• 공업화학
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• 제4권1호
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• pp.153-161
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• 1993

$700-900^{\circ}C$의 온도범위와 여러 산소분압 조건에서 고체전해질 연료전지의 양극인 $La_{0.9}Sr_{0.1}MnO_3$에서 산소의 환원반응특성을 조사하였다. AC 임피던스법과 전류중단법에 의해 산소환원반응의 전하전달저항을 측정하였는데 두 방법으로 구한 간이 서로 잘 일치하였다. 전기화학적 산소환원반응의 활성화에너지는 대기압 조건에서 174kJ/mol의 값을 보였고, 산소분압에 따른 전하전달저항의 측정결과로 부터 이 전극에서 전기화학적 산소환원반응의 율속단계는 전하전달과정임을 알 수 있었다.

• 대한화학회지
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• 제28권3호
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• pp.194-202
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• 1984

陽이온 交換한 天然제올라이트에 依한 有機黃化合物의 液相吸着特性을 考察하였다. 平衡吸着量은 天然제올라이트의 交換한 陽이온과 吸着質인 有機黃化合物의 構造에 影響을 받고 있음을 알 수 있었다. 또한 平衡吸着量은 메르캅탄(mercaptane), 설파이드(sulfide), 디설파이드(disulfide), 치오펜(thiopen) 順으로 減小하였으며, 치오펜 誘導體의 경우는 ${\pi}$ 電子가 많아짐에 따라 吸着能은 교환 이온의 polarizing power에 比例하였다. 吸着速度로부터 有機黃化合物의 吸着은 pore 내의 擴散이 律速段階임을 알수 있었고, 水分과 같은 작은 吸着質은 micro pore에 吸着이 일어나는 反面, 有機黃化合物은 transitional-pore에 吸着이 일어났다.

• 대한화학회지
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• 제39권12호
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• pp.932-939
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• 1995

시프 염기 구리(II) 착물에 의한 과산화수소 분해속도를 측정하였다. 과산화수소와 구리(II)-시프염기 착물의 반응속도는 $Cu^{II}BSDT$ 및 $Cu^{II}BSTP$인 경우 pH에 따라 증가하였으나 $Cu^{II}BSTT$의 경우 증가하였다가 감소하였다. 이 반응의 메카니즘은 과산화수소의 시프염기 구리(II) 착물의 탈양성자를 거친 다음에 속도결정단계에서 퍼옥소 구리착물이 생성되는 반응과정과 일치한다.

• Elastomers and Composites
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• 제37권2호
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• pp.124-133
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• 2002

온화한 조건($80{\sim}110^{\circ}C$, 대기압)하에서 비누화반응에 의해 폐 PBT의 입자를 해중합하여다. PBT의 해중합은 KOH 보다 NaOH가 보다 효과적이었으며, 반응온도가 증가하고 입자의 크기가 작을수록 해중합은 증가하였다. 해중합속도는 표면반응이 율속단계로서 PBT 입자표면에 생성물이 형성되지 않은 미반응핵 모델에 의해 표현할수 있었다. 겉보기활성화에너지는 98.1KJ/mol 이었으며, 85.1, $105{\mu}m$인 PBT 입자를 6시간 동안 해중합하였을때 TPA의 회수율은 약 95%정도였다.

• Translational and Clinical Pharmacology
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• 제26권3호
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• pp.134-140
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• 2018

This study aimed to develop a UPLC-MS/MS method for determining plasma levels of L-aspartic acid and L-asparagine and the activity of L-asparaginase. L-aspartic acid, L-asparagine, and L-aspartic acid-2,3,3-$d_3$ were extracted from human plasma by protein precipitation with sulfosalicylic acid (30%, v/v). The plasma samples were analyzed using an Imtakt Intrada amino acid analysis column with 25 mM ammonium formate and 0.5% formic acid in acetonitrile as the mobile phase with step gradient method at a flow rate of 0.5 mL/min. The injection volume was $5{\mu}L$, and the total run time was 15 min. Inter- and intra-batch accuracies (%) ranged from 96.62-106.0% for L-aspartic acid and 89.85-104.8%, for L-asparagine, and the coefficient of variation (CV%) did not exceed 7%. The validation results for L-aspartic acid and L-asparagine satisfied the specified criterion, however, the results for L-asparaginase activity assay showed a borderline validity. This study could be a foundation for further development of therapeutic drug monitoring systems using UPLC-MS/MS.

• Advances in concrete construction
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• 제11권2호
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• pp.141-149
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• 2021

This study is a basic research for evaluating the buildability of cementitious materials for three-dimensional (3D) printing. In the cement paste step, the thixotropy behavior according to the resting time, which represents the time interval between each layer, was analyzed. In addition, the relationship between the thixotropy behavior and 3D concrete printing buildability was derived by proposing a measurement method that simulates the 3D concrete printing buildup process. The analysis of the tendency of the thixotropy behavior according to the resting time revealed that the area of the hysteresis loop (AHyst) showed a tendency to increase and then converge as the resting time increased, which means hysteresis loop approach critical resting time for sufficient buildability. In the thixotropy behavior analysis that simulates the 3D concrete printing buildup process, the buildup ratio, which is the recovery rate of the shear stress, showed a tendency to increase and then converge as the resting time increased, which are similar results like hysteresis loop. It was concluded that AHyst and the buildup ratio can be used as parameters for determining the resting time, and they have close relationships with 3D concrete printing buildability.

• 한국독성학회:학술대회논문집
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• 한국독성학회 2006년도 추계학술대회
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• pp.65-74
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• 2006

Modem drug discovery requires rapid pharmacokinetic evaluation of chemically diverse compounds for early candidate selection. This demands the development of analytical methods that offer high-throughput of samples. Naturally, liquid chromatography / tandem mass spectrometry (LC-MS/MS) is choice of the analytical method because of its superior sensitivity and selectivity. As a result of the short analysis time(typically 3-5min) by LC-MS/MS, sample preparation has become the rate- determining step in the whole analytical cycle. Consequently tremendous efforts are being made to speed up and automate this step. In a typical automated 96-well SPE(solid-phase extraction) procedure, plasma samples are transferred to the 96-well SPE plate, internal standard and aqueous buffer solutions are added and then vacuum is applied using the robotic liquid handling system. It takes only 20-90 min to process 96 samples by automated SPE and the analyst is physically occupied for only approximately 10 min. Recently, the ultra-high flow rate liquid chromatography (turbulent-flow chromatography)has sparked a huge interest for rapid and direct quantitation of drugs in plasma. There is no sample preparation except for sample aliquotting, internal standard addition and centrifugation. This type of analysis is achieved by using a small diameter column with a large particle size(30-5O ${\mu}$m) and a high flow rate, typically between 3-5 ml/min. Silica-based monolithic HPLC columns contain a novel chromatographic support in which the traditional particulate packing has been replaced with a single, continuous network (monolith) of pcrous silica. The main advantage of such a network is decreased backpressure due to macropores (2 ${\mu}$m) throughout the network. This allows high flow rates, and hence fast analyses that are unattainable with traditional particulate columns. The reduction of particle diameter in HPLC results in increased column efficiency. use of small particles (<2 urn), however, requires p.essu.es beyond the traditional 6,000 psi of conventional pumping devices. Instrumental development in recent years has resulted in pumping devices capable of handling the requirements of columns packed with small particles. The staggered parallel HPLC system consists of four fully independent binary HPLC pumps, a modified auto sampler, and a series of switching and selector valves all controlled by a single computer program. The system improves sample throughput without sacrificing chromatographic separation or data quality. Sample throughput can be increased nearly four-fold without requiring significant changes in current analytical procedures. The process of Bioanalytical Method Validation is required by the FDA to assess and verify the performance of a chronlatographic method prior to its application in sample analysis. The validation should address the selectivity, linearity, accuracy, precision and stability of the method. This presentation will provide all overview of the work required to accomplish a full validation and show how a chromatographic method is suitable for toxirokinetic sample analysis. A liquid chromatography/tandem mass spectrometry (LC-MS/MS) method developed to quantitate drug levels in dog plasma will be used as an example of tile process.

• Bulletin of the Korean Chemical Society
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• 제31권5호
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• pp.1199-1203
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• 2010

Second-order rate constants ($k_N$) have been measured spectrophotometrically for Michael-type reactions of 1-(X-substituted phenyl)-2-propyn-1-ones (2a-f) with a series of alicyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The $k_N$ value increases as the incoming amine becomes more basic and the substituent X changes form an electron-donating group (EDG) to an electron-withdrawing group (EWG). The Br${\o}$nsted-type plots are linear with ${\beta}_{nuc}$ = 0.48 - 0.51. The Hammett plots for the reactions of 2a-f exhibit poor correlations but the corresponding Yukawa-Tsuno plots result in much better linear correlations with ${\rho}$ = 1.57 and r = 0.46 for the reactions with piperidine while ${\rho}$ = 1.72 and r = 0.39 for those with morpholine. The amines employed in this study are less reactive in MeCN than in water for reactions with substrates possessing an EDG, although they are ca. 8 pKa units more basic in the aprotic solvent. This indicates that the transition state (TS) is significantly more destabilized than the ground state (GS) in the aprotic solvent. It has been concluded that the reactions proceed through a stepwise mechanism with a partially charged TS, since such TS would be destabilized in the aprotic solvent due to the electronic repulsion between the negative-dipole end of MeCN and the negative charge of the TS. The fact that primary deuterium kinetic effect is absent supports a stepwise mechanism in which proton transfer occurs after the rate-determining step.

• Bulletin of the Korean Chemical Society
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• 제33권10호
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• pp.3253-3257
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• 2012

Second-order rate constants for the reactions of phenyl Y-substituted-phenyl carbonates 5a-g with Z-substituted-phenoxides ($k_{Z-PhO^-}$) have been measured spectrophotometrically in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. 4-Nitrophenyl phenyl carbonate (5e) is up to 235 times more reactive than 4-nitrophenyl benzoate (4e). The Br$\o$nsted-type plot for the reactions of 5e with Z-substituted-phenoxides is linear with ${\beta}_{nuc}=0.54$, which is typical for reactions reported previously to proceed through a concerted mechanism. Hammett plots correlated with ${\sigma}^o$ and ${\sigma}^-$ constants for the reactions of 5a-f with 4-chlorophenoxide exhibit highly scattered points. In contrast, the Yukawa-Tsuno plot results in an excellent linear correlation with ${\rho}_Y=1.51$ and r = 0.52, indicating that the leaving-group departure occurs at the rate-determining step (RDS). A stepwise mechanism, in which leaving-group departure occurs at RDS, has been excluded since the incoming 4-$ClPhO^-$ is more basic and a poorer nucleofuge than the leaving Y-substituted-phenoxides. Thus, the reaction has been concluded to proceed through a concerted mechanism. Our study has shown that the modification of the nonleaving group from benzoyl to phenyloxycarbonyl causes a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway) as well as an increase in the reactivity.

• Bulletin of the Korean Chemical Society
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• 제34권7호
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• pp.2023-2028
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• 2013

A kinetic study is reported for the nucleophilic substitution reactions of phenyl Y-substituted-phenyl carbonates (5a-5k) with piperidine in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [piperidine] for the reactions of substrates possessing a strong electron-withdrawing group (EWG) in the leaving group (i.e., 5a-5i) are linear and pass through the origin. In contrast, the plots for the reactions of substrates bearing a weak EWG or no substituent (i.e., 5j or 5k) curve upward, indicating that the electronic nature of the substituent Y in the leaving group governs the reaction mechanism. Thus, it has been suggested that the reactions of 5a-5i proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate (i.e., $T^{\pm}$) while those of 5j and 5k proceed through a stepwise mechanism with two intermediates (i.e., $T^{\pm}$ and its deprotonated form $T^-$). The slope of the Br${\o}$nsted-type plot for the second-order rate constants (i.e., $k_N$ or $Kk_2$) changes from -0.41 to -1.89 as the leaving-group basicity increases, indicating that a change in the rate-determining step (RDS) occurs. The reactions of 5a-5k with piperidine result in larger $k_1$ values than the corresponding reactions with ethylamine.