enhancement patterns on MR images in experimentally implanted rabbit VX2 tumor model, and to estimate the possibility of tissue specific contrast agent for MnPC in comparison with the hepatobiliary agent. Materials and Methods : Phthalocyanine (PC) was chelated with paramagnetic ions, manganese (Mn). 2.01 g (5.2 mmol) of phthalocyanine was mixed with 0.37 g (1.4 nlmol) of Mn chloride at $310^{\circ}C$ for 36 hours and then purified by chromatography ($CHCl_3:\;CH_3OH=98:2$, volume ratio) to obtain 1.04 g $(46\%)$ of MnPC (molecular weight = 2000 daltons). The T1/T2 relaxivity (R1/R2) for MnPC were determined at a 1.5 T (64 MHz) MR spectrometer. VX2 tumor model was experimentally implanted in the liver parenchyma of rabbits. All MR studies were performed on 1.5 T. The human extremity radio frequency coil of a bird cage type was employed. MR images were acquired at 17 to 24 days after VX2 carcinoma implantation.4 mmol/kg MnPC and 0.01 mmol/kg Mn-DPDP were injected via the ear vein of rabbits. T1-weighted images were obtained with spin-echo (TR/TE=516/14 msec) and fast multiplanar spoiled gradient recalled (TR/TE : 80/4 msec, $60^{\circ}$ flip angle) pulse sequence. Fast spin-echo (TR/TE=1200/85 msec) was used to obtain the T2-weighted images. Results : The value of T1/T2 relaxivity (R1/R2) of MnPC was $7.28\;mM^{-1}S^{-1}$ and $55.56\;mM^{-1}S^{-1}$ respectively at 1.5 T (64 MHz). Because the T2 relaxivity of MnPC that bonded strongly, covalently manganese with phthalocyanine was very high, the signal intensity of liver parenchyma was decreased on postcontrast T2-weighted images and we could easily distinguish the VX2 carcinoma within the liver parenchyma. When MnPC was administrated intravenously, the tumor margin delineation was more remarkable than Mn-DPDP-enhanced images. The enhancement of liver parenchyma with MnPC persisted at relatively high levels over at least one hour after injection of the contrast agents. Conclusion : The hepatic uptake and biliary excretion of MnPC, which are similar to Mn-DPDP, suggest that this agent is a new liver-specific agent. Also, MnPC seems to be used as a dual contrast agent (T1 and T2) with high T2 relaxivity. However, it is warranted that MnPC needs further investigation as a potential contrast agent for MR imaging of the liver. That is, further characterizations of MnPC are needed in vivo and in vitro before clinical trials. The diagnostic potential of MnPC will also have to be examined more in the animal models of additional types.