• Bulletin of the Korean Chemical Society
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• v.9 no.3
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• pp.153-156
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• 1988

Ab initio calculations are performed for $ArCO_2^+$ and $ArCO_2$. Between the two configurations of $ArCO_2^+$ the orbital interactions and the higher order correlation calculations favor the T-shape, and their interaction energies are calculated to be approximately half the experimental values using 6-31G$^{\ast}$ basis set. In $ArCO_2$, the calculations qualitatively favor the T-structure, which is compatible with the experiment. However, the true interaction energy is obscured since it is within the BSSE limit at this basis set size and the correlation level. Addition of sp type diffuse functions increase the interaction energies by a considerable amount, but the BSSE estimated by CP method are responsible for the significant portion of the difference. The possible equilibrium structure of the $Ar^+-CO_2$ complex, where the charge is localized on Ar, is suggested as having a linear structure. The potential energy surface and the amount of charge transfer are shown to be sensitive to the type and balancing of basis set.

• Korean Journal of Fisheries and Aquatic Sciences
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• v.12 no.2
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• pp.95-102
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• 1979

Brevibacterium flavum treated with phenol derivatives, guaiacol and o-vanillin has been revealed the marked increased ability in glutamic acid fermentation as 14.2 g/l in o-vanillin treated, 12.5 g/l in guaiacol treated while the 7.0 g/1 in nontreated cell. The increased ability of phenol derivatives treated cells in glutamic acid fermentation was ascribed to the formation of charge-transfer complex between phenols and oxygen. The charge-transfer complex effectively supply the oxygen to the fermention system in spite of high potential gradient in oxygen transfer formed by high cell concentration as insulator on film of air-liquid interface.

• Bulletin of the Korean Chemical Society
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• v.31 no.6
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• pp.1615-1620
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• 2010

Bis-[dipyrido[3,2-$\alpha$:2',3'-c]phenazine)$_2$(1,10-phenanthroline)$_2Ru_2$]$^{2+}$ complexes (bis-Ru(II) complexes) tethered by linkers of various lengths were synthesized and their binding properties to DNA investigated by normal absorption and linear dichroism spectra, and fluorescence techniques in this study. Upon binding to DNA, the bis-Ru(II) complex with the longest linker (1,3-bis-(4-pyridyl)-propane), exhibited a negative $LD^r$ signal whose intensity was as large as that in the DNA absorption region, followed by a complicate $LD^r$ signal in the metal-to-ligand charge transfer region. The luminescence intensity of this bis-Ru(II) complex was enhanced. The observed $LD^r$ and luminescence results resembled that of the [Ru(1,10-phenanthroline)$_2$ dipyrido[3,2-$\alpha$:2',3'-c]phenazine]$^{2+}$ complex, whose dipyrido[3,2-$\alpha$:2',3'-c]phenazine (dppz) ligand has been known to intercalate between DNA bases. Hence, it is conclusive that both dppz ligands of the bis-Ru(II) complex intercalate. The binding stoichiometry, however, was a single intercalated dppz per ~ 2.3 bases, which violates the "nearest binding site exclusion" model for intercalation. The length between the two Ru(II) complexes may be barely long enough to accommodate one DNA base between the two dppz ligands, but not for two DNA bases. When the linker was shorter (4,4'-bipyridine or 1,2-bis-(4-pyridyl)-ethane), the magnitude of the LD in the dppz absorption region, as well as the luminescence intensity of both bis-Ru(II) complexes, was half that of the bis-Ru(II) complex bearing a long linker. This observation can be elucidated by a model whereby one of the dppz ligands intercalates while the other is exposed to the aqueous environment.

• Journal of the Korean Chemical Society
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• v.23 no.5
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• pp.314-319
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• 1979

The electronic spectrum of marine dinoflagellate antenna pigment, peridinin, has been described in terms of PPP SCF MO CI computations and fluorescence polarization of the peridinin component in photosynthetic pigment complex of Amphidinium carterae. The main absorption band at 470 nm, $^1B{\leftarrow}A$, is polarized nearly along the long molecular axis. There appear to be two ${\pi}{\rightarrow}{\pi}^*$ transitions (C and $D{\leftarrow}A$) in the socalled "cis" peak region, and they are polarized roughly parallel to the main $B{\leftarrow}A$ absorption. In addition, we have found that the carbonyl group undergoes very 1ittle reorganization of the electronic structure in going from the ground to the $^1B$ excited states of peridinin, while the allenic group shows a strong charge transfer tendency in producing an electron-deficient allente allene group in the excited state.

• Journal of Energy Engineering
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• v.22 no.4
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• pp.399-405
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• 2013

The gas motion inside the engine cylinder plays a very important role in determining the thermal efficiency of an internal combustion engine. A precise information of in-cylinder three dimensional complex gas motion is crucial in optimizing engine design. Homogeneous charge compression ignition (HCCI) engine is a combustion concept, which is a hybrid between Otto and Diesel engine. The turbulent diffusion leads to increased rates of momentum, heat and mass transfer. The in-cylinder turbulence flow was found to affect the present HCCI combustion mainly through its influence on the wall heat transfer. This study investigates the effect of piston geometry shape on the turbulent flow characteristics of in-cylinder from the numerical analysis using the LES model and the results obtained can offer guidelines of the combustion geometries for better combustion process and engine performance.

• Applied Chemistry for Engineering
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• v.9 no.6
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• pp.811-816
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• 1998

Rebar corrosion in cement mortar containing chloride ions was investigated by electrochemical AC impedance spectroscopy. Corrosion of mild steel bar was accelerated by an acceleration test equipment in short period. Impedance values obtained from AC-impedance method could be adapted to the proposed electrochemical equivalent circuit model and they were consistent with calculated values obtained by CNLS fitting method. The weight loss of rebar could be calculated by charge transfer resistance($R_2$) with time and it was close to real value.

• Bulletin of the Korean Chemical Society
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• v.27 no.12
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• pp.2002-2010
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• 2006

This study examined the quenching of ofloxacin (OFL) and flumequine (FLU) fluorescence by $Cuj^{2+}$, $Ni^{2+}$, $Co^{2+}$ and $Mn^{2+}$ in an aqueous solution. The change in the fluorescence intensity and lifetime was measured at various temperatures as a function of the quencher concentration. According to the Stern-Volmer plots, the fluorescence emission was quenched by both collisions (dynamic quenching) and complex formation (static quenching) with the same quencher but the effect of static quenching was larger than that of dynamic quenching. Large static and dynamic quenching constants for both OFL and FLU support significant ion-dipole and orbital-orbital interactions between fluorophore and quencher. For both molecules, the static and dynamic quenching constants by $Cu^{2+}$ were the largest among all the metal quenchers examined in this study. In addition, both the static and dynamic quenching mechanisms by $Cu^{2+}$ were somewhat different from the quenching caused by other metals. Between $Ni^{2+}$ and FLU, a different form of chemical interaction was observed compared with the interaction by other metals. The change in the absorption spectra as a result of the addition of a quencher provided information on static quenching. With all these metals, the static quenching constant of FLU was larger than those of OFL. The fluorescence of OFL was quite insensitive to both the dynamic and static quenching compared with FLU. This property of OFL can be explained by the twisted intramolecular charge transfer in the excited state.

• Journal of Hydrogen and New Energy
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• v.24 no.1
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• pp.61-69
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• 2013

Polymer exchange membrane (PEM) fuel cells have multifunctional properties, and bipolar plates are one of the key components in these fuel cells. Generally, a bipolar plate has a gas flow path for hydrogen and oxygen liberated at the anode and cathode, respectively. In this study, the influence of iodine applied to a bipolar plate was investigated. Accordingly, we compared bipolar plates with and without iodine coating, and the performances of these plates were evaluated under operating conditions of $75^{\circ}C$ and 100% relative humidity. The membrane and platinum-carbon layer were affected by the iodine-coated bipolar plate. Bipolar plates coated with iodine and a membrane-electrode assembly (MEA) were investigated by electron probe microanalyzer (EPMA) and energy-dispersive x-ray spectroscopy (EDS) analysis. Polarization curves showed that the performance of a coated bipolar plate is approximately 19% higher than that of a plate without coating. Moreover, electrochemical impedance spectroscopy (EIS) analysis revealed that charge transfer resistance and membrane resistance decreased with the influence of the iodine charge transfer complex for fuel cells on the performance.

• Polymer(Korea)
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• v.32 no.6
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• pp.580-586
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• 2008

Copolyimides were synthesized from 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 1,3-bis(3-aminophenoxy)benzene (BAPB) with different mole ratios of 2,2-bis[4-(4-aminophenoxy)pheny1]hexafluoropropane (BAPP). The solution cast film of poly(amic acid) (PAA) was heat treated at different temperatures to create copolyimide films. The PI copolymer films were found to exhibit good optical transparencies. The thermomechanical properties, morphology, and optical transparency of PI films were examined using fourier transform infrared spectroscopy (FT-IR), wide-angle X-ray diffraction (XRD), scanning electron microscopes (SEM), differential scanning calorimeter(DSC), thermo-gravimetric analyzer (TGA), universal tensile machine (UTM), and IN - Vis. spectrometer. The glass transition temperature ($T_g$), ultimate strength, and initial modulus linearly increased with increasing BAPP mole fraction. However, thermal stability($T_D{^i}$) of the copolyimide remains constant regardless of BAPP loadings. It was found, however, that the optical transparency decreases slightly upon increasing the BAPP content because of the formation of the charge transfer complexes.

• Bulletin of the Korean Chemical Society
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• v.19 no.9
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• pp.897-906
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• 1998

A new synthesis has been developed for 1-thia-4,7-diazacyclononane and the complexation behavior of a particular derivative has been explored. The pentadentate ligand 4,7-bis(2-pyridylmethyl)-l-thia-4,7-diazacyclononane ([9]$N_2SPY_2$) and its iron(Ⅱ) and manganese(Ⅱ) complexes were prepared and characterized. Magnetic moments of 5.17 and 5.90 μB respectively, indicate that the iron(Ⅱ) and manganese(Ⅱ) complexes are high spin. Charge transfer transitions (d-π*) occur for [Fe(Ⅱ)([9]$N_2SPY_2)(X)]^{n+}$at 27027, 25000, and 24390 cm-1 for X=$H_2O$, Cl-, and OH-, respectively. In acetonitrile solution, the cyclic voltammogram of the manganese(Ⅱ) complex exhibits a redox couple at 0.92 V vs. NHE while the redox potentials for [Fe(Il)([9]$N_2SPY_2)(X)]^{n+}$ are 0.70, 0.66, and 0.37 V vs. NHE for X=$H_2O$, Cl-, and OH-, respectively. The d-π* charge transfer energy and Fe(Ⅱ)/Fe(Ⅲ) redox potential for [Fe(Ⅱ)([9]$N_2SPY_2)(X)]^{n+}$ increase in the same order: $H_2O>Cl^- >OH^-$. The crystal structures of the iron(Ⅱ) and manganese(Ⅱ) complexes reveal that the metal ions are sixcoordinate, binding to four nitrogen atoms and a sulfur atom from the pentadentate ligand, as well as a chloride anion, with the chloride and sulfur atoms in cis positions. The two metals have similar coordination geometries, which are closer to trigonal prismatic than octahedral. In both iron and manganese complexes, the M-N($sp_3$) trans to Cl- is 0.07 Å longer than the one cis to Cl- , and M-N($sp^2$) trans to S is 0.05 longer than the one cis to S atom.