• Journal of Plant Biology
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• 제19권4호
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• pp.95-99
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• 1976

This work deals with different extraction media and reaction mixtures on photosystem II activity of Spinach chloroplasts. The photoreduction rate of ferricyanide and DPIP by intact chloroplasts which extracted with four kinds of extraction media; S-Tris-N pH 7.2, 8.0, S-Tricine-N pH 7.2, 8.0, was measured in five kinds of reaction mixtures; S-Tris-N pH 7.2, 8.0, S-Tricine-N pH 7.2, 8.0, 0.05 M-Tris pH 7.2. The extraction medium which shows the highest photoreduction rate was S-Tris-N at pH 7.2 and S-Tricine-N at pH 8.0. As to the reaciton mixture, S-Tricine-N pH 8.0 showed the highest rate. On the complex effects of extraction media and reaction mixtures, the highest photordeuction rate of Hill oxidant by intact chloroplasts was obtained by S-Tris-N pH 7.2 extraction medium and S-Tricine-N pH 8.0 reaction mixture. The second highest activity was obtained by S-Tricine-N pH 8.0 extraction medium and reaction mixture.

• 대한화학회지
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• 제36권1호
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• pp.81-86
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• 1992

M(S-S,ph)(N-N,H) (M = Ni(II), Pd(II), Pt(II); (S-S,ph) = 1,2-diphenylethylenedithiolate; (N-N,H)=1,10-phenanthroline) 착물의 친전자성 및 친핵성 리간드 반응을 조사하였다. norbornadiene과의 반응성은 중심금속의 역결합의 정도에 의존하며 2,5-dithia-3,4-diphenyl-tricyclo[4,4,1,0]-undeca-3,8-diene을 생성하였다. methyl iodide와의 반응은 (N-N,H) 리간드의 이탈 능력에 지배되며 메틸화된 $M(S-S,ph)_2$ 착물을 생성하였다. 이 반응의 주생성무리은 열 분해에 의해 얻어진 ${\alpha},{\alpha}{\prime}$,-bismethylthiostibene $(CH_3S-SCH_3,ph)$의 구조로부터 M(S-S,CN)(N-N,H)((S-S,CN) = 1,2-dicyanoethylenedithiolate)의 새로운 혼합 리간드 착물을 합성하였다.

• Bulletin of the Korean Chemical Society
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• 제23권6호
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• pp.851-856
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• 2002

The Reaction of S-methyl-S-cysteine(L-Smc) with racemic $s-cis-[Co(demba)Cl_2]-1$ (Hydmedba = $NN'-dimethylethylenediamine-NN'-di-\alpha-butyric$, acid) yields ${\Delta}$-s-cis-[Co(dmedba)(L-Smc)] 2 with N, O-chelation. Oxidation of sulfur of 2 with $H_2O_2$ in a 1 : 1 mole ratio gives ${\Delta}$-s-cis[Co(dmedba)(L-S(O)mc)] 3 having an uncoordinated sulfenate group. Oxidation of sulfur of L-Sm with $H_2O_2in$ a 1: 1 mole ratio produces S-methyl-L-cysteinesulfenate (L-S(O)me) 5. Direct reaction of 1 with 5 in basic medium gives an N.O-chelated ${\Delta}$s-cis[Co(dmedba)(L-S(O)mc)-N.O], which turmed out be same as obtained by oxidation of 2, while an N, S-chelated ${\Delta}$-s-cis-[Co(dmedba)(S-S(O)mc)-N,O] complex 4 is obtained in acidic medium from the reaction of 1 with 5. This is one of the rare $[$Co^{III}$(N_2O_2-type$ ligand)(amino acid)] type complex preparations, where the reaction conditions determine which mode of N, O and N, S caelation modes is favored.

• 대한화학회지
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• 제30권4호
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• pp.383-388
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• 1986

2-phenylethylarenesulfonates와 피리딘과의 아세토니트릴 용매중에서의 반응속도를 40∼60${\circ}C$, 1 ~ 2,000 bar에서 전기 전도도법으로 측정하였다. 반응속도는 온도가 높아지고 압력이 커짐에 따라 증가하였으며 아세톤 용매내에서 benzyl benzenesulfonate와 파라딘과의 반응속도보다 느렸다. 2-phenylethyl m-nosylate의 활성화 부피${\Delta}V^{\neq}$와 활성화 엔트로피 TEX>${\Delta}S^{\neq}$는 benzenesuflonate보다 음의 값으로 컸다. 따라서 본 반응의 2-phenylethyl계가 전이 상태에서 벤질계보다 $S_N2$성이 크다고 추정된다. Hammett도시한 결과는 압력의 증가에 따라 값이 감소하여 $S_N2$성이 증가하였다. 이들의 모든 결과로 부터 고압하에서의 본 반응은 $S_N2$메카니즘으로 진행되며 압력의 증가는 $S_N2$반응성을 더욱 조장하였다.

• 대한화학회지
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• 제23권1호
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• pp.37-41
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• 1979

Benzyl m-nitrobenzenesulfonate와 N,N-dimethylaniline類와의 反應速度를 아세톤 溶媒에서 電氣傳導度法으로 測定하였다. N,N-디메틸아닐린의 反應性에 關한 置換基效果와 直線 自由에너지 關係를 考察하였다. 反應速度常數 k는 2.55∼487 $10^{-4}l{\cdot}mol^{-l}{\cdot}sec^{-1} (35^{\circ}C)$였으며 置換基가 電子를 주는 能力이 클수록 反應은 빨랐다. Hammett 도시에서 置換基常數 ${\sigma}$와 ${\sigma}p$-MeO = -0.35의 새로운 값을 使用했을때 ${\rho}$ = -1.37의 좋은 直線이 얻어졌다. 本反應의 경우 r값은 브롬화벤질에 比해 큰 값을 가졌다. Bronsted 圖示에서 溶媒效果에 基因된 p-MeO基를 除外하고는 좋은 直線이 얻어졌으며 C${\cdot}{\cdot}{\cdot}$O 結合의 쪼개짐이 結合 形成보다 優先的인 $S_N2$ 轉移狀態를 갖는다고 推定된다.

• Bulletin of the Korean Chemical Society
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• 제30권7호
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• pp.1535-1538
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• 2009

We present calculations for $S_N$2/E2 reactions in protic solvents (t-butyl alcohol, ethylene glycol). We focus on the role of the hydroxyl (-OH) groups in determining the $S_N$2/E2 rate constants. We predict that the ion pair E2 mechanism is more favorable than the naked ion E2 reaction in ethylene glycol. E2 barriers are calculated to be much larger (~ 9 kcal/mol) than $S_N$2 reaction barriers in protic solvents, in agreement with the experimental observation [Kim, D. W. et al. J. Am. Chem. Soc. 2006, 128, 16394] of no E2 products in the reaction of CsF in t-butyl alcohol.

• Bulletin of the Korean Chemical Society
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• 제17권5호
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• pp.428-432
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• 1996

Amino acid cobalt(Ⅲ) complexes of 1,3-diminopropane-N,N'-di-α-(β-methyl)-pentanoic acid (H2dpdmp), uns-cis-[Co(dpdmp)(aa)] (aa=glycine, S-alanine, R-aspartic acid, sarcosine) have been prepared from the reaction between the uns-cis-[Co(dpdmp)Cl2]- complex and the corresponding amino acid. In the reaction with the uns-cis-[Co(dpdmp)Cl2]- complex, glycine and S-alanine have yielded both merridional and facial isomers, while R-aspartic acid and sarcosine, only merridional isomers. The stereospecific substitution reaction of R-aspartic acid to racemic uns-cis-[Co(dpdmp)Cl2]- complex has yielded two merridional diastereomers; ΛR-uns-cis- and ΛR-uns-cis-[Co(dpdmp)(R-asp)]. It is of interest to note that this is one of the few CoⅢ(ONNO)(aa) type complex preparations, which gives only one isomer with stereospecificity. On the other hand, two merridional products obtained from the reaction of sarcosine with racemic uns-cis-[Co(dpdmp)Cl2]- are turned out to be mixtures of optical isomers.

• 공업화학
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• 제8권5호
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• pp.777-783
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• 1997

n-propanol 용매내에서 titanium n-propoxide($Ti(O^nPr)_4$)의 가수분해반응에 의하여 $TiO_2$ 미분말을 합성하였고, 가수분해속도를 자외선 분광법에 의하여 측정하였다. 분말합성은 water/alkoxide의 농도비가 약 300정도에서 실시하였으며, 물농도, 반응온도, 반응시간 및 반응용액의 산 염기효과에 의한 합성조건을 조사하였다. 반응은 $Ti(O^nPr)_4$의 농도에 비하여 물농도를 과량으로 하여 유사일차반응으로 진행시켰고, 반응속도상수를 Guggenheim method로 계산하였다. 또한 물의 동위원소효과($D_2O$)를 측정하여 반응에 관여하는 물분자의 촉매성을 확인하였다. 실험결과 중성 및 염기성 용액 조건에서 $TiO_2$미분말이 합성되었고, 미세구조 관찰로부터 $TiO_2$입자는 직경 $0.4-0.7{\mu}m$ 정도의 구형입자로 확인되었으며, 물의 농도와 반응온도가 증가할수록, 반응시간이 감소할수록 입자크기는 작아지는 경향을 보였다. 물의 동위원소효과로부터, 물분자는 nucleophilic catalysis로 작용하고 있으며, 반응속도로부터 전이상태에 참여하는 n-value와 열역학적 파라미터를 계산한 결과, $Ti(O^nPr)_4$의 가수분해반응은 이분자 반응인 associative $S_N2$ mechanism으로 진행하는 것으로 추정되었다.

• 대한전기학회논문지
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• 제45권2호
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• pp.242-248
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• 1996

The properties of TiN/TiSi$_{2}$ bilayer formed by a rapid thermal annealing is investigated when thin SiO$_{2}$ film exists at the Ti-Si interface. The competitive reaction for the TiN/TiSi_2 bilayer occurs above 600 .deg. C. The thickness of the TiSi$_{2}$ layer decreases with increasing SiO$_{2}$ film thickness and also decreases with increasing anneal temperture When the competitive reaction for the TiN/TiSi$_{2}$ bilayer is occured by rapid thermal annealing, the composition of TiN layer represents TiN$_{x}$O$_{y}$ due to the SiO$_{2}$ layer at the Ti-Si interface but the structures of the TiN and TiSi$_{2}$ layers were not changed.d.d.

• Bulletin of the Korean Chemical Society
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• 제21권9호
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• pp.919-922
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• 2000

The cyclization reaction of N-(2-hydroxyethyl)-N'-phenylthioureas 2 containingambident nucleophile was ex-amined in the combination of a variety ofbases and p-toluenesulfonyl chloride (TsCl).N-(2-Hydroxyeth-yl) thioureas 2 were readily obtained in high yields from the reaction of the corresponding 1,2-aminoalcohols with phenyl isothiocyanate, avoiding the need for O-protection.The use of a one-pot reaction (NaOH/TsCl) was found to be most effective in producing the requisite 2-phenylaminothiazolines (S-cyclization) 3 in the case ofthioureas 2a-2e derived from N-unsubstituted aminoalcohols,while in the thioureas 2f and 2g prepared from N-substituted aminoalcohols the combination of Et3N and TsCl led to the S-cyclization products.