• 대한화학회지
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• 제11권3호
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• pp.85-88
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• 1967

5-Phenyl-tetrazole은 光分解하면 질소 한 分子를 放出하며 1,3-dipole인 C-phenyl-nitrilei-mine을 形成한다. 그러나 이때 dipolarphile의 存在下에서 1,3-dipole-cyclo-addition은 일으키지 않으며 二重合體인 3,6-diphenyl-1,4-dihydro-1,2,4,5-tetrazine(III)을 거쳐 最終産物로서 3,6-diphenyl-1,2,4,5-tetrazine(IV), 2,5-diphenyl-1,2,4-triazole, 4-amino-3,5-diphenyl-1,2,4-triazole, benzonitrile, ammonia 그리고 nitrogen을 生成한다.

• Journal of Photoscience
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• 제12권3호
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• pp.155-162
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• 2005

Results of studies of SET-promoted dipole-forming photochemical group transfer reactions of phthalimide and ${\alpha}-ketoamide$ derivatives are discussed. Azomethine ylide forming photochemical reactions, which are initiated by intramolecular SET from tethered silylmethyl-, carboxymethyl-, and ${\beta}-hydroxyethyl$ containing electron donors to excited states of phthalimides, related maleimides, and conjugated imides, are presented first. Following this, investigations of regioselective 1,4-dipole forming photochemical reactions of N-trialkylsilylmethyl- and N-trialkylstannyl-${\alpha}$-ketoamides are described.

• 한국재료학회지
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• 제20권9호
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• pp.457-462
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• 2010

Adsorption of a water molecule on a Si (001) surface and its dissociation were studied using density functional theory to study the distribution of -OH fragments on the Si surface. The Si (001) surface was composed of Si dimers, which buckle in a zigzag pattern below the order-disorder transition temperature to reduce the surface energy. When a water molecule approached the Si surface, the O atom of the water molecule favored the down-buckled Si atom, and the H atom of the water molecule favored the up-buckled Si atom. This is explained by the attractions between the negatively charged O of the water and the positively charged down-buckled Si atom and between the positively charged H of the water and the negatively charged up-buckled Si atom. Following the adsorption of the first water molecule on the surface, a second water molecule adsorbed on either the inter-dimer or intra-dimer site of the Si dimer. The dipole-dipole interaction of the two adsorbed water molecules led to the formation of the water dimer, and the dissociation of the water molecules occurred easily below the order-disorder transition temperature. Therefore, the 1/2 monolayer of -OH on the water-terminated Si (001) surface shows a regular distribution. The results shed light on the atomic layer deposition process of alternate gate dielectric materials, such as $HfO_2$.

• Bulletin of the Korean Chemical Society
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• 제31권12호
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• pp.3549-3552
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• 2010

The complex formation between diazocalix[4]dipropyl (1) and diazocalix[4]crown-6 ether (2) with alkali, alkaline earth and transition metal ions was investigated by voltammetry. Electrochemical properties of compounds 1 and 2 and their selectivity toward metal ions were evaluated in $CH_3CN$ solution by comparison of voltammetric behaviors of two phenols in each compound. Compounds 1 and 2 showed almost same voltammetric behavior which is two irreversible oxidation peaks caused by intramolecular hydrogen bonding between two phenols in 1 and 2. While, however, upon interacting with various metal ions, 1 with two propyl ether groups showed no significant changes in voltammetry, 2 with crown ether group caused significant voltammetric changes upon the addition of $Ba^{2+}$ to 2. Their behavior is closely related to the complex formation by entrapment of metal ion into crown ether cavity, and ion-dipole interaction between metal ion and two phenolic groups in calix[4]crown-6.

• 대한화학회지
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• 제25권4호
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• pp.228-235
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• 1981

피리딘, ${\beta}$-피코린 및 3,5-루티딘과 요오드사이에 형성되는 전하이동착물을 사염화탄소 용액에서 자외선분광광도법을 사용하여 연구한 결과 $C_5H_5N{\cdot}I_2$, ${\beta}-C_5H_4(CH_3)N{\cdot}I_2$ 및 3,5-$C_5H_3(CH_3)_2N{\cdot}I_2$ 형의 1:1 분자착물이 형성됨을 알았다. 이들 착물생성에 대한 흡수최대는 온도가 상승함에 따라 blue shift되므로 이를 고려하여 각 온도에서의 평형상수를 구했다. 이 값으로부터 이들 착물생성에 대한 ${\Delta}H$, ${\Delta}G$및 ${\Delta}S$ 이 열역학적 파라미터를 산출하였다. 이 결과 착물의 상대적 안정도가 다음 순서로 증가함을 알수가 있었다. Pyridine < ${\beta}$-Picoline < 3,5-Lutidine. 이러한 결과는 dipole moment, steric hindrance effect 및 positive inductive effect에 의한 electron density의 증가 때문인 것으로 설명할 수 있었다. 그리고 polymethylbenzene-iodine CT-complex와도 비교 검토하였다.

• Bulletin of the Korean Chemical Society
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• 제6권1호
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• pp.37-40
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• 1985

The electrical conductance and UV absorbance of 4,N-dimethyl Pridinium Iodide (NDMPI) were measured in the ethanol volume percentage, 95, 90, 80 and 60 of an ethanol-water mixture at 15, 25, 35 and $45^{\circ}C$. Ionic association constants(K) of NDMPI were evaluated in accordance with a combined method of conductance UV absorbance. The ion size parameter (${\gamma}_{\pm}$) and dipole momemt (${\mu}_{A+D-}$) of NDMPI were obtained from the values of K and dielectric constant. The ${\mu}_{A+D-}$- values were in good agreement with the values of transition moment(${\mu}_{mn}$) which is calculated form the UV peak values. The large negative values of the electrical enthalpy (${\Delta}H_{el}^{\circ}$) and entropy (${\Delta}H_{el}^{\circ}$ ) have proved that NDMPI had a positive hydration. The positive values of entropy (${\Delta}S^{\circ}$) means the formation of NDMPI ion goes with dehydration.

• 한국미생물·생명공학회지
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• 제28권1호
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• pp.26-32
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• 2000

Electrostatic forces contribute to the high degree of enzyme transition state complementarity in enzyme catalyzed reaction and such forces are modified by the solvent through its dielectric constant and polar properties. The contributions of electrostatic interaction to the formation of ES complex and the stabilization of transition state of the trypsin catalyzed reaction were probed by kinetic studied with high pressure and solvent dielectric constant. A good correlation has been observed between the increase of catalytic efficiency of trypsin and the decrease of solvent dielectric constant. Activation volume linearly decreased as the dielectric constant of solvent decreased, which means the increase in the reaction rae. Moreover, the decrease of activation volume by lowering the solvent dielectric constant implies a solvent penetration of the active with and a reduction of electrostatic energy for the formation of dipole of the active site oxyanion hole. When the 야electric constant of the solvents was lowered to 4.7 unit, the loss of activation energy and that of free energy of activation were 2.262 KJ/mol and 3.169 KJ/mol, respectively. The results of this study indicate that the high pressure kinetics combined with solvent effects can provide unique information on enzyme reaction mechanisms, and the controlling the solvent dielectric constant can stabilize the transition state of the trypsin-catalyzed reaction.

• 대한전자공학회논문지SD
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• 제45권5호
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• pp.19-25
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• 2008

본 연구에서는 유기반도체인 펜타센과 소스-드레인 금속전극사이에 $C_{60}$을 홀주입층으로 적용한 유기박막트랜지스터를 제작하여 $C_{60}$을 삽입하지 않은 소자와의 전기적특성을 비교하였다. $C_{60}/Au$ 이중전극을 사용한 소자의 경우 Au단일전극을 사용한 소자와 비교하였을 때 전하이동도는 0.298 $cm^2/V{\cdot}s$에서 0.452 $cm^2/V{\cdot}s$ 문턱전압의 경우 -13.3V에서 -10.8V로 향상되었으며, contact resistance를 추출하여 비교하였을 경우 감소함을 확인할 수 있었다. 이러한 성능의 향상은 $C_{60}$을 Au와 pentacene 사이에 삽입하였을 경우 Au-pentacene 간의 원하지 않는 화학적 반응을 막아줌으로써 홀 주입장벽를 감소시켜 홀 주입이 향상되었기 때문이다. 또한 Al을 전극으로 적용한 OTFT도 제작하였다. 기존에 Al은 OTFT에 단일전극으로 사용하였을 경우 둘간의 높은 홀 주입장벽으로 인해 채널이 거의 형성되지 않았으나, $C_{60}/Al$ 이중전극을 사용한 소자의 경우 전하이동도와 전류점멸비은 0.165 $cm^2/V{\cdot}s$, $1.4{\times}10^4$ 으로써 Al를 단일전극으로 사용하는 소자의 전기적 특성에 비해 크게 향상되어진 소자를 제작할 수 있었다. 이는 $C_{60}$과 Al이 접합시에 interface dipole의 형성으로 Al의 vacuum energy level이 변화로 인한 Al의 work function이 증가되어 pentacene과 Al간의 hole injection barrier가 감소되었기 때문이다.

• Journal of Pharmaceutical Investigation
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• 제25권1호
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• pp.9-17
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• 1995

To stabilize omeprazole(OMP), ethylenediamine(ED) complex of omeprazole(OMPED) was prepared by reaction between OMP and ED in methanol, and the complex formation was confirmed by the instrumental analysis, i.e., IR, DSC, EA, NMR, MS and XRD. The rates of decomposition of OMP and OMPED in aqueous solution and the shelf lives at standard temperature were measured by accelerated stability analysis. The results are summarized as follows; The mole ratio of OMP and ED in OMPED complex is 1:1, the energy of formation within OMPED might be combined between polar imidazole group of OMP with induced a dipole amine group in the readily polarizable ED molecule. At standard temperature the degradation rate constant of OMP in aqueous solution is $2.540{\times}10^{-2}\;hr^{-1}$ and the shelf life is 4.15 hrs, and in the case of OMPED the degradation rate constant is $7.986{\times}10^{-4}\;hr^{-1}$ and the shelf life is 131.96 hrs. So, the OMPED has about 31 times longer shelf life than OMP. The activation energy of OMP and OMPED are 5.23 and 18.55 kcal $mole^{-1}$ respectively. The stability of OMP is dependent chiefly on pH in the solutions and it decomposes readily in acidic medium by hydrogen ion catalized reaction but becomes stable beyond pH 9.0. In case of the ED-complex, OMPED is stable in neutral as well as in dilute acidic solutions even in pH 6, OMPED is very stable to light(UV), that is, the rate constant and shelf life of OMP are $k=1.0188{\times}10^{-2}\;day^{-1}$, $T_{90%}=4.5 \;days$, on the other hand, the those of OMPED are $k=7.138{\times}10^{-4}\;day^{-1}$, $T_{90%}=64.1\;days$, respectively. From the above results, it is thought that new dosage forms could be developed by using the OMPED as a potential OMP complex.

• Bulletin of the Korean Chemical Society
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• 제32권spc8호
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• pp.2955-2959
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• 2011

Second-order rate constants for nucleophilic substitution reactions of 2,4-dinitrophenyl benzenesulfonate 1a with a series of alicyclic secondary amines in MeCN have been measured spectrophotometrically and compared with those reported previously for the corresponding reactions performed in aqueous medium to investigate the effect of medium on reactivity and reaction mechanism. The amines employed in this study are found to be more reactive in the aprotic solvent than in $H_2O$. The reactions of 1a in MeCN result in a linear Br${\o}$nsted-type plot with ${\beta}_{nuc}$ = 0.58, which contrasts to the curved Br${\o}$nsted-type plot reported previously for the corresponding reactions performed in the aqueous medium (i.e., ${\beta}_2$ = 0.86 and ${\beta}_1$ = 0.38). Accordingly, it has been concluded that the reaction mechanism changes from a stepwise mechanism to a concerted pathway upon changing the medium from $H_2O$ to MeCN. Reactions of Y-substituted phenyl benzenesulfonates 1a-c with piperidine in MeCN result in a linear Br${\o}$nsted-type plot with ${\beta}_{lg}$ = -1.31, indicating that expulsion of the leaving group is significantly more advanced than bond formation in the transition state. The trigonal bipyramidal intermediate ($TBPy^{\pm}$) proposed previously for the reactions in $H_2O$ would be highly unstable in MeCN due to strong repulsion between the negative charge in $TBPy^{\pm}$ and the negative dipole end of MeCN. Thus, destabilization of $TBPy^{\pm}$ in MeCN has been concluded to change the reaction mechanism from a stepwise mechanism to a concerted pathway.