• Bulletin of the Korean Chemical Society
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• v.27 no.9
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• pp.1310-1314
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• 2006

Sulfur-substituted $LiMn_{0.9}Cr_{0.1}O_{2-x}S_x$ $(0\;\leq\;x\;\leq\;0.1)$ layered oxides have been prepared by solid state reaction under inert atmosphere. From powder X-ray diffraction analyses, all the present lithium manganates were found to be crystallized with monoclinic-layered structure. Electrochemical measurements clearly demonstrated that, in comparison with the pristine $LiMn_{0.9}Cr_{0.1}O_2$, the sulfur-substituted derivatives exhibit smaller discharge capacities for the entire cycle range but the recovery of discharge capacity after the initial several cycles becomes faster upon sulfur substitution. The effect of the sulfur substitution on the chemical bonding nature of $LiMn_{0.9}Cr_{0.1}O_{2-x}S_x$has been investigated using X-ray absorption spectroscopic (XAS) analyses at Mn and Cr K-edges. According to Mn K-edge XAS results, the trivalent oxidation state of manganese ion remains unchanged before and after the substitution whereas the local structure around manganese ions becomes more distorted with increasing the substitution rate of sulfur. On the other hand, the replacement of oxygen with sulfur has negligible influence on the local atomic arrangement around chromium ions, which is surely due to the high octahedral stabilization energy of $Cr^{+III} $ ions. Based on the present experimental findings, we have suggested that the decrease of discharge capacity upon sulfur substitution is ascribable to the enhanced structural distortion of $MnO_6$ octahedra and/or to the formation of covalent Li-S bonds, and the accompanying improvement of cyclability would be related to the depression of Mn migration and/or to the pillaring effect of larger sulfur anion.

• Bulletin of the Korean Chemical Society
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• v.34 no.2
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• pp.415-420
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• 2013

Effect of chemical substitution at the para-position of the thiophenoxyl radical has been theoretically investigated in terms of energetics, structures, charge densities and orbital shapes for the ground and first electronically excited states. It is found that the adiabatic energy gap increases when $CH_3$ or F is substituted at the para-position. This change is attributed to the stabilization of the ground state of thiophenoxyl radical through the electron-donating effect of F or $CH_3$ group as the charge or spin of the singly-occupied molecular orbital is delocalized over the entire molecule especially in the ground state whereas in the excited state it is rather localized on sulfur and little affected by chemical substitutions. Quantitative comparison of predictions based on four different quantum-mechanical calculation methods is presented.

• Bulletin of the Korean Chemical Society
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• v.11 no.1
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• pp.65-69
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• 1990

The nucleophilic substitution reactions of naphthalene-1,5-disulfonyl chloride and 4-fluorosulfonylbenzenesulfonyl chloride with p-substituted anilines and methyl substituted pyridines in methanol-acetonitrile mixtures and hydrolyses of those disulfonyl halides have been studied by means of conductometric and polarographic methods. A large difference in the selective parameter, ${\rho}_N$ between mono-sulfonyl chloride and disulfonyl halide can be taken as an evidence that the second $SO_2Cl$ grolup of naphthalene-1,5-disulfonyl chloride also takes part in the reaction in contrast to sulfonyl fluoride in 4-fluorosulfonylbenzenesulfonyl chloride, which only acts as a substituent in the nucleophilic substitution reaction.

• Current Photovoltaic Research
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• v.3 no.1
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• pp.27-31
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• 2015

It is known that sulfide at the $Cu(In,Ga)Se_2$ ($CIGSe_2$) surface plays a positive role in $CIGSe_2$ solar cells. We investigated the substitution of S with Se on the $CIGSe_2$ surface in S atmosphere. We observed that the sulfur content in the $CIGSe_2$ films changed according to sulfurization temperature and Cu/(In+Ga) ratio. The sulfur content in the $CIGSe_2$ films increased with increasing the annealing temperature and Cu/(In+Ga) ratio. Also Cu migration toward the surface increased at higher temperature. Since high Cu concentration at the $CIGSe_2$ surface is detrimental role, it is necessary to reduce the S annealing temperature as low as $200^{\circ}C$. The cell performance was improved at $200^{\circ}C$ sulfurization.

• Bulletin of the Korean Chemical Society
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• v.15 no.10
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• pp.860-864
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• 1994

2nd-order rate constants have been measured spectrophotometrically for the reactions of 4-nitrophenyl benzoate (1), S-4-nitrophenyl thiobenzoate (2) and 4-nitrophenyl thionbenzoate (3) with alkoxides, aryloxides and thioaryloxides in absolute ethanol at 25.0 ${\pm}0.1$${\circ}C$. The substitution of O by polarizable S in the leaving group has little affected the reactivity of 2 toward the charge localized species (eg. $EtO^-$ and $CF_3CH_2O^-$), while the effect of the similar replacement in the carbonyl group has led to a decrease in reactivity by a factor of 10. However, the reactivity of these esters toward charge delocalized aryloxides has been found to be in the order $1<3{\le}2$. The effect of replaced sulfur atom on reactivity becomes more significant for the reaction with polarizable thioaryloxides, i.e. the reactivity increases in the order $1<2{\ll}3$. The difference in reactivity for the present system is attributed to a polarizability effect.

• Bulletin of the Korean Chemical Society
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• v.23 no.9
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• pp.1257-1262
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• 2002

$[(C_2B_9H_{11})Mo(CO)_3]_2PPN_2$ $(2{\cdot}PPN_2)$, a new precursor for the oxidative decarbonylation reaction, was synthesized in high yield by the one-electron oxidation reaction of $[(C_2B_9H_{11})Mo(CO)_3]PPN_2$. $2{\cdot}PPN_2$ was structurally characterized, showing a dimeric nature with long (3.321 ${\AA}$) Mo-Mo bonding. Reaction of $2{\cdot}PPN_2$ with sulfur gave the completely decarbonylated product $[(C_2B_9H_{11})Mo({\mu}-S)(S)]_2PPN_2$ ($3{\cdot}PPN_2$). The ligand substitution of the terminal sulfur ligands in $3{\cdot}PPN_2$ to oxygen ligands was carried out with the use of PhIO to give $[(C_2B_9H_{11})Mo({\mu}-S)(O)]_2PPN_2$ ($4{\cdot}PPN_2$). The structures of $3{\cdot}PPN_2$ and $4{\cdot}PPN_2$ were also studied.

• Journal of Electrochemical Science and Technology
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• v.9 no.2
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• pp.133-140
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• 2018

$Sr_{0.92}Y_{0.08}Ti_{0.5}Fe_{0.5}O_{3-{\delta}}$ (SYTF0.5) is investigated as an alternative anode in $H_2$ fuels containing $H_2S$ (0-200 ppm). Although additional ionic conductivity is introduced by aliovalent substitution of $Ti^{4+}$ by $Fe^{3+}$ in the B-site, the SYTF0.5 has lower electrical conductivity than that of the $Sr_{0.92}Y_{0.08}TiO_{3-{\delta}}$. Due to the mixed ionic and electronic conductive (MIEC) property exhibited in the SYTF0.5 anode, the electrochemical performance of the SYTF0.5 anode is improved, as well as the sulfur tolerance. The maximum power densities in $H_2$ at $900^{\circ}C$ for the SYT anode and the SYTF0.5 anode were 56.9 and $98.6mW/cm^2$, respectively. The maximum power density in the SYTF0.5 anode at 200 ppm of $H_2S$ concentration decreased by only 12.9% (86.3 to $75.2mW/cm^2$).

• Archives of Pharmacal Research
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• v.17 no.3
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• pp.170-174
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• 1994

We have synthesized various 6-substituted 2-oxo-purine nucleosides from key intemediate, 6-[(4-methylphenylthio)-2-oxo-9(2, 3, 5tri-o-acetyl-$\beta$-D-ribofuanoslyl)]-2, 3- dihydropurine in relatively high yields by one step nucleophilic substitution. Various isoguanosine, xanthosine analogs and other 2-oxo-purine nucleosides containing nitrogen, sulfur and oxygen at C-6 of purine base were easily obtained by this method. The structures of the products were established on the basis of their spectral data studies. And cytotoxicity of resulting synthetic 6-substituted-2-oxo-purine nucleosides against some tumor cell-lines was examined. $Ed_{50}$ values of these synthetic compounds were above $100\;{\mu}g/ml$ except isoguanosine, $N^6$-methyl isoguanosine and thioxanthosine analogs.

• Journal of the Korea institute for structural maintenance and inspection
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• v.18 no.1
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• pp.119-127
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• 2014

The application of sulfur polymer emulsion (SPE) as an acrylate substitute for semi-rigid pavement grout was evaluated, and the performance improvement by employing PVA fibers were also evaluated. The result indicated that the filling ratio of semi-rigid pavement material decreased as the fiber content increased, but it was measured to be 92~94% in every mixing condition, which satisfies the target performance, 90%. The maximum Marshall stability value of semi-rigid pavement material was measured to be 25.4 kN, which is about 4.7 times higher than the Korean Standard required for semi-rigid pavement material, 5.0 kN. The dynamic stability evaluation of semi-rigid pavement material indicated that the resistance to deformation from the wheel tracking test was improved by an SPE substitution, and in every mixing condition, the deformation converged to a constant value after 45 minutes with the same dynamic stability of 31,500 times/mm. The strain at the flexural failure was about 0.53%, which shows superior rigidity to asphalt pavements. The examination of abrasion resistance and impact resistance showed that the loss ratio was 9.8~6.0% in every mixing condition, which indicates a good abrasion resistance. Also, when fiber content ratio was 0.3%, the impact resistance was 2.82 times higher compared to plain (i.e., when fibers were not added). In the limited range of this study, an SPE substitution ratio of 30% was found to be an optimal level considering the mechanical and durability performance. In addition, it is thought that semi-rigid pavement material with superior performance could be manufactured if fiber content ratio up to 0.3% is applied depending on the purpose of use.

• The Korean Journal of Food And Nutrition
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• v.31 no.1
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• pp.62-69
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• 2018

Pumpkin (Cucurbita moschata Duch.) seed is rich in protein and sulfur-containing amino acids. Tofu is a protein gel made from soybean, which is rich in lysine but lacking in sulfur-containing amino acids. This study was conducted to investigate the use of pumpkin seeds in tofu manufacture and to determine its quality and texture characteristics. Soybean was substituted with pumpkin seed to obtain pumpkin seed tofu at the following ratios: 10%, 30%, 50%, and 70% (P10, P30, P50 and P70). Tofu manufactured only with soybean was used as a control (Con). The higher rate of pumpkin seed substitution significantly decreased the moisture content and yield rate (p<0.05). In contrast, pH value and turbidity were significantly increased with the increase in the amount of pumpkin seed (p<0.05). The L-value (81.74~79.04), a-value (-0.19~-3.89) and b-value (12.40~9.84) of samples significantly decreased with the amount of pumpkin seed (p<0.05). No significant difference in syneresis was found among the samples (p<0.05). The hardness tended to decrease with the increase in the amount of pumpkin seed. The microstructure analysis revealed that the pore size of pumpkin seed tofu was smaller than that of Con. These results suggest that the pumpkin seed protein is a useful ingredient in the manufacture of tofu. Increasing the pumpkin seed substitution levels improves the texture of tofu.