• Bulletin of the Korean Chemical Society
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• v.35 no.3
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• pp.721-724
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• 2014

We have explored the potential energy surface for the dissociation of the pyridazine molecular ion using G3 model calculations. The pathways have been obtained for the formation of five possible $C_4H_4^{+{\bullet}}$ isomers by the loss of $N_2$ and the consecutive $H^{\bullet}$ loss. It is predicted that the methylenecyclopropene radical cation is the predominant product in the loss of $N_2$, which is formed via the allenylcarbene radical cation, and $CH_2=C-C{\equiv}CH^+$ is the predominant product in the consecutive $H^{\bullet}$ loss.

• Bulletin of the Korean Chemical Society
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• v.32 no.7
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• pp.2301-2305
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• 2011

The potential energy surface (PES) for the loss of HCN or HNC from the pyrazine molecular ion was determined based on quantum chemical calculations using the G3//B3LYP method. Four possible dissociation pathways to form four $C_3H_3N^{+{{\bullet}}$ isomers were examined. A Rice-Ramsperger-Kassel-Marcus quasi-equilibrium theory model calculation was performed to predict the dissociation rate constant and the product branching ratio on the basis of the obtained PES. The resultant rate constant for the HCN loss agreed with the previous experimental result. The kinetic analysis predicted that the formation of $CH=CHN{\equiv}CH^{+{\bullet}}+HCN$ was predominant, which occurred by three consecutive steps, a C-C bond cleavage to form a linear intermediate, a rearrangement to form an H-bridged intermediate, and elimination of HCN.

• YAKHAK HOEJI
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• v.39 no.1
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• pp.48-54
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• 1995

Coupling of tetracycline(Tc) to dithiocarbamate chitosan(DTCC) via chelate bond was investigated varying reaction time, concentration, temperature, pH, and Ca(II)/Tc ratio. The amount of Tc bound to matrix increased to give a maximum and decreased as the reaction proceeded. The degree and rate of dissociation of Tc complex were affected by the reaction temperature, and pH. By running the reaction at low temperature and pH, the degree of dissociation was greatly diminished. Properties of drug-release from DTCC-Ca(II)-Tc complex were studied by batch- and flow-method and release of Tc and CA(II) by flow method followed nearly zero-order. DTCC-Ca(II)-Tc showed very prolonged antimicrobial activity compared to that of free Tc.

• Mass Spectrometry Letters
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• v.10 no.1
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• pp.32-37
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• 2019

The ${\pi}-{\pi}$ interactions of the peptide-dimer and peptide-trimer complexes were investigated in the (VQIVYK + LYQLEN) and (VQIVYK + NNQQNY) mixing solutions. The results showed that tyrosine (Y) residues were critical in the formation of hetero peptide-dimers and -trimers during the early oligomerization process. We used collision-induced dissociation (CID) along with electrospray ionization mass spectroscopy (ESI-MS) to obtain the structural information of the hetero-dimers and -trimers. We chose three amyloidogenic peptides-VQIVYK, NNQQNY, and LYQLEN-from tau protein, yeast prion-like protein Sup35, and insulin chain A, respectively. Hetero-dimer, -trimer, -tetramer, and -pentamer complexes were observed in the mass spectra. The tandem mass spectrum of the hetero-dimer and hetero-trimer showed two different fragmentation patterns (covalent and non-covalent bond dissociation). Y-Y interaction structures were also proposed for the hetero-dimer and -trimer complexes.

• Bulletin of the Korean Chemical Society
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• v.16 no.2
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• pp.157-163
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• 1995

The adsorption and decomposition of NO on a stepped Pt(111) surface have been studied using thermal desorption spectroscopy and Auger electron spectroscopy. NO adsorbs molecularly in two different states of the terrace and the step, which are distinguishable in thermal desorption spectra. NO dissociates via a bent species at the step sites on the basis of vibrational spectrum data reported previously. The dissociation of NO is an activation process : the activation energy is estimated to be about 2 kcal/mol. Increase in the NO dissociation with adsorption temperature is explained by a process controlled by diffusion of the dissociated atomic nitrogen from the step to the terrace of the surface. In addition to NO and N2, the desorption peak of N2O is observed. We conclude that the formation of N2O is attributed to surface reaction of NO and N adsorbed on the surface.

• Korean Journal of Materials Research
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• v.21 no.4
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• pp.220-224
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• 2011

Zircon has excellent thermal, chemical, and mechanical properties, but it is hard to make a dense sintered product because of dissociation during the sintering process. This study analyzes how the addition of $SiO_2$ and $Al_2O_3$ affects the mechanical properties of sintered zircon, particularly in regards to reducing the thermal dissociation and improving the mechanical properties of $ZrSiO_4$. Zircon specimens containing different amounts of $SiO_2$ and $Al_2O_3$ were prepared and sintered to observe how the mechanical properties of $ZrSiO_4$ changed according to the differing amount of $SiO_2$ and $Al_2O_3$. The $ZrSiO_4$ that was used for the starting material was ground by ball mill to an average particle size of 3 ${\mu}m$. The $SiO_2$ and $Al_2O_3$ that was used for additives were ground to an average particle size of 3 ${\mu}m$ and 0.5 ${\mu}m$, respectively. Adding $SiO_2$ resulted in transformation in the liquid phase at high temperatures, which had little effect on suppressing the thermal dissociation but enhanced the mechanical properties of $ZrSiO_4$. When $Al_2O_3$ was added, the mechanical properties of $ZrSiO_4$ decreased due to the formation of pores and abnormal grains in the microstructure of the sintered zircon.

• Korean Journal of Materials Research
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• v.20 no.9
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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 $HfO_2$.

• Journal of the Korean Chemical Society
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• v.30 no.4
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• pp.335-450
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• 1986

The thermodynamic dissociation constants of $[Co(en)]_3Cl_3\;and\;[Co(NH_3)_6Cl_3$ in aqueous solutions at $25{\circ}$ and at the pressure from 1 bar to 2000 bars were measured by conductometric method. The dissociation constants were increased with pressure elevation because of volume decreasing by the formation of charged ions during dissociation reaction. That is, the $pK^T$ values of $[Co(en)]_3Cl_3$ were 2.16 for I bar, 2.08 for 500 bars, 2,08 for 1000 bars, 2.05 for 1500 bars and 2.03 for 2000 bars, respectively and those of $[Co(NH_3)_6Cl_3$ were 2.02 for 1 bar 1.96 for 500 bars, 1.90 for 1000 bars, 1. 88 for 1500 bars and 1. 87 for 2000 bars, respectively. Comparing and analyzing the values of Stokes' radii and $K^T$, the formation of ion pair compound was affected by not only the electrostatic interaction, but also the Interal Conjugate Base(ICB), which was increased by the elevation of the pressure.

• Journal of the Korean Chemical Society
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• v.44 no.5
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• pp.403-409
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• 2000

The formation and dissociation rates of $Zn^{2+}$ Complexes with l,4,7,10-tetraaza-13,16-diox-acyclooctadecane-N,N',N",N'"-tetraacetic acid (1), 1,4,7,10-tetraaza-13,16- dioxacyclooctadecane-N,N',N",N'"-tetramethylacetic acid (2), and 1,4,7,10-tetraaza-13,16- dioxacyclooctadecane-N,N',N",N'"-tetrapropionic acid(3) have been measured by stopped-flow and conventional spectrophotometry. Observations were made at 25.0$\pm$0.1 $^{\circ}C$ and at an ionic strength of 0.10 M NaClO$_4$. The formation reactions of $Zn^{2+}$ ion with 1 and 2 took place by the rapid formation of an intermediate complex (ZnH$_3L^+$) in which the $Zn^{2+}$ ion is incompletely coor-dinated. This might then lead to be a final product in the rate-determining step.ln the pH range 4.76-5.76, the diprotonated (H2L2-) form is the kinetically active species despite of its low concentration. The stability con-stants (log$K_{(ZnH$_3$3$L^+$)}$) and specific water-assisted rate constants (koH) of intermediate complexes have been deter-mined from the kinetic data. The dissociation reactions of $Zn^{2+}$ complexes of 1,2, and 3 were investigated with $Cu^{2+}$ ions as a scavenger in acetate buffer. All complexes exhibit acid-independent and acid-catalyzed con-tributions. The effect of buffer and $Cu^{2+}$ concentration on the dissociation rate has also been investigated. The ligand effect on t dissociation rate of $Zn^{2+}$ complexes is discussed in terms of the side-pendant armsand the chelate ring sizes of the ligands.

• Applied Biological Chemistry
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• v.2
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• pp.9-14
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• 1961

The formation of sulfide from sulfate has been discussed from the thermodynamic principles. No mechanism of the reaction has been presented. From the stoichiometric and Nernst equations for the conversion of sulfate into sulfide, it was concluded that the formation of sulfide from sulfate can take place more readily if pH of a medium is low. The difficulty of this conversion increases with increasing pH. As pH of a medium increases, the degree of dissociation of H₂S into S= increases and this, in turn, renders the chance of precipitation of sulfide as FeS easier. Higher the pH of a soil or medium, greater is the S= concentration. The concentration of ferrous ion required to remove dissolved sulfide in a medium by forming insoluble FeS decreases with increasing pH. From the theory it was pointed out that an application of lime and iron rich foreign substances to a soil may be effective in causing the removal of dissolved sulfide from solution.