• Bulletin of the Korean Chemical Society
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• 제33권1호
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• pp.48-54
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• 2012

The $[Fe_4S_4]^{2+}$ clusters with 2-, 3-, and 4-pyridinemethanethiolate (S2-Pic, S3-Pic, and S4-Pic, respectively) terminal ligands have been synthesized from the ligand substitution reaction of the $(^nBu_4N)_2[Fe_4S_4Cl_4]$ (I) cluster. The new $(^nBu_4N)_2[Fe_4S_4(SR)_4]$ (R = 2-Pic; II, 3-Pic; III, 4-Pic; IV) clusters were characterized by FTIR and UV-Vis spectroscopy. Cluster II was crystallized in the monoclinic space group C2/c with a = 24.530 (5) $\AA$, b = 24.636(4) $\AA$, c = 21.762(4) $\AA$, ${\beta}=103.253(3)^{\circ}$, and Z = 8. The X-ray structure of II showed two unique 2:2 site-differentiated $[Fe_4S_4]^{2+}$ clusters due to the bidentate-mode coordination by 2-pyridinemethanethiolate ligands. Cluster III was crystallized in the same monoclinic space group C2/c with a = 26.0740(18) $\AA$, b = 23.3195(16) $\AA$, c = 22.3720(15) $\AA$, ${\beta}=100.467(2)^{\circ}$, and Z = 8. The 3-pyridinemethanethiolate ligand of III was coordinated to the $[Fe_4S_4]^{2+}$ core as a terminal mode. Cluster IV with 4-pyridinemethanethiolate ligands was found to have a similar structure to the cluster III. Fully reversible $[Fe_4S_4]^{2+}/[Fe_4S_4]^+$ redox waves were observed from all three clusters by cyclic voltammetry measurement. The electrochemical potentials for the $[Fe_4S_4]^{2+}/[Fe_4S_4]^+$ transition decreased in the order of II, III and IV, and the reduction potential changes by the ligands were explained based on the structural differences among the complexes. The complex III was reacted with sulfonium salt of $[PhMeSCH_2-p-C_6H_4CN](BF_4)$ in MeCN to test possible radical-involving reaction as a functional model of the [$Fe_4S_4$]-SAM (S-adenosylmethionine) cofactor. However, the isolated reaction products of 3-pyridinemethanethiolate-p-cyanobenzylsulfide and thioanisole suggested that the reaction followed an ionic mechanism and the products formed from the terminal ligand attack to the sulfonium.

• 공업화학
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• 제16권2호
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• pp.243-249
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• 2005

회분식/순환식증류 반응시스템에서 Amberlyst 이온교환수지와 황산의 첨가에 따른 젓산의 에스테르화 반응을 고찰하였다. 회분식증류 반응시스템에서는(n-butanol/lactic acid = 4, $100^{\circ}C$) 물의 함유량이 적을수록, n-butanol/lactic acid의 몰비가 증가할수록 에스테르화 전환율이 높게 나타났다. 알코올의 종류에 따른 에스테르화 전환율을 비교 해본 결과 단순한 구조의 메탄올과 치환반응성이 뛰어난 tert-부탄올이 에탄올, n-부탄올, iso-부탄올에 비해 치환 반응에 의한 에스테르화 전환율이 높은 것으로 나타났다. 지속적으로 물을 제거하는 순환식증류 반응 시스템에서는 (n-butanol/ammonium lactate = 4, $115^{\circ}C$) Amberyst-15 고체산 촉매를 사용한 경우가 황산촉매를 사용한 경우보다 에스테르반응 전환율이 높게 나타났다. 고체산 촉매를 반응초기에 투입한 경우에는 에스테르 반응이 지속적으로 진행되었으나 황산촉매의 경우에는 초기단계의 반응속도에는 영향을 미치지 않는 것으로 나타났다. 이는 반응 초기에 투입한 황산이 ammonium lactate간의 반응을 통해 ammonium sulfate를 생성하는 중화반응에 우선적으로 참여하기 때문인 것으로 사료된다.

• 공업화학
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• 제9권5호
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• pp.704-709
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• 1998

${\alpha}$-Methyl styrene과 maleic anhydride를 공단량체로 사용하여 유리전이온도가 높고 내열성이 우수한 poly (${\alpha}$-methylstyrene-co-maleic anhydride) (MSMA) 기재 고분자 (substrate polymer)를 합성하고 여기에 니트로기를 가진 발색단을 고분자반응을 이용하여 도입하는 반응 및 생성된 비선형 광학 고분자의 전기 광학 특성에 대해 조사하였다. MSMA 기재 고분자에 hydroxyl기를 가지는 azo계 발색단 (chromophore) 2-[4-(4-nitrophenylazo)-N-ethylphenylamino]ethanol (DR1)을 고분자 반응 (polymer reaction)으로 maleic anhydride에 ester 결합으로 도입할 때 4-dimethylaminopyridine (DMAP) 촉매만을 쓴 것 (MSMA-D)보다 DMAP와 3-dicyclohexyl carbodiimid (DCC)를 동시에 사용한 경우 (MSMA-DC)가 DR1 발색단의 도입율이 높게 나타났다. 비선형 광학 고분자 (MSMA-DC)의 전기광학계수 ($r_{33}$)는 파장이 632.8 nm인 광원에서 18 pm/V의 값을 나타냈으며 열적 안정성도 유리전이 온도 ($T_g$)가 $175^{\circ}C$ 이상으로 우수하게 나타났다.

• Plant Biotechnology Reports
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• 제5권2호
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• pp.127-134
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• 2011

The biotransformation potential of cell suspension cultures generated from Withania somnifera leaf was investigated, using withanolides, i.e. withanolide A, withaferin A, and withanone as precursor substrates. Interestingly, the cell suspension cultures showed inter-conversion of withanolides, as well converted to some unknown compounds, released to the culture media. The bio-catalyzed withanolide was detected and quantified by TLC and HPLC, respectively. There is noticeable conversion of withanolide A to withanone, and vice versa though at a lower level. The type of reaction of this biotransformation appears to be substitution of 20-OH group to 17-OH in withanolide A. In this paper, we present for the first time the possibility of biotransformation by inter-conversion of withanolides of pharmacological importance through cell suspension culture of W. somnifera. The possible role of putative cytochrome $P_{450}$ hydroxylases is implicated in the conversion.

• Bulletin of the Korean Chemical Society
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• 제33권2호
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• pp.663-669
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• 2012

The nucleophilic substitution reactions of dibutyl chlorophosphate (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $55.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; kH/kD) are secondary inverse ($k_H/k_D$ = 0.86-0.97) with the strongly basic anilines while primary normal ($k_H/k_D$ = 1.04-1.10) with the weakly basic anilines. The DKIEs, steric effects of the two ligands, activation parameters, cross-interaction constants, variation trends of the kH/kD values with X, and mechanism are discussed for the anilinolyses of the nine ($R_1O$)($R_2O$)P(=O)Cl-type chlorophosphates. A concerted mechanism is proposed with a backside nucleophilic attack transition state for the strongly basic anilines and with a frontside attack involving a hydrogen-bonded four-center-type transition state for the weakly basic anilines on the basis of the magnitudes, secondary inverse and primary normal, and variation trends of the $k_H/k_D$ values with X.

• Bulletin of the Korean Chemical Society
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• 제33권3호
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• pp.1037-1041
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• 2012

The nucleophilic substitution reactions of (2R,4R,5S)-(+)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $5.0^{\circ}C$. The anilinolysis rate of 3 involving a cyclic five-membered ring is considerably fast because of small negative value of the entropy of activation (${\Delta}S^\neq=-2cal\;mol^{-1}\;K^{-1}$) over considerably unfavorable enthalpy of activation (${\Delta}H^\neq=18.0\;kcal\;mol^{-1}$). Great enthalpy and small negative entropy of activation are ascribed to sterically congested transition state (TS) and bulk solvent structure breaking in the TS. A concerted $S_N2$ mechanism with a backside nucleophilic attack is proposed on the basis of the secondary inverse deuterium kinetic isotope effects, $k_H/k_D$ < 1.

• Bulletin of the Korean Chemical Society
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• 제33권3호
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• pp.1047-1051
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• 2012

The nucleophilic substitution reactions of (2R,4R,5S)-(+)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide with X-pyridines are investigated kinetically in acetonitrile at $5.0^{\circ}C$. The free energy relationships for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Ac. Unusual positive $\rho_X$ (= +4.73) and negative ${\beta}_X$ (= -0.75) values are obtained with the weakly basic pyridines, and rationalized by the isokinetic relationship with isokinetic temperature at $t_{ISOKINETIC}=39.3^{\circ}C$. A concerted mechanism involving a change of nucleophilic attacking direction from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines is proposed on the basis of greater magnitudes of selectivity parameters ($\rho_X$ = -6.15 and ${\beta}_X$ = 1.11) with the strongly basic pyridines compared to those ($\rho_X$ = 4.73 and ${\beta}_X$ = -0.75) with the weakly basic pyridines.

• KDI Journal of Economic Policy
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• 제25권1호
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• pp.3-54
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• 2003

본 연구는 공적자금상환을 위해 도입된 특별예금보험료 부과의 함의를 분석한다. 금융기관은 특별예금보험료를 추가적인 비용으로 인식하여 그 비용의 일부를 금융소비자에게 전가하려는 행위를 보일 것으로 예상된다. 계량분석 결과 금융기관은 금리에 민감하게 반응하는 대출보다는 예금으로 비용의 전가를 시도할 것으로 추정되었다. 그리고 부보대상예금의 상대적 비중이 고자산계층보다 저자산계층에서 높다는 가계자산 포트폴리오의 특징으로 인해 특별예금보험료 부과는 저자산계층에게 보유자산에 대비하여 상대적으로 높은 손실분담구조가 될 수 있음을 시사한다.

• 한국결정성장학회지
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• 제12권2호
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• pp.73-79
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• 2002

코발트, 니켈, 구리 그리고 귀금속분말에 적용할 수 있는 polyol법은 균질한 크기와 형상을 갖는 금속분말합성에 매우 효과적인 공정이다 이 때 polyol은 용매, 환원제 그리고 보호제의 역학을 한다 $AgNO_3$글 촉매제로 첨가하여 비균질계 핵생성 반응을 야기할 경우 서브마이크폰 크기(0.5$\mu$m)의 코발트 분말을 한성학 수 있었다. 또한 촉매제인 Ag 핵의 수출 변화시키므로써 코발트 분말의 입도를 제어할 수 있음을 확인하였다.

• 한국수소및신에너지학회논문집
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• 제8권4호
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• pp.161-171
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• 1997

$AB_2$ type Zr-based Laves phase alloys have been studied for potential application as negative electrode in Ni/MH batteries. However, They have a serious disadvantage of poor activation behavior in KOH solution. In this work, a new method of alloy design method was tried for improving Zr-based alloy activation. this method has focused on phase controlling to make multi-phase microstructure. In the case of multi-phase Zr-V-Mn-Ni shows good performance in activation, but activation mechanism has not been known. So, we were in search of elucidating this mechanism, Using morphological and electrochemical analysis, we could find that surface morphology and electocatalytic activity of the alloy change during immersion in KOH solution. V-rich second phases are selectively corroded and dissolved and then become Ni-rich phases. Resulting from these surface reaction in KOH solution, self-hydrogen charging occurs through Ni-rich phase. However, the alloy has poor cyclic durability because of such a corrosion mechanism. Therefore, finally we developed durable alloys by substitution of other alloying element.