• Bulletin of the Korean Chemical Society
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• v.35 no.3
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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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• v.29 no.11
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• pp.2241-2246
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• 2008

• Bulletin of the Korean Chemical Society
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• v.29 no.5
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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.

• Journal of the Korean Chemical Society
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• v.47 no.5
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• pp.472-478
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• 2003

In this work, the zeolite/diglycidylether of bisphenol A(DGEBA) systems were investigated in terms of the cure kinetics and mechanical interfacial properties of the composites. The 4, 4-diamino diphenyl methane(DDM) was used as a curing agent for epoxy. Two types of zeolite(PZ) were prepared with 15 and 35 wt% KOH treatments(15-BZ and 35-BZ, respectively) for 24 h, and their surface characteristics were studied by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction(XRD). Cure kinetics of the composites were examined in the context of differential scanning calorimetry(DSC), and mechanical interfacial properties were investigated in critical stress intensity factor($K_{IC}$) and critical strain energy release rate($G_{IC}$). In the results of XPS and XRD, sodium ion(Na) of zeolite was exchanged for potassium ion(K), resulting from the treatment of KOH. Also, $Si_{2p}/Al{2p}$ composition ratios of the treated zeolite were increased, which could be attributed to the weakening of Al-O bond in framework. Cure activation energy($E_a$) of 15-BZ composites was decreased, whereas KIC and $G_{IC}$ were increased, compared with those of the pure zeolite/DGEBA composites. It was probably accounted that the acidity of zeolite was increased by surface treatments and the cure reaction between zeolite and epoxy was influenced on the increased acidity of zeolite.

• Bulletin of the Korean Chemical Society
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• v.19 no.7
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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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• v.33 no.10
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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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• v.16 no.2
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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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• v.28 no.9
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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.

• Journal of Radiopharmaceuticals and Molecular Probes
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• v.5 no.1
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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.

• Applied Chemistry for Engineering
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• v.19 no.1
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• pp.51-58
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• 2008

A series of oleic acid esters containing mercaptobenzothiazole and dialkylenedithiocarbamate, which are potential environmentally friendly lubricating grease additives, were synthesized as 90% yield through several method such as nucleophilic substitution of dialkyl amine and carbon disulfide, reduction reaction, and condensation reaction. The structures of the additives were confirmed by $^1H$-NMR, FT-IR and EA analysis. The additives (1 wt%) were soluble in 100 N BO except C4-DTC-OE and soluble in soybean oil. The tribological properties as lubricating additives in 100 N BO were evaluated using 4-ball tester and the results showed as follows: Bz-thia-OE < C4-DTC-OE < Pyrro-DTC-OE < C8-DTC-OE. Whereas, the 4-ball anti-wear properties were not shown in soybean oil.