• 한국세라믹학회지
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• 제35권12호
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• pp.1343-1350
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• 1998

A study is made of mechanical properties of unglazed matrix as a funtion of sintering temperature and crack patterns in layer structur pottery consisting of glaze and substrate and in matrix which is sintered at 120$0^{\circ}C$ and 130$0^{\circ}C$ respectively. The mechanical properties of matrix are increased due to density and vitrification to 130$0^{\circ}C$ The interface of glazed bilayer reveals the reactive intermediate layer. Herzian indentation testing is used to investigate the evolution of damage modes as a function of load. In the materials sintered at 120$0^{\circ}C$ quasi-plastic deformation is developed at the matrix and the cone-like cracks initiate at the glazing top surface and additionally upward-extending transverse cracks initiate at the internal in-just initiate at the glazing top surface which pass through the interface with increasing of indentation load. Finally the dominant damage mode shifts from substrate quasi-plasticity to coating fracture with increasing sintering temperature.

• Bulletin of the Korean Chemical Society
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• 제31권6호
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• pp.1621-1627
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• 2010

The investigation of the catalytic activity of supported rhodium(I) complex [Rh(P-S)$(CO)_2$] (P-S; polymer anchored salicylic acid) toward the reductive carbonylation of nitrobenzene in DMF medium has been reported. Use of basic cocatalysts in the reaction medium enhanced the percentage of more useful phenyl carbamates. Spectroscopic studies indicate that the reaction proceeds through a dimer species [Rh(HS)(CO)(C(O)$OCH_3$)(${\mu}-OCH_3)]_2$ and phenyl isocyanate is formed as an intermediate. A plausible reaction mechanism based on the identification of reactive intermediates from the soluble rhodium variety has been proposed for the carbonylation process.

• 한국식품영양과학회지
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• 제26권6호
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• pp.1252-1257
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• 1997

In order to investigate the immunomodulatory mechanism of white ginseng, the effects of total saponin of Ginsenoside Rb$_2$component on the phagocytosis and reactive oxygen intermediate(ROI) production of mouse peritoneal macrophages were studied. Both phagocytosis assay nitrobluetetrazolium reduction test showed 20$\mu\textrm{g}$/ml concentration of total saponin significantly increased the activity of phagocytosis and production of ROI. Also cytokine gene expression of the macrophages was analyzed using reverse transcription polymerase chain reaction. In the RT-PCR assay, 20$\mu\textrm{g}$/ml concentration of either total saponin or Ginsenoside Rb$_2$increased IL-1 and TNF expression of the macrophages.

• Bulletin of the Korean Chemical Society
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• 제35권8호
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• pp.2448-2452
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• 2014

Second-order rate constants ($k_N$) have been measured spectrophotometrically for $S_NAr$ reactions of Y-substituted-phenoxy-2,4-dinitrobenzenes (1a-1g) with hydrazine and glycylglycine in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. Hydrazine is 14.6-23.4 times more reactive than glycylglycine. The magnitude of the ${\alpha}$-effect increases linearly as the substituent Y becomes a stronger electron-withdrawing group (EWG). The Br${\o}$nsted-type plots for the reactions with hydrazine and glycylglycine are linear with ${\beta}_{lg}=-0.21$ and -0.14, respectively, which is typical for reactions reported previously to proceed through a stepwise mechanism with expulsion of the leaving group occurring after rate-determining step (RDS). The Hammett plots correlated with ${\sigma}^{\circ}$ constants result in much better linear correlations than ${\sigma}^-$ constants, indicating that expulsion of the leaving group is not advanced in the transition state (TS). The reaction of 1a-1g with hydrazine has been proposed to proceed through a five-membered cyclic intermediate ($T_{III}$), which is structurally not possible for the reaction with glycylglycine. Stabilization of the intermediate $T_{III}$ through intramolecular H-bonding interaction has been suggested as an origin of the ${\alpha}$-effect exhibited by hydrazine.

• 한국세라믹학회지
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• 제35권1호
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• pp.23-32
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• 1998

전융실리카 분말로 소결하여 만든 sihca preform을 마그네슘이 함유된 용융 알루미늄에 침적시킨후 공기중에서 반응시켜 Al2O3/Al 복합체를 제조하였다. 복합체 제조시 반응온도의 변화에 대해 용융 알루미늄의 침투거동을 조사한 결과 3가지 영역, 즉 저온영역(75$0^{\circ}C$-85$0^{\circ}C$), 중온영역(90$0^{\circ}C$-95$0^{\circ}C$), 고온영역(100$0^{\circ}C$$\leq$)으로 구분되었다. 저온영역에서는 반응온도에 비례해서 침투속도가 증가하였으나, 중간온도 영역은 치환반응에 의해 생성된 알루미나의 상전이에 따른 영향으로 저온영역인 85$0^{\circ}C$에서보다 오히려 침투속도가 감소하였다. 고온영역중 100$0^{\circ}C$이상에서 침투가 일어나지 않는 것은 용융 알루미늄중의 마그네슘이 먼저 실리카와 반응하여 silica preform의 표면에 치밀한 스피넬층을 형성하기 때문으로 판명되었다.

• Bulletin of the Korean Chemical Society
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• 제25권9호
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• pp.1379-1384
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• 2004

Rearrangements of 1,3-oxathiolane sulfoxides 8 and 9 in the presence of base are described from a mechanistic viewpoint of sigmatropic and elimination reactions. In the presence of triethylamine the (Z)-sulfoxide 8 gave the corresponding thiolsulfinate 10 by way of dimerization of the sulfenic acid intermediate 2 at room temperature while the (E)-sulfoxide 9 was recovered even after refluxing in ethyl acetate by the reversal of the [2,3]-sigmatropic rearrangement of the sulfenic acid 4. Triethylamine promoted the developing charge separation in the transition state of the sigmatropic rearrangement of the (Z)-sulfoxide 8 to facilitate the ring opening to the sulfenic acid 2. The reason for more facile ring opening of the (Z)-sulfoxide 8 in comparison with the corresponding (E)-sulfoxide 9 is attributable to the differences in the reactivity of the hydrogen adjacent to the carbonyl group. Triethylamine was not strong base to deprotonate the carbonyl-activated methylene hydrogen of the (E)-sulfoxide 9 but enough to catalyze the sigmatropic process of the sulfoxides. The sulfenic acid 2 dimerized to the thiolsulfinate 10 while the sulfenic acid 4 proceeded the sigmatropic ring closure. In the presence of strong base such as potassium hydroxide, the elimination reaction was predominant over the sigmatropic rearrangement. In this reaction condition, both sulfoxides 8a and 9a gave a mixture of the disulfide 12, the isomeric disulfide 14, and the sulfinic acid 13. Under the strong alkaline condition an elimination of activated hydrogen from the carbon adjacent to the carbonyl group to furnish the sulfenic acid 2a and the isomeric sulfenic acid 18. The formation of the transient intermediate in the reaction was proven by isolation of the isomeric disulfide 14. The reactive entity was regarded as the sulfenic acid rather than sulfenate anion under these reaction conditions.

• 한국광물학회지
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• 제16권1호
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• pp.107-123
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• 2003

본 연구는 0가 철 (ZVI)의 설치위치와 전극의 배열에 따른 다양한 조합의 전기적 투수성 반응벽을 대상으로 트리클로로에틸렌의 탈염소화 반응에 의한 정화시 ZVI의 부식에 기인하는 광물상침전물에 대해 알아보고, 이에 대한 조절 요소를 알아보고자 한다. 광물학적 연구 결과, 지하수 유입부의 ZVI 시료는 상대적으로 많은 레피도크로사이트, 훼리하이드라이트 혹은 철 수산화물과 (phospho)siderite가 산출되는 반면, 용출부의 ZVI 시료는 아카가나이트, 자철석/마그헤마이트, 그리고 중간 산물인 green rust (CR) I 과 CR II가 산출되었다. 이러한 광물 조합의 변화는 용존 산소 및 pH의 상승에 주로 기인한 것으로 나타났다. 또한 전기적 투수성 반응벽 내에 산출되는 광물상 침전물들의 조절 요소들은 (1) pH, (2) 용존산소, (3) 철의 부식시 중간 산물, (4) 음이온 종류 등으로 밝혀졌다.

• Bulletin of the Korean Chemical Society
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• 제32권6호
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• pp.1907-1911
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• 2011

A kinetic study is reported for nucleophilic substitution reactions of 4-pyridyl X-substituted benzoates 7a-e with a series of alicyclic secondary amines in H2O. The Br${\o}$nsted-type plot for the reactions of 4-pyridyl benzoate 7c is linear with ${\beta}_{nuc}$ = 0.71. The corresponding reactions of 2-pyridyl benzoate 6, which is less reactive than 7c, resulted in also a linear Br${\o}$nsted-type plot with ${\beta}_{nuc}$ = 0.77. The fact that the more reactive 7c results in a smaller ${\beta}_{nuc}$ value appears to be in accord with the reactivity-selectivity principle. The aminolysis of 7c has been suggested to proceed through a stepwise mechanism in which breakdown of the intermediate is the rate-determining step (RDS). The Hammett plot for the reactions of 7a-e with piperidine consists of two intersecting straight lines, i.e., ${\rho}_X$ = 1.47 for substrates possessing an electron-donating group (EDG) and ${\rho}_X$ = 0.91 for those possessing an electron-withdrawing group (EWG). In contrast, the corresponding Yukawa-Tsuno plot exhibits excellent linear correlation with ${\rho}_X$ = 0.79 and r = 0.56. Thus, it has been concluded that the nonlinear Hammett plot is not due to a change in the RDS but is caused by stabilization of the ground state of the substrates possessing an EDG through resonance interaction between the EDG and the C=O bond of the substrates.

• Journal of Microbiology and Biotechnology
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• 제30권8호
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• pp.1252-1260
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• 2020

(R)-2-(4-hydroxyphenoxy)propionic acid (HPOPA) is a key intermediate for the preparation of aryloxyphenoxypropionic acid herbicides (R-isomer). In order to improve the HPOPA production from the substrate (R)-2-phenoxypropionic acid (POPA) with Beauveria bassiana CCN-A7, static cultivation and H₂O₂ addition were attempted and found to be conducive to the task at hand. This is the first report on HPOPA production under static cultivation and reactive oxygen species (ROS) induction. On this premise, the cultivation conditions and fermentation medium compositions were optimized. As a result, the optimal carbon source, organic nitrogen source, and inorganic nitrogen source were determined to be glucose, peptone, and ammonium sulfate, respectively. The optimal inoculum size and fermentation temperature were 13.3% and 28℃, respectively. The significant factors including glucose, peptone, and H₂O₂, identified based on Plackett-Burman design, were further optimized through Central Composite Design (CCD). The optimal concentrations were as follows: glucose 38.81 g/l, peptone 7.28 g/l, and H₂O₂ 1.08 g/l/100 ml. Under the optimized conditions, HPOPA titer was improved from 9.60 g/l to 19.53 g/l, representing an increase of 2.03-fold. The results obtained in this work will provide novel strategies for improving the biosynthesis of hydroxy aromatics.

• Bulletin of the Korean Chemical Society
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• 제29권10호
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• pp.1915-1919
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• 2008

Second-order rate constants ($k_N$) have been measured spectrophotometrically for reactions of 3,4-dinitrophenyl benzoates (5b) with a series of alicyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. The kinetic data have been compared with the data reported previously for the corresponding reactions of 2,4- dinitrophenyl benzoates (5a) to investigate the effect of changing the nucleofuge from 2,4-dinitrophenoxide to 3,4-dinitrophenoxide on reactivity and mechanism. The kinetic results show that aminolyses of 5a and 5b proceed through the same mechanism, i.e., a zwitterionic tetrahedral intermediate ($T^{\pm}$) with a change in the rate-determining step (RDS). Substrate 5a is more reactive than 5b when breakdown of $T^{\pm}$ is the RDS but less reactive when formation of $T^{\pm}$ is the RDS. Dissection of kN values into the microscopic rate constants (e.g., $k_1$ and $k_2/k_{-1 }$ ratio) has revealed that 5a results in larger $k_2/k_{-1}$ ratios but smaller k1 values than 5b for all the amines studied. Since 2,4-dinitrophenoxide is less basic and a better nucleofuge than 3,4-dinitrophenoxide, the larger $k_2/k_{-1}$ ratios determined for the reactions of 5a than for those of 5b are as expected. The steric hindrance exerted by the ortho-nitro group on 5a contributes to the smaller k1 values found for the reactions of 5a than for those of 5b.