• 대한화학회지
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• 제16권6호
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• pp.334-340
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• 1972

메틸 클로로 티올, 메틸클로로 티오노 및 메틸 클로로 디티오 훠메이트에 대하여 CNDO/2 계산을 실시하였다. 결과로 이들 화합물은 trans형이 안정한 것임을 밝혔다. 또 유황 원자는 산소원자에 비하여 그 고립쌍 전자들을 ${\pi}$-결합 형성에 사용하려는 경향이 적고 티올 훠메이트의 경우는 메틸기의 hyperconjugation에 의하여 안정화됨을 알았다. 가용매 반응성의 순서는 양이온의 안정도와 일치하며 이것은 알려진 $S_N1$형 반응 메카니즘과 부합된다.

• Bulletin of the Korean Chemical Society
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• 제31권12호
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• pp.3583-3587
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• 2010

Furoxanthiols PFT and BPFT possessing thiomethyl or thiobenzyl groups in the furoxan ring were designed and synthesized as potential light-sensitive alkyne precursors on a gold surface. The synthesis of thiofuroxans PFT and BPFT was performed from the corresponding halofuroxans 1b and 2c, respectively, by the substitution with potassium thioacetate in ethyl acetate/ethanol or DMF, followed by basic hydrolysis as the key reactions. Electron-beammediated fragmentation of furoxans 1c and 2d in a mass spectrometer afforded the corresponding aryl alkyne fragments, with the evolution of NO in high preference. In the cases of thiofuroxans PFT and BPFT, carbon-sulfur bond cleavage was observed as a representative fragmentation, producing M-SH and M-SAc peaks, which competed with the release of NO. In the fragmentation of mono-aryl furoxan 1c, the release of molecule of NO was predominately observed to produce an M-NO fragment as a base peak by the formation of trimembered thiiranium or azirine intermediate.

• 한국건축시공학회지
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• 제17권4호
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• pp.313-320
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• 2017

화력발전소의 전력 생산을 위한 연료의 연소 시 발생한 황산화물의 제거과정에서 생산되는 배연탈황석고의 경우 현재까지는 적극적인 재활용이 되지 않고 있다. 본 연구는 화력발전소의 배연탈황공정인 건식, 습식공법을 통해 발생된 배연탈황석고의 슬래그 자극재로써의 활용가능성을 연구하기 위하여 일정량의 건식 및 습식 배연탈황석고를 고로슬래그 미분말에 치환하고, 슬래그 페이스트를 제작한 후, 그에 따른 수화반응 특성과 압축강도 특성을 분석해서 슬래그 자극재나 천연석고의 대체재로서 역할을 할 수 있는지 검토하고자 하였다. 본 연구의 결과에 따르면, 건식 배연탈황석고의 경우 별도의 알칼리 자극이 없어도 슬래그를 충분히 자극하는 것으로 보이며, 습식배연탈황석고의 경우 일정수준 이상의 알칼리 자극이 주어져야만 충분한 슬래그 자극효과를 볼 수 있는 것으로 나타났다. 또한 건식과 습식 배연탈황석고를 슬래그 페이스트에 적정량 치환하면 슬래그 페이스트의 압축강도 개선효과를 얻을 수 있는 것으로 나타났다. 추후 추가적인 연구를 통해 치환율에 따른 강도증진 성상을 정량적으로 규명하면 배연탈황석고의 효율적 경제적 재활용이 가능하게 될 것으로 사료된다.

• Molecules and Cells
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• 제39권8호
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• pp.594-602
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• 2016

Alkyl hydroperoxide reductase subunit C from Pseudomonas aeruginosa PAO1 (PaAhpC) is a member of the 2-Cys peroxiredoxin family. Here, we examined the peroxidase and molecular chaperone functions of PaAhpC using a site-directed mutagenesis approach by substitution of Ser and Thr residues with Cys at positions 78 and 105 located between two catalytic cysteines. Substitution of Ser with Cys at position 78 enhanced the chaperone activity of the mutant (S78C-PaAhpC) by approximately 9-fold compared with that of the wild-type protein (WT-PaAhpC). This increased activity may have been associated with the proportionate increase in the high-molecular-weight (HMW) fraction and enhanced hydrophobicity of S78C-PaAhpC. Homology modeling revealed that mutation of $Ser^{78}$ to $Cys^{78}$ resulted in a more compact decameric structure than that observed in WT-PaAhpC and decreased the atomic distance between the two neighboring sulfur atoms of $Cys^{78}$ in the dimer-dimer interface of S78C-PaAhpC, which could be responsible for the enhanced hydrophobic interaction at the dimer-dimer interface. Furthermore, complementation assays showed that S78C-PaAhpC exhibited greatly improved the heat tolerance, resulting in enhanced1 survival under thermal stress. Thus, addition of Cys at position 78 in PaAhpC modulated the functional shifting of this protein from a peroxidase to a chaperone.

• Bulletin of the Korean Chemical Society
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• 제32권7호
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• pp.2423-2427
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• 2011

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for nucleophilic substitution reactions of 3,4-dinitrophenyl diphenylphosphinothioate 9 with alkali metal ethoxides (EtOM, M = Li, Na, K) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOM] is linear for the reaction of 9 with EtOK. However, the plot curves downwardly for those with EtOLi and EtONa while it curves upwardly for the one with EtOK in the presence of 18-crown-6-ether (18C6). Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constant for the reaction with dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the reactivity increases in the order $k_{EtOLi}$ < $k_{EtONa}$ < $k_{EtO^-}$ ${\approx}$ $k_{EtOK}$ < $k_{EtOK/18C6}$, indicating that the reaction is inhibited by $Li^+$ and $Na^+$ ions but is catalyzed by 18C6-crowned $K^+$ ion. The reactivity order found for the reactions of 9 contrasts to that reported previously for the corresponding reactions of 1, i.e., $k_{EtOLi}$ > $k_{EtONa}$ > $E_{EtOK}$ > $k_{EtO^-}$ ${\approx}$ $k_{EtOK/18C6}$, indicating that the effect of changing the electrophilic center from P=O to P=S on the role of $M^+$ ions is significant. A four-membered cyclic transition-state has been proposed to account for the $M^+$ ion effects found in this study, e.g., the polarizable sulfur atom of the P=S bond in 9 interacts strongly with the soft 18C6-crowned $K^+$ ion while it interacts weakly with the hard $Li^+$ and $Na^+$ ions.

• BMB Reports
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• 제29권5호
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• pp.429-435
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• 1996

To investigate the structure-antagonistic relationship of the cyclohexapeptide L-659,877, a selective NK-2 tachykinin receptor antagonist, seven analogues were chemically synthesized by a solid phase method. The agonistic and antagonistic activities of the analogues were evaluated by contraction assay using the smooth muscle of guinea pig trachea (GPT) containing the NK-2 receptor. It was shown that the aromatic ring of Phe at position 3 and the sulfur group of Met at position 6 in L-659,877 were essential for binding to the NK-2 receptor. Decrease in antagonistic activity of L-659,877 caused by substituting Leu for Nle at position 5 indicates that the ${\gamma}$ methyl group and side chain length of Leu plays an important role in its antagonistic action. Although the activity was slightly lower than L-659,877, cyclo $[{\beta}Ala^{8}]NKA(4-10)$ (analogue 1) showed potential antagonistic activity for the NK-2 receptor. It was confirmed that the expansion of the ring in L-659,877 by substitution of ${\beta}Ala$ for Gly at position 4 stabilized its conformation monitored by CD spectra. The results suggest that analogue 1 can be used as a new leader compound to design a more powerful, selective, and stable NK-2 receptor antagonist.

• 자원환경지질
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• 제25권3호
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• pp.275-282
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• 1992

Mineral chemistry and stable isotope compositions of sericites from the Sangdong mine in the Kimhae area, Kyungsangnamdo, were studied. The Sangdong sericite deposit occurs in rhyolitic tuff of late Cretaceous age and considers to have been fonned by the hydrothennal alteration. The sericites are classified as $2M_1$ polytype and are characterized by less celadonite substitution indicating muscovite-phengite series. Their compositions are very close to that of the ideal muscovite but net layer charge ranges 1.71~1.91 which is less than 2 per formula unit of ideal muscovite. Predominant interlayer cation is K and K/(K+Na) ratio ranges 0.91 and 0.93. ${\delta}^{18}O$ values of sericites and quartz separated from the ore range 7.70~9.07 and 8.20~10.87‰, respectively. The formation temperature of sericite can be estimated as $315{\sim}340^{\circ}C$( based on ${\delta}^{18}O$ value of sericite and ${\delta}D$ value of of Cretaceous meteoric water. Their formation temperature discrepancy between coexisting sericite and quartz indicates that they are in isotopically inequilibrium. Two types of quartz, coarse grained phenocrysts and micrcrystalline aggregates are observed and the former must have been formed during volcanic eruption and remained isotopically unexchanged during hydrothermal alteration period. ${\delta}^{14}S$ values of pyrites range 1.9~4.5‰ which is within a range of volcanogenic sulfur, indicating magmatic source.

• 분석과학
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• 제5권2호
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• pp.203-211
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• 1992

Ni-36.5at.%Al 합금에서 결정립계에서의 scavenging 원소로 알려진 V를 첨가하여 이 합금의 파괴거동 및 마르텐사이트 미세조직에 미치는 V의 영향에 대해 조사하였다. 시편의 파단면은 주사전자현미경으로 관찰하였고 EDX spectrometer를 사용하여 파단면의 조성을 분석하였으며 투과전자현미경으로 마르텐사이트 내부조직의 변화에 대해 조사하였다. V의 첨가로 입계파괴에서 입내파괴로 파괴 모드의 변화를 나타내었으며 EDX spectrometer로 분석한 결과 입내에 비해 입계에 Al의 함량이 상대적으로 증가되는 양상을 보여 주었다. Ni-36.5at.%Al 합금의 경우 마르텐사이트 플레이트는 내부쌍정으로 이루어져 있으나 V의 첨가에 따라 twinned 마르텐사이트 조직은 사라지며 stacking fault와 고밀도의 전위를 가진 modulated 조직이 점차 지배적으로 형성되는 것이 관찰되었다. Stacking fault를 분석한 결과 Al과 V의 치환에 따른 extrinsic fault였으며 high-energy 상태인 이 stacking fault가 있는 부위에 유해 원소인 S가 편석됨으로써 결정립계에서의 파괴를 줄일 수 있었다.

• 대한화학회지
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• 제40권5호
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• pp.357-364
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• 1996

아세톡시 1,3-옥사티올란 1의 이성체들의 입체화학을 두 가지 방법에 의해 결정하였다. 첫째, 산촉매하에서 디히드로옥사티인 2로의 전환되는 반응속도 차이에 의해 알파이성체 7과 베타이성체 9의 구조를 결정하였다. 이탈기인 아세톡시기가 황원자와 트랜스 위치에 있을 때 1,3-옥사티올란 고리에 대한 입체장애가 적은 이성체가 알파이성체 7이며 반응속도가 느린 이성체가 베타이성체 9이었다. 둘째, 술폭시드의 각각의 diastereomer들의 중수소 치환반응에서, methine 수소가 중수소로 치환된 화합물은 시스이성체 15, 17, 그리고 메틸기의 수소가 중수소로 치환된 화합물은 트랜스이성체 16, 18이었다. Methine 또는 메틸기의 수소의 중수소로의 치환은 [2,3] 시그마트로픽 전위에 의한 입체특이적 개환 및 폐환의 결과였다.

• Journal of Industrial and Engineering Chemistry
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• 제68권
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• pp.187-195
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• 2018

$Sr_{0.92}Y_{0.08}Ti_{1-x}Ni_xO_{3-{\delta}}$ (SYTN) was investigated in the presence of $H_2S$ containing fuels to assess the feasibility of employing oxide materials as alternative anodes. Aliovalent substitution of $Ni^{2+}$ into $Ti^{4+}$ increased the ionic conductivity of perovskite, leading to improved electrochemical performance of the SYTN anode. The maximum power densities were 32.4 and $45.3mW/cm^2$ in $H_2$ at $900^{\circ}C$ for the SYT anode and the SYTN anode, respectively. However, the maximum power densities in 300 ppm of $H_2S$ decreased by 7% and by 46% in the SYT and the SYTN anodes, respectively. To enhance the sulfur tolerance and to improve the electrochemical properties, the surface of SYTN anode was modified with samarium doped ceria (SDC) using the sol-gel coating method. For the SDC-modified SYTN anode, the cell performance was mostly recovered in the pure $H_2$ condition after 500-ppm $H_2S$ exposure in contrast to the irreversible cell performance degradation exhibited in the unmodified SYTN anode.