• Bulletin of the Korean Chemical Society
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• 제27권9호
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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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• 제34권2호
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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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• 제11권1호
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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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• 제3권1호
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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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• 제15권10호
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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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• 제23권9호
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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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• 제9권2호
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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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• 제17권3호
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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.

• 한국구조물진단유지관리공학회 논문집
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• 제18권1호
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• pp.119-127
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• 2014

본 연구에서는 유황폴리머에멀젼 (SPE)을 반강성 포장용 주입재의 아크릴레이트 대체재로서 활용가능성과 성능향상재료 (PVA섬유)에 대한 역학적 성능과 내구성능을 평가하였다. 평가결과, 반강성 포장재의 충전률은 섬유의 혼입률이 증가함에 따라 충전률이 저하되었지만, 모든 배합조건에서 평균 92~94%로 측정되어 목표 성능인 90%를 만족하였다. 반강성 포장재의 마샬안정도 값은 최대 25.4kN으로 측정되어 반강성 포장재의 국내 기준인 5.0 kN 보다 약 4.7배 우수한 것으로 나타났다. 반강성 포장재의 동적안정도 평가결과, 휠 트래킹시험에 따른 변형저항성은 SPE를 대체한 배합조건이 보다 우수하였고, 모든 배합조건에서 45분 이후에는 변형량이 일정한 값에 수렴되어 동적안정도가 31,500회/mm로 동일한 결과를 나타내었다. 파단변형률은 최대 0.53% 정도로 나타나 아스팔트 포장재보다 우수한 강성으로 나타났다. 마모저항성 및 충격저항성 검토결과 모든 배합조건에서 손실률이 9.8~6.0%로 나타나 우수한 내마모성을 나타내었으며, 섬유를 0.3% 혼입한 경우 혼입하지 않은 Plain에 비하여 2.82배의 내충격성 향상을 나타내었다. 역학적성능 및 내구성능 등을 모두 고려하여 볼 때, 이 연구 범위에서는 SPE 대체율 30%가 적정 수준이고, 혼입률 0.3% 범위에서 PVA 섬유를 적용하면 우수한 인성을 갖는 반강성 포장재 제조가 가능 할 것으로 판단된다.

• 한국식품영양학회지
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• 제31권1호
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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.