• Bulletin of the Korean Chemical Society
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• 제35권3호
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• pp.770-774
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• 2014

The bond dissociation energy (BDE) of the chemical bond between the carbon and oxygen atoms of a simple TEMPO-derivative is calculated by employing the density functional theory, the $2^{nd}$ order M${\phi}$ller-Plesset (MP2) perturbation theory, and complete basis set (CBS) methods. We find that BDE of the positive ion of the TEMPO-derivative is larger at least by 7 kcal/mol than that of the negative ion, which implies that the dissociation reaction rate of the positive ion should be slower than that of the negative ion. Such theoretical predictions are contrary to the results of our previous experiments (Anal. Chem. 2013, 85, 7044), in which the larger energy was required for negative o-TEMPO-Bz-C(O)-peptides to undergo the dissociation reactions than for the positive ones. By comparing our theoretical results to those of the experiments, we conclude that the dissociation reaction of o-TEMPO-Bz-C(O)-peptide should occur in a complicated fashion with a charge, either positive or negative, probably being located on the amino acid residues of the peptide.

• Bulletin of the Korean Chemical Society
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• 제29권11호
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• pp.2241-2246
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• 2008

• Bulletin of the Korean Chemical Society
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• 제29권5호
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• pp.1051-1054
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• 2008

The entropy production in a non-equilibrium state based on the reversible Oregonator model of the Belousov-Zhabotinskii (BZ) reaction system has been studied. The reaction affinity and the reaction rate for the individual steps have been calculated by varying the concentrations of key variables in the system. The result shows a linear relationship between the reaction affinity and the reaction rate in the given concentration range. However, the overall entropy calculated on the basic assumption that the entropy in a reaction system corresponds to the summation of a product of reaction affinity and reaction rate of individual steps shows a nonlinearity of the reaction system. The results well agrees with the fact that the entropy production is not linear or complicated function in a non-linear reaction system.

• 대한화학회지
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• 제47권5호
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• pp.472-478
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• 2003

본 연구에서는 표면처리된 제올라이트에 따른 제올라이트/DGEBA의 경화 동력학과 기계적 계면특성을 고찰하였다. 경화제는 4, 4''-diamino diphenyl methane(DDM)을 사용하였으며, 제올라이트는(PZ) 15와 35 wt% KOH (15-BZ 그리고 35-BZ)로 표면처리하여 XPS와 XRD로 분석하였다. 경화 동력학은 DSC로 분석하였으며, 시편의 기계적 계면특성은 임계응력 세기인자(critical stress intensity factor, $K_{IC}$)와 임계변형에너지 방출속도(critical strain energy release rate, GIC)를 통하여 알아보았다. XPS와 XRD의 결과로부터, KOH로 표면처리된 제올라이트는 나트륨 (Na)이 칼륨(K)으로 이온교환되었으며, 표면처리로 인한 Al-O의 결합세기의 약화로 $Si_{2p}/Al{2p}$의 값이 증가하였다. 동적 DSC와 기계적 계면특성 결과로부터, 제올라이트/DGEBA 중에서 15-BZ의 경화 활성화에너지($E_a$)는 감소하였으며, $K_{IC}$와 $G_{IC}$는 증가하였다. 이러한 결과들은 제올라이트의 표면처리에 의해 산성도가 증가하였으며, 이렇게 증가된 산성도가 제올라이트와 에폭시 사이의 경화반응에 영향을 준 것으로 관찰된다.

• Bulletin of the Korean Chemical Society
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• 제19권7호
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• pp.743-746
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• 1998

The Belousov-Zhabotinskii (BZ) reaction, which is composed of a bromate-organic acid-metal catalyst and an acidic solution is a commonly employed chemical oscillating reaction system. Cyclohexanedione (CHD) has been used as an initial organic substrate in oscillation systems. We studied each system of 1,4-CHD/BrO3-/Ce4/H+ and 1,3-CHD/BrO3-/Ce4+/H+ oscillating reactions, and studied the control of oscillating characters in a CHD/BrO3-/Ce4+/H+ batch system using a mixed substrate of 1,4-CHD and 1,3-CHD under a fixed total CHD concentration. In the mixed reactions, 1,4-CHD was used as a main substrate and small amounts of 1,3-CHD were used in order to vary the oscillatory behaviours by changing the mixing amount ratio of two substrates.

• Bulletin of the Korean Chemical Society
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• 제33권10호
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• pp.3397-3406
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• 2012

Three types of spherulitic morphologies have been investigated in dual substrate mode of Belousov-Zhabotinsky (BZ) type reaction system. Prior to growth of spherulites, three distinct patterning behaviors have been observed sequentially during the reaction process. Initial and the early-phase of reaction showed the emergence of concentric ring-like wave patterns. A colloidal-state of reaction consists of numerous fine solid particles, which forms primarily some nucleation centers of dendritic characters. The nucleation centers were found to grow in sizes and shapes with the progress of reaction. It leads to growth of dendritic-like spherulitic crystal patterns. The resultant spherulites showed transitions in their morphologies, including sea-weeds and rhythmic spherulitic crystal patterns, by the effects substituted organic substrate and in the higher concentration of bromate-initiator respectively. The branching mechanism and crystal ordering of spherulitic textures were studied with help of optical microscope (OPM) and scanning electron microscope (SEM). Characteristics of crystal phases were also evaluated using X-ray diffraction (XRD) and differential thermal analysis (DTA). Results indicated that the compositions of reactants and crystal orderings were interrelated with morphological transitions of spherulites as illustrated and described.

• Macromolecular Research
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• 제16권2호
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• pp.108-112
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• 2008

Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) analysis of nonpolar polymeric materials is affected by the sample preparation as well as the matrix and cationizing agent. This study examined the influence of silver salt types on the MALDI analysis of polybutadiene (PB). Silver trifluoroacetate (AgTFA), silver benzoate (AgBz), silver nitrate ($AgNO_3$), and silver p-toluenesulfonate (AgTS) were used as the silver salts to compare the MALDI mass spectra of PB. The mixture solution of PB and 2,5-dihydroxybenzoic acid (DHB), as a matrix dissolved in THF, was spotted on the sample plate and dried. A droplet of the aqueous silver salt solution was placed onto the mixture. The mass spectrum with AgBz showed the clear $[M+Ag]^+$ ion distribution of PB while the mass spectrum with AgTFA did not show $[M+Ag]^+$ ions but only silver cluster ions. The mass spectra with $AgNO_3$ and AgTS did not show a clear $[M+Ag]^+$ ion distribution. The difference in the formation of $[M+Ag]^+$ ions of PB depending on the silver salts was attributed to the silver cation transfer reaction between the silver salt and the matrix (DHB). The mass spectrum showed a clear $[M+Ag]^+$ ion distribution of PB when the conjugate acid of the silver salt was less acidic than the matrix.

• Bulletin of the Korean Chemical Society
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• 제28권9호
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• pp.1489-1492
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• 2007

Belousov-Zhabotinsky (BZ) reaction containing oxalic acid and acetone as a mixed organic substrate catalyzed by Ce(IV) in a flow system has been investigated. The reaction system is analyzed by varying flow rate, inflow concentrations, and temperature. Interchangeable oscillating patterns are observed in a certain range of concentrations, and above or below the condition a steady state is obtained. The increase in temperature increases the frequency and decreases the amplitude of oscillations. The apparent activation energy for the system is calculated by using the Arrhenius equation, which means that temperature has a greater effect on the reaction. Bifurcation phase diagrams for the system show the region of oscillations or steady states along with a small region of multistability. Further the behavioral trend observed in this system is discussed by mechanistic character of the system.

• 대한방사성의약품학회지
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• 제5권1호
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• pp.18-25
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• 2019

2-Nitroimidazole derivatives have been reported to accumulate in hypoxic tissue. We prepared a novel $^{99m}Tc-MAG_3$-2-nitroimidazole and evaluated the feasibility for hypoxia imaging agent. $Bz-MAG_3$-2-nitroimidazole was synthesized by direct coupling of $Bz-MAG_3$ and 2-nitroimidazole using dicyclohexylcarbodiimide. $Bz-MAG_3$-2-nitroimidazole was labeled with $^{99m}Tc$ in the presence of tartaric acid and $SnCl_2-2H_2O$ at $100^{\circ}C$ for 30 min. And the reaction mixture was purified by $C_{18}$ Sep-pak cartridge. The labeling efficiency and the radiochemical purity were checked by ITLC-SG/acetonitrile. The tumor was grown in balb/c mice for 8~13 days after the subcutaneous injection of tumor cells, CT-26 (murine colon adenocarcinoma cell). Biodistribution study and tumor autoradiography were performed in the xenografted mice after i.v injection of 74 kBq/0.1 mL and 19 MBq/0.1 mL of $^{99m}Tc-MAG_3$-2-nitroimidazole, respectively. In vivo images of $^{99m}Tc-MAG_3$-2-nitroimidazole in tumor bearing mice were obtained 1.5 hr post injection. The labeling efficiency was $45{\pm}20%$ and the radiochemical purity after purification was over 95%. Paper electrophoresis confirmed negative charge of $^{99m}Tc-MAG_3$-2-nitroimidazole. $^{99m}Tc-MAG_3$-2-nitroimidazole was very stable at room temperature and its protein binding was 53%. The $^{99m}Tc-MAG_3$-2-nitroimidazole exhibited high uptake in the liver, stomach and intestine. In biodistribution study using tumor bearing mice, the uptakes (% ID/g) of the tumor were $0.5{\pm}0.1$, $0.4{\pm}0.0$, $0.2{\pm}0.1$ and $0.1{\pm}0.1$ at 5, 15, 30 min and 4 hrs. Tumor/muscle ratio were $1.4{\pm}0.1$, $2.2{\pm}0.83$, $3.0{\pm}0.9$, and 3.7 (n=2) for 5, 15, 30 min and 4 hrs. The uptake in hypoxic area was found higher than in non-hypoxic area of tumor tissue by autoradiography. In vivo images showed the relatively faint uptake to the hypoxic tumor region. $^{99m}Tc-MAG_3$-2-nitroimidazole was successfully synthesized and found feasible for imaging hypoxia.

• 공업화학
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• 제19권1호
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• pp.51-58
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• 2008

내마모제로 사용하기 위하여 mercaptobenzothiazole 및 디알킬렌디티오카바메이트 그룹을 함유하는 환경친화적인 올레인산 에스테르를 디알킬아민과 이황화탄소의 치환반응, 디클로로아세톤과의 치환반응, $NaBH_4$을 사용한 환원반응 및 올레인산과의 축합반응 등의 과정을 행하여 90% 이상의 수율로 합성하였다. 중간 생성물 및 내마모제의 구조적 특성은 FT-IR, $^1H$-NMR 스펙트럼 및 원소분석으로 분석하였으며 광유계 오일(100 N) 및 식물유에서의 용해성을 1 중량%에서 평가한 결과 잘 용해되었다. 또한, 합성한 내마모제의 열 안정성을 TGA로 분석하였으며 초기 5 wt% 분해온도가 구조에 따라 $192^{\circ}C$에서 $217^{\circ}C$의 안정성을 나타내었다. CEC L-33-A-93 방법으로 생분해도를 평가한 결과 89%에서 99%의 생분해도를 나타내어 환경친화적인 내마모제임을 확인하였다. 내마모제의 윤활특성을 100 N 윤활기유 및 식물유에 첨가하여 4구 마모시험기를 사용하여 평가한 결과, 100 N BO에서 4-ball 마모흔의 직경은 Bz-thia-OE < C4-DTC-OE < Pyrro-DTC-OE < C8-DTC-OE의 순으로 큰 값을 나타내어 내마모성능이 나쁘게 나타났다. 한편, 식용유에서는 4-ball 마모흔의 직경이 0.8260 mm에서 0.9637 mm를 나타내어 내마모제의 첨가효과가 나타나지 않았다.