• Journal of the Korean Ceramic Society
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• v.34 no.10
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• pp.1083-1091
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• 1997

As one of the chemical powder fabrication methods, the powder preparation method by using oxalate has the following advantages; (1) easy to control the chemical stoichiometry, (2) easy to fabricate homogeneous and fine particles, and (3) easy to be thermaly decomposed at low temperature. In the present study, the initial morphology and size distribution of the powder were controlled and the homogeniaty was improved. By carefully controlling the pH with NH4OH, the Bi(Pb)-Sr-Ca-Cu-O superconducting powders were prepared and investigated for their properties. The microstructures and the superconducting properties of the pelletized samples were investigated. Also, the microstructures and electrical properties of the samples prepared by tape casting method were investigated. The fabricated powders were spherical with less than 400 nm, but most of them were agglomerated to be 1~3 ${\mu}{\textrm}{m}$ in size. The critical temperature of the pelletized sample annealed at 84$0^{\circ}C$ for 72 hours in air was 110K. And the critical currents of annealed samples in air prepared by tape casting process for 24 hours and 72 hours were 0.6 A (Jc=600A/$\textrm{cm}^2$) and 1.9A (Jc=1, 900A/$\textrm{cm}^2$) respectively.

• Journal of the Korean Chemical Society
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• v.30 no.1
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• pp.57-62
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• 1986

Oxidation of $[Mo_3O_4(C_2O_4)_3(H_2O)_3]^{2-}$ with HCr$O_4^-$ yields the molybdenum(Ⅳ) complex, $[Mo_2O_5(C_2O_4)_2(H_2O)_2]^{2-}$. Stoichiometry for the reaction of $[Mo_3O_4(C_2O_4)_3(H_2O)_3]^{2-}$ with HCr$O_4^-$ are expressed as $2Mo_3^{IV} + 4Cr^{VI} {\to} 3Mo_2^{VI} + 4Cr^{III}$. Observed rate constants are dependent on hydrogen ion concentration. The kinetic data are consistent with a mechanism in which three successive single-electron steps convert $Cr^{VI}$to $Cr^{III}$ by way of intermediate $Cr^V$ and $Cr^{IV}$. Detailed mechanisms are presented and discussed.

• Journal of the Korean Chemical Society
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• v.25 no.6
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• pp.383-389
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• 1981

Thianthrene cation radical perchlorate reacts with N-arylsulfonamides such as p-toluenesulfonanilide, benzenesulfonanilide, N-(2-methylphenyl)benzenesulfonamide, and N-phenyl-p-toluenesulfonanilide to give 5-(p-N-p-toluenesulfonamidophenyl)-(1a), 5-(p-N-benzenesulfonamidophenyl)-(1b), 5-(4-N-benzenesulfonamido-3-methylphenyl)-(1c), and 5-(p-N-phenyl-N-p-toluenesulfonamidophenyl thianthrenium perchlorate (1d), respectively. In the meantime, 1d reacts further with thiathrene cation ratical to form diperchlorate(1e). The structure of 1a~1e is very similar to 5-(p-acetamidophenyl) thianthrenium perchlorate which has been obtained from the reaction with acetanilide. However, the discrepancy in the stoichiometry between two reactions indicates that the reaction with sulfonamide appears not to proceed with a single mechanism.

• Bulletin of the Korean Chemical Society
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• v.24 no.9
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• pp.1293-1302
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• 2003

Rate constants at various temperatures and activation parameters are reported for solvolyses of acyl chlorides (RCOCl), with R = Me, Et, i-Pr, t-Bu, cyclopentylmethyl, benzyl, thiophenylmethyl, 2-phenylethyl, diphenylmethyl, and phenylthiomethyl in 100% ethanol, 100% 2,2,2-trifluoroethanol (TFE), 80% v/v ethanol/ water and 97% w/w TFE/water. Additional rate constants for solvolyses with R = Me, t-Bu, and $PhCH_2$ are reported for TFE/water and TFE/ethanol mixtures, and for solvolyses with R = t-Bu, and PhCH2 are reported for 1,1,1,3,3,3-hexafluoropropan-2-ol/water mixtures, as well as selected kinetic solvent isotope effects (MeOH/MeOD and TFE). Taft plots show that electron withdrawing groups (EWG) decrease reactivity significantly in TFE, but increase reactivity slightly in ethanol. Correlation of solvent effects using the extended Grunwald-Winstein (GW) equation shows an increasing sensitivity to solvent nucleophilicity for EWG. The effect of solvent stoichiometry in assumed third order reactions is evaluated for TFE/ethanol mixtures, which do not fit well in GW plots for R = Me, and t-Bu, and it is proposed that one molecule of TFE may have a specific role as electrophile; in contrast, reactions of substrates containing an EWG can be explained by third order reactions in which one molecule of solvent (ethanol or TFE) acts as a nucleophile, and a molecule of ethanol acts as a general base catalyst. Isokinetic relationships are also investigated.

• Bulletin of the Korean Chemical Society
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• v.30 no.5
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• pp.1135-1138
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• 2009

Hollow Sn and Pb nanoparticles have been prepared by a rapid injection of an aqueous solution of $SnCl_2$- poly(vinylpyrrolidone) (PVP, surfactant) and $Pb(OAc)_2${\cdot}$3H_2O-PVP$ into an aqueous solution of sodium borohydride (reducing agent) in simple, one-pot reaction at room temperature under an argon atmosphere, respectively. The two hollow nanoparticles have been fully characterized by TEM, HRTEM, SAED, XRD, and EDX analyses. Upon exposure to air, the black Pb hollow nanoparticles are gradually transformed into a mixture of Pb, litharge (tetragonal PbO), massicot (orthorhombic PbO), and $Pb_5O_8$. The order and speed of mixing of the reactants between the metal precursor-PVP and the reductant solutions and stoichiometry of all the reactants are crucial factors for the formation of the two hollow nanocrystals. The Sn and Pb hollow nanoparticles were produced only when 1:(1.5-2) and 1:3 ratios of the Sn and Pb precursors to $NaBH_4$ were employed with a rapid injection, respectively.

• Bulletin of the Korean Chemical Society
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• v.31 no.6
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• pp.1615-1620
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• 2010

Bis-[dipyrido[3,2-$\alpha$:2',3'-c]phenazine)$_2$(1,10-phenanthroline)$_2Ru_2$]$^{2+}$ complexes (bis-Ru(II) complexes) tethered by linkers of various lengths were synthesized and their binding properties to DNA investigated by normal absorption and linear dichroism spectra, and fluorescence techniques in this study. Upon binding to DNA, the bis-Ru(II) complex with the longest linker (1,3-bis-(4-pyridyl)-propane), exhibited a negative $LD^r$ signal whose intensity was as large as that in the DNA absorption region, followed by a complicate $LD^r$ signal in the metal-to-ligand charge transfer region. The luminescence intensity of this bis-Ru(II) complex was enhanced. The observed $LD^r$ and luminescence results resembled that of the [Ru(1,10-phenanthroline)$_2$ dipyrido[3,2-$\alpha$:2',3'-c]phenazine]$^{2+}$ complex, whose dipyrido[3,2-$\alpha$:2',3'-c]phenazine (dppz) ligand has been known to intercalate between DNA bases. Hence, it is conclusive that both dppz ligands of the bis-Ru(II) complex intercalate. The binding stoichiometry, however, was a single intercalated dppz per ~ 2.3 bases, which violates the "nearest binding site exclusion" model for intercalation. The length between the two Ru(II) complexes may be barely long enough to accommodate one DNA base between the two dppz ligands, but not for two DNA bases. When the linker was shorter (4,4'-bipyridine or 1,2-bis-(4-pyridyl)-ethane), the magnitude of the LD in the dppz absorption region, as well as the luminescence intensity of both bis-Ru(II) complexes, was half that of the bis-Ru(II) complex bearing a long linker. This observation can be elucidated by a model whereby one of the dppz ligands intercalates while the other is exposed to the aqueous environment.

• Journal of the Korean Chemical Society
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• v.53 no.2
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• pp.152-158
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• 2009

Spectrophotometric investigation of the interaction of Cefpodoxime proxetil (CFP) with $Ca^{2+},\;Mg^{2+},\;Mn^{2+},\;Fe^{3+},\;Co^{2+},\;Ni^{2+},\;Cu^{2+}$ and $Zn^{2+}$ in acidic medium showed the formation of 1:1 complex. The absorption spectrum of pure drug exhibits two prominent peaks at 270 and 345 nm. Its spectra scanned at several pH exhibited two isosbestic points (305 and 330 nm) indicating the presence of zwitterionic condition of drug in solution phase. The fluorescence emission spectra of CFP in presence of different concentrations of metal ions showed enhancement in fluorescence intensity which is ascribed to chelating enhancement fluorescence effect (CHEF). The stoichiometry of the complexes was determined by Job’s and Benesi-Hildebrand method. The stability of the complexes follow the order $Ca^{2+}\;<\;Mg^{2+}\;<\;Co^{2+}\;<\;Ni^{2+}\;<\;Zn^{2+}\;<\;Mn^{2+}\;<\;Cu^{2+}\;<\;Fe^{3+}$.

• Journal of the Korean Chemical Society
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• v.19 no.2
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• pp.104-115
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• 1975

The electrochemical reduction of iodine in non-aqueous media have been studied by polarography, chronopotentiometry, cyclic voltammetry and controlled potential coulometry at dropping mercury electrode and platinum, gold and amalgamated platium electrodes. In amphiprotic solvents such as methanol, ethanol, isopropanol and pyridine, iodine were reduced to iodide ions via one step reduction involving 1 electron and in aprotic solvents such as acetonitrile, dimethylformamide and dimethylsulfoxide via two step reduction involving all 3 electrons. The reductions of iodine give well defined polarograms at dropping mercury electrode and irreversible chronopotentiograms at platinum electrode, but less defined irreversible chronopotentiograms at gold and amalgamated platinum electrodes, those are all diffusion controlled. The diffusion coefficients of iodine in various solvents were estimated from the chronopotentiometric data and Sand equation.

• Journal of the Korean Vacuum Society
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• v.7 no.4
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• pp.320-327
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• 1998

The chemical aspects of nitridated surface of sapphire(0001) have been studied by X-ray photoelectron spectroscopy. Nitridated layer was formed by remote plasma enhanced-ultrahigh vacuum deposition at a low temperature range. It was confirmed that this nitridated surface was mainly consists of AIN layer. The relative amounts of nitrogen reacted with AL on the sapphire surface and their surface morphology were investigated with X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) as a function of radio-frequency power, reaction temperature, and reaction time. The amounts of atomic nitrogen activated by plasma which was subsequently incorporated into sapphire were increased with RF power. But the amounts of nitrogen reacted with AI in sapphire was initially increased and then remained constant. However, the relative amounts of AIN were nearly constant with irrespective of nitridation temperature and time. Furthermore, a depth porfile of nitridated layer with XPS showed that the nitridated surface consisted of three layers with different stoichiometry.

• Bulletin of the Korean Chemical Society
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• v.15 no.2
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• pp.132-138
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• 1994

Bis(diethylamino)aluminum hydride was utilized in a systematic study of the approximate rates and stoichiometry of the reaction of excess reagent with 55 selected organic compounds containing representative functional groups under standardized conditions (THF, $0^{\circ}C$, reagent to compound=4 : 1) in order to define the characteristics of the reagent for selective reductions. The reducing action of BEAH was also compared with that of the parent aluminum hydride. The reducing action of the reagent is quite similar to that of aluminum hydride, but the reducing power is much weaker. Aldehydes and ketones were readily reduced in 1-3 h to the corresponding alcohols. However, unexpectedly, a ready involvement of the double bond in cinnamaldehyde was realized to afford hydrocinnamyl alcohol. The introduction of diethylamino group to the parent aluminum hydride appears not to be appreciably influential in stereoselectivity on the reduction of cyclic ketones. Both p-benzoquinone and anthraquinone utilized 2 equiv of hydride readily without evolution of hydrogen, proceeded cleanly to the 1,4-reduction products. Carboxylic acids and acid chlorides underwent reduction to alcohols slowly, whereas cyclic anhydrides utilized only 2 equiv of hydride slowly to the corresponding hydroxylacids. Especially, benzoic acid with a limiting amount of hydride was reduced to benzaldehyde in a yield of 80%. Esters and lactones were also readily reduced to alcohols. Epoxides examined all reacted slowly to give the ring-opened products. Primary and tertiary amides utilized 1 equiv of hydride fast and further hydride utilization was quite slow. The examination for possibility of achieving a partial reduction to aldehydes was also performed. Among them, benzamide and N,N-dimethylbenzamide gave ca, 90% yields of benzaldehyde. Both the nitriles examined were also slowly reduced to the amines. Unexpectedly, both aliphatic and aromatic nitro compounds proved to be relatively reactive to the reagent. On the other hand, azo- and azoxybenzenes were quite inert to BEAH. Cyclohexanone oxime liberated 1 equiv of hydrogen and utilized 1 equiv of hydride for reduction, corresponding to N-hydroxycyclohexylamine. Pyridine ring compounds were also slowly attacked. Disulfides were readily reduced with hydrogen evolution to the thiols, and dimethyl sulfoxide and diphenyl sulfone were also rapidly reduced to the sulfides.