• Journal of the Korean Chemical Society
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• v.37 no.1
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• pp.36-42
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• 1993

In the presence of $Ca^{2+}$ ion, the charge transfer (CT) interaction of nonionic surfactants, $nonylphenol-(ethylene oxide)_n\;[NP-(EO)_n; n = 11, 40, 100]$ with iodine in aqueous solution were investigated by UV-visible spectrophotometer. The characteristics of spectra depended on the concentration of $Ca^{2+}$ ion and the number of EO unit. Above CMC, the intensity of the CT band by the addition of $Ca^{2+}$ ion for the $NP-(EO)_{11}$ and $NP-(EO)_{40}$ increased and then decreased, while for the $NP-(EO)_{100}$ continuously increased. The increase in the intensity of CT band were attributed to the compactness of micelle in the presence of $Ca^{2+}$ ion. These phenomena may be explained by the fact that the linear ethylene oxide (EO) chain, to be free configuration in aqueous solution, could form a pseudo-crown ether structures capable of forming complexes with $Ca^{2+}$ ion.

• 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 Photoscience
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• v.8 no.1
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• pp.33-37
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• 2001

Picosecond absorption spectroscopy has been employed in the study of the solvent dynamics of 1, 2, 4, 5-tetracyanobenzene/biphenyl derivative radical ion pairs, and the resulting rates of radical ion pair separation are faster in acetonitrile than in dichloromethane. In an effort to account quantitatively for such solvent effect on the rate of radical ion pair separation, an equation for the rate of radical ion pair separation is introduced, in which the rate depends exponentially on the electrostatic interaction energy in the radical ion pair. In our analysis of the types of electrostatic interaction energy based on the conducting spheres in dielectric continuum was chosen, and the rate equation employing this electrostatic energy provided information on the distance on the distance of radical ion pair separation and solvation energy of the radical ion pair, thereby providing quantitative explanation for the observed solvent effect on the rate of radical ion pair sepaaration.

• Bulletin of the Korean Chemical Society
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• v.9 no.3
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• pp.179-182
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• 1988

A simple correlation between cross interaction constants ${\rho}_{ij}$ and bond lengths in the transition state was obtained ; it has been shown that ${\rho}_{ij}$ corresponds to force constant of activation, which in turn is related to bond length by Badger's rule involving only universal constants. A satisfactory correlation between 4-31G ab initio calculated values of bond length and force constant for C-X streching in the transition state of the methyl transfer reaction, $X^-\;+\;CH_3X\;=\;XCH_3\;+\;X^-$, indicated that Badger's rule can be extended to bonds in the transition state. Independence of ${\rho}_{ij}$ values from the variable charge transmission of reaction centers has been demonstrated with nearly constant, experimentally determined I${\rho}$XYI values, and hence similar degree of bond formation, for various $S_N2$ reactions.

• Bulletin of the Korean Chemical Society
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• v.34 no.1
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• pp.211-220
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• 2013

The characteristic fluorescence properties of quercetin (QCT) and apigenin (API) were studied in various $CH_3OH-H_2O$ and $CH_3CN-H_2O$ mixed solvents. The structure of QCT is completely planar. API is not planar at the ground state but becomes nearly planar at the excited state. If the molecules are excited to the $S_1$ state in organic solvents, QCT exhibits no fluorescence due to excited state intramolecular proton transfer (ESIPT) between the -OH and the carbonyl oxygen, but API shows significant fluorescence because ESIPT occurs slowly. If the molecules are excited to the $S_2$ state, both QCT and API exhibit strong $S_2{\rightarrow}S_o$ emission without any dual fluorescence. As the $H_2O$ composition of both solvents increases, the fluorescence intensity decreases rapidly due to the intermolecular hydrogen bonding interaction. The theoretical calculation further supports these results. The change in fluorescence properties as a function of the solvatochromic parameters was also studied.

• Bulletin of the Korean Chemical Society
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• v.18 no.11
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• pp.1166-1172
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• 1997

[FeⅢ(BLPA)DBC]BPh4, a new functional model for the catechol dioxygenases, has been synthesized, where BLPA is bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine and DBC is 3,5-di-tert-butylcatecholate dianion. The BLPA complex has a structural feature that iron center has a six-coordinate geometry with N4O2 donor set. It exhibits EPR signals at g=5.5 and 8.0 which are typical values for the high-spin FeⅢ (S=5/2) complex with axial symmetry. The BLPA complex reacts with O2 within a few hours to afford intradiol cleavage (75%) and extradiol cleavage (15%) products which is very unique result of all [Fe(L)DBC] complexes studied. The iron-catecholate interaction of BLPA complex is significantly stronger, resulting in the enhanced covalency of the metal-catecholate bonds and low energy catecholate to FeⅢ charge transfer bands at 583 and 962 nm in CH3CN. The enhanced covalency is also reflected by the isotropic shifts exhibited by the DBC protons, which indicate increased semiquinone character. The greater semiquinone character in the BLPA complex correlates well with its high reactivity towards O2. Kinetic studies of the reaction of the BLPA complex with 1 atm O2 in CH3OH and CH2Cl2 under pseudo-first order conditions show that the BLPA complex reacts with O2 much slower than the TPA complex, where TPA is tris(2-pyridylmethyl)amine. It is presumably due to the steric effect of the methyl substituent on the pyridine ring. Nevertheless, both the high specificity and the fast kinetics can be rationalized on the basis of its low energy catecholate to FeⅢ charge transfer bands and large isotropic NMR shifts for the BLPA protons. These results provide insight into the nature of the oxygenation mechanism of the catechol dioxygenases.

• Bulletin of the Korean Chemical Society
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• v.25 no.2
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• pp.298-300
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• 2004

An alternative molecular porphyrin-phthalocyanine aggregate was prepared and characterized with UV-visible and X-ray absorption spectroscopies. UV-visible experiments evidence 1-dimensional porphyrin-phthalo-cyanine array formed by mixing $SnTPPCl_2 ({\lambda}_{max}=429,\;{\varepsilon}=2.4{\times10^ 5 /M{\cdot}cm)\;and\;NiPc(OBu)_8({\lambda}_{max}=744 nm,\;{\varepsilon}= 2.0{\times}10^ 5 /M{\cdot}cm)$ in solution. In the UV-visible spectrum of the porphyrin-phthalocyanine array, $(SnPNiPc)_n$, a new Q-band appeared at 844 nm with decrease of the Q-band peak of $NiPc(OBu)_8$ at 744 nm. The red-shift of Q-band evidences an alternative porphyrin-phthalocyanine array formed in solution through metal-halide interaction rather than ${\pi}-{\pi}$ facial interaction, in which nickel of $NiPc(OBu)_8$ coordinates with chloride of $SnTPPCl_2$ through self assembly. Ni K-edge XANES (X-ray absorption near edge structure) spectra also support the axial ligation of nickel to chloride. The square planar structure of $NiPc(OBu)_8$ turns to an octahedral structure in (SnPNiPcSnP) by axial ligation. A higher energy-shift (0.2 eV) of the preedge peak of (SnPNiPcSnP) indicaties partial oxidation of nickel by charge transfer from NiPc$(OBu)_8$ to SnTPPCl$_2$.

• Journal of the Korean Chemical Society
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• v.15 no.6
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• pp.352-358
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• 1971

The interaction between dimethylsulfoxide molecules and some organic molecules, i.e.nitrobenzene, m-dinitrobenzene, o-dinitrobenzene, 1,3,5-trinitrobenzene, m-xylene, mesitylene, bibenzyl, biphenyl, o-phenanthrene, naphthalene, has been studied. The organic molecules exhibit negative deviation from Raoult's law due to the formation of the charge transfer complexes with dimethylsulfoxide. The stability constants of the complexes were determined spectrophotometrically, and also some thermodynamic functions were calculated. The binding energies of the complexes appear in the range of -1 ∼ -4 kcal/mole. The stability depends on the polarity and basicity of the solvent used.

• Rapid Communication in Photoscience
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• v.4 no.3
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• pp.73-75
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• 2015

Cr(VI) reduction was successfully achieved in the presence of cationic micelles (CMs) under visible light illumination. Micelle formation of cationic surfactants seems to be critical in Cr(VI) reduction. Cr(VI) was reduced very fast above the critical micelle concentration (cmc) of CTAB solutions, but was not reduced at all either below or around the cmc of CTAB. The reduction rate of Cr(VI) was enhanced in the absence of dissolved oxygen, supporting that the removal of Cr(VI) should be achieved via a reductive pathway. When CTAB was substituted by Brij 35 or SDS, the reduction of Cr(VI) was negligible. This indicates that the electrostatic interaction between Cr(VI) and headgroups of surfactants is important in the visible light-induced Cr(VI) reduction in micellar solutions.

• Journal of Magnetics
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• v.10 no.2
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• pp.71-75
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• 2005

An effective method, i.e., the solid atom method, is suggested to obtain the Coulomb interaction parameter, U, and the Hund exchange coupling constant, J, for use in the LDA+U calculation. The par~meters are obtained self-consistently during the LDA+U calculation. The method is applied to typical transition metal oxides and $MnB^{VI}(B^{VI}=S,Se,Te)$. The U values for the transition metal oxides have similar magnitude to previous calculations although they are obtained by a much simpler method. $MnB^{VI}s$ have been characterized as crossroads materials between charge transfer and band insulators by the LDA+U calculation.