• 중국학논총
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• 제72호
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• pp.47-70
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• 2021

In this paper, the focus was on the review of Ming General Nan Fangwei's activities during the Choson period and existing relevant historical artifacts & literacy works. Nan Fangwei's hometown was Jiangxi(江西) Changjiang(昌江; Jingdezhen景德鎭). Unfortunately, it has not been known where his descendants migrated later. During Jingdezhen Riot(景德鎭民亂), he went to serve as the head of the grass roots. After surrendering, he became a general in the Ming military base. During Jeongyujae War(丁酉再亂), he entered Chosun as a Youji general(遊擊) and participated in dozens of large and small battles. However, the defeat of Jungro-gun (中路軍) led him to a feud with the Ming's military authorities and to return him, which gave him a hard time to be forcibly dislodged to a remote region. Nan Fangwei established Namwon Guanwang Shrine(南原 關王廟). Since then, it has been preserved in Namwon Wangjeong-dong(王亭洞) through several reconstruction and reconstruction works. In addition, he took good care of people by strictly cracking down on their subordinates with high integrity and virtuous deeds at the military base. Being deeply touched by his morality and virtue, the people of Gongju(公州) established 'Youji general Nan Fangwei Jongdeokbi(〈遊擊將藍公種德碑〉)'. In addition, when he had his leisure time, he collected Korean Chinese poems from various figures and edited and published 'Chosun Poetry Collection(《朝鮮詩選全集》)', which he played a catalyst to promote high-quality Korean poems to Chinese literacy community.

• Nano
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• 제13권11호
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• pp.1850132.1-1850132.14
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• 2018

The direct synthesis of metal-organic frameworks (MOFs) with acidic and basic active sites is challenging due to the introduction of functional groups by post-functionalization method often jeopardize the framework integrity. Herein, we report the direct synthesis of acid-base bifunctional MOFs with tuning acid-base strength. Employing modulated hydrothermal (MHT) approach, microporous MOFs named $UiO-66-NH_2$ was prepared. Through the ring-opening reaction of 1,3-propanesultone with amino group, $UiO-66-NH_2-SO_3H-type$ catalysts can be obtained. The synthesized catalysts were well characterized and their catalytic performances were evaluated in one-pot glucose to 5-HMF conversion. Results revealed the acid-base bi-functional catalyst possessed high activity and excellent stability. This work provides a general and economically viable approach for the large-scale synthesis of acid-base bi-functional MOFs for their potential use in catalysis field.

• Bulletin of the Korean Chemical Society
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• 제24권4호
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• pp.431-436
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• 2003

Solvolytic rate constants at 25℃ are reported for solvolyses of cinnamyl bromide (1) in binary mixtures of water with acetone, ethanol, methanol, methanol-d, and 2,2,2-trifluoroethanol. Product selectivities are reported for solvolyses of 1 in aqueous ethanol and methanol. Rate ratios in solvents of the same $Y_{Br}$ value and different nucleophilicity provide measures of the minimum extent of nucleophilic solvent assistance (e.g. $[k_{40EW}/k_{97TFE}]$Y = 2.88, EW = ethanol-water). With use of the extended Grunwald-Winstein equation, the l and m values are similar to the values of 0.43 and 0.88 obtained for the solvolyses of 1 using the equation (see below) which includes a parameter (I) for solvation of aromatic rings. The magnitude of l and m values associated with a change of solvent composition predicts the $S_{N1}$ reaction mechanism rather than an $S_{N2}$ channel. Product selectivities (S), defined by S = [ether product]/[alcohol product]×[water]/[alcohol solvent] are related to four rate constants for reactions involving one molecule of solvent as nucleophile and another molecule of solvent as general base catalyst. A linear relationship between 1/S and molar ratio of solvent is derived theoretically and validated experimentally for solvolyses of the above substrates from water up 75% 1/S = $(k_{wa}/k_{aw})$([alcohol solvent]/[water]) + $k_{ww}/k_{aw}$ alcohol-water. The results are best explained by product formation from a “free” carbocation intermediate rather than from a solvent-separated ion pair.

• Korean Chemical Engineering Research
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• 제56권3호
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• pp.416-420
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• 2018

A comprehensive kinetic study has been conducted on dimethyl carbonate synthesis by transesterification reaction of ethylene carbonate with methanol. An alkali base metal (KOH) was used as catalyst in the synthesis of DMC, and its catalytic ability was investigated in terms of kinetics. The experiment was performed in a batch reactor at atmospheric pressure. The reaction orders, the activation energy and the rate constants were determined for both forward and backward reactions. The reaction order for forward and backward reactions was 0.87 and 2.15, and the activation energy was 12.73 and 29.28 kJ/mol, respectively. Using the general factor analysis in the design of experiments, we analyzed the main effects and interactions according to the MeOH/EC, reaction temperature and KOH concentration. DMC yield with various reaction conditions was presented for all ranges using surface and contour plot. Furthermore, the optimal conditions for DMC yield were determined using response surface method.

• Bulletin of the Korean Chemical Society
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• 제1권3호
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• pp.113-114
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• 1980

Lumichrome (7,8-dimethylalloxazine) exhibits two fluorescence emission maxima at 440 and 540 nm in pyridine-dioxane. These emission band maxima are attributable to radiative decays from the excited states of lumichrome and its flavin tautomer, 7,8-dimethylisoalloxazine, respectively. The growth of the latter can be followed upon excitation of the former with a 2-nanosecond light pulse generated from the nitrogen plasma discharge lamp. The excited state tautomerism results from proton transfer from N-1 to N-10 position during the lifetime of the lumichrome singlet excited state. The rate depends on the concentration of general base, pyridine, and it is an order of magnitude slower than diffusion-controlled processes.

• Bulletin of the Korean Chemical Society
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• 제35권8호
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• pp.2263-2270
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• 2014

Solvolysis rate constants of 2-phenylethyl-(2-$PhCH_2CH_2OCOCl$, 1) and 2,2-diphenylethyl chloroformate (2,2-$Ph_2CHCH_2OCOCl$, 2), together with the previously studied solvolyses of ${\alpha}$- and ${\beta}$-substituted chloroformate ester derivatives, are reported in pure and binary solvents at $40.0^{\circ}C$. The linear free energy relationship (LFER) and sensitivities (l and m) to changes in solvent nucleophilicity ($N_T$) and solvent ionizing power ($Y_{Cl}$) of the solvolytic reactions are analyzed using the Grunwald-Winstein equation. The kinetic solvent isotope effects (KSIEs) in methanol and activation parameter values in various solvents are investigated for 1 and 2. These results support well the bimolecular pathway with same aspects. Furthermore, the small negative values of the entropies of activation of solvolysis of 1 and 2 in the highly ionizing aqueous fluoroalcohols are consistent with the ionization character of the rate-determining step, and the KSIE values of 1.78 and 2.10 in methanol-d indicate that one molecule of solvent acts as a nucleophile and the other acts as a general-base catalyst. It is found that the ${\beta}$-substituents in alkyl chloroformate are not the important factor to decide the solvolysis reaction pathway.

• 한국산학기술학회논문지
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• 제17권7호
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• pp.420-424
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• 2016

본 연구에서는 지속적으로 심각한 대기오염의 문제로 실내 공기청정의 중요성이 대두되는 점을 감안하여 광촉매 단위기술을 개발하고자 건식 박막 공정 중 일반적으로 사용되어지는 RF 마그네트론 스퍼터링을 이용하여 $WO_3$ 단층막을 증착하였다. 초기 진공도는 $1.8{\times}10^{-6}$ [Torr]를 기준하여 최적의 스퍼터링 공정조건인 RF 100[W], 7[mTorr]진공 조건에서 Ar:$O_2$ 반응가스의 비율을 70[sccm] : 2[sccm]으로 하여 제작된 $WO_3$ 단층막은 380[nm]-780[nm]의 가시광 영역에서 80% 이상의 높고 일정한 광투과 특성을 확인하였다. 공기 청정 효과를 확인 위해 제작된 $WO_3$ 박막의 광촉매 특성을 조사하기 위해 메틸렌블루 내에서의 흡광도 및 농도변화를 광조사 시간 변화에 따라 측정하였다. 그 흡광도 측정결과 시간에 따라 흡광도 특성이 보임을 확인하였고, 5시간 경과 후 기존 메틸렌블루 농도 대비 80% 수준의 농도로 낮아지는 것을 확인하였다. 이런 결과로 부터 스퍼터링법에 의해 제작된 기능성 $WO_3$박막의 광분해 특성을 통해 형광등의 반사갓 혹은 LED등의 렌즈에 활용 된다면 차세대 조명원의 공기청정 효과를 증진시킬 수 있는 박막을 개발하였다.

• Bulletin of the Korean Chemical Society
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• 제24권9호
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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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• 제34권1호
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• pp.49-53
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• 2013

Second-order rate constants have been measured spectrophotometrically for the reactions of phenyl Y-substituted-phenyl carbonates 7a-g with butane-2,3-dione monoximate ($Ox^-$) in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The ${\alpha}$-nucleophile $Ox^-$ is 53-95 times more reactive than the corresponding normal-nucleophile 4-$ClPhO^-$ toward 7a-g, indicating that the ${\alpha}$-effect is operative. The magnitude of the ${\alpha}$-effect (e.g., the $k_{Ox^-}/k_{4-ClPhO^-}$ ratio) is independent of the electronic nature of the substituent Y. The cause of the ${\alpha}$-effect for the reactions of 7a-g has been suggested to be ground-state (GS) effect rather than transition-state (TS) stabilization through a six-membered cyclic TS, in which $Ox^-$ behaves a general acid/base catalyst. This idea is further supported by the result that $OH^-$ exhibits negative deviation from the linear Br${\o}$nsted-type plot composed of a series of aryloxides, while $Ox^-$ deviates positively from the linearity. Differential solvation of the GS of $Ox^-$ and 4-$ClPhO^-$ has been suggested to be responsible for the ${\alpha}$-effect exerted by $Ox^-$.

• 한국식품과학회지
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• 제48권4호
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• pp.341-346
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• 2016

HPA는 식품으로 섭취되는 녹말을 분해하는데 있어서 매우 중요한 역할을 수행하는 효소이기 때문에 HPA 효소 활성의 억제는 당뇨와 비만과 같은 질환의 예방과 치료에 있어서 의미를 가진다. 따라서 HPA는 당뇨병 치료와 비만 예방을 위한 새로운 식 의약품 소재 개발을 위한 주요 타깃 효소 중 하나이며, 새로운 소재의 개발을 위해서는 HPA의 반응 메커니즘을 비롯하여 천연 기질 분해 특성에 대한 이해가 반드시 필요하다. 본 연구에서는 HPA의 동질효소 중 연구가 거의 진행되지 않은 HPA II에 대한 효소 특성화를 진행하고자 P. pastoris 시스템을 이용하여 재조합 HPA II를 생산하였으며, 녹말 분해와 관련된 효소적 특성을 분석하였다. HPA II는 10 mM NaCl까지 농도 의존적으로 효소활성이 증가하였으며, 최적 활성을 위한 pH는 0 mM NaCl 조건에서 pH 6.5이었으나 10 mM NaCl조건에서 pH 7.5로 이동하는 특성을 보였으며, 이는 HPA I을 포함하는 염소이온 의존형 아밀레이스가 나타내는 전형적인 특징이다. 염소이온 존재 시 최적 pH가 염기성 pH 영역으로 이동하는 것은 염소 이온과 효소의 결합에 의해 HPA II의 산/염기 촉매 잔기의 $pK_a$값이 커진다는 것을 의미하며, 염소이온을 첨가하였을 때 녹말에 대한 가수분해 활성의 증대 정도가 산성 pH 영역보다 염기성 pH 영역에서 두드러지게 나타났다는 점이 이를 뒷받침하였다. 반응속도론적 분석 결과에 따르면 염소이온 존재 시 효소활성의 증대는 대부분 전환수(turnover number)의 증대에 의한 것으로 나타났으며, 가용성 녹말 보다 곡류 녹말에 대한 전환수의 증대가 크게 나타났다. 염소이온은 활성의 증대뿐만 아니라 고농도의 기질 조건에서 기질에 의한 효소 활성 억제 양상을 심화시키는 것으로 나타났다. 결론적으로 HPA II의 특징은 HPA I과 거의 유사한 경향을 나타내었으며, 염소이온 첨가여부에 따른 HPA II의 가수분해활성 결과를 바탕으로 향 후 HPA에 대한 곡류 녹말 가수분해 활성 억제제 개발을 위한 연구를 추진할 계획이다.