• 대한화학회지
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• 제37권1호
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• pp.36-42
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• 1993

$Ca^{2+}$ 이온 존재하에서 비이온성 계면활성제, $nonylphenol-(ethylene oxide)_n\;[NP-(EO)_n; n = 11, 40, 100]$와 요오드간의 charge transfer (CT) 상호작용을 UV-Visible spectrophotometer를 이용하여 수용액중에서 조사하였다. Spectra의 특성은 $Ca^{2+}$ 이온 농도와 EO 갯수에 의존하였다. CMC 이상에서 $NP-(EO)_{11}$과 $NP-(EO)_{40}$에 대한 $Ca^{2+}$이온 첨가에 따른 CT band는 증가하다가 다시 감소하였으며, $NP-(EO)_{100}$에 대해서는 계속적인 증가를 보였다. CT band의 강도가 증가하는 것은 $Ca^{2+}$이온 존재하에서 미셀 구조가 더욱 조밀해진데 따른 요오드와의 donor-acceptor overlap 증가로 볼 수 있다. 이러한 현상들은 수용액 중에서 상태적으로 자유로이 여러가지 배향을 가질 수 잇는 선형 ethylene oxide(EO) 사슬이 유사 크라운 에테르 구조를 형성하여 $Ca^{2+}$ 이온과 착물을 형성할 수 있는 가능성을 보여준다.

• Bulletin of the Korean Chemical Society
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• 제27권12호
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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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• 제8권1호
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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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• 제9권3호
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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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• 제34권1호
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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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• 제18권11호
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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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• 제25권2호
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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$_2$.

• 대한화학회지
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• 제15권6호
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• pp.352-358
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• 1971

열가지 유기물질, 즉 니트로벤젠, m-디니트로벤젠, o-디니트로벤젠 1,3,5-트리니트로벤젠, m-크실렌, 메시틸렌, 비벤질, 비페닐, o-페난트린, 및 나프탈린등과 dimethylsulfoxide사이의 상호작용을 검토했다. 이 유기분자들은 모두 라울의 법칙에서 음의 편차를 나타내며, 전하전이착물을 형성한다고 생각된다. 그 착물의 안정도상수를 분광광도법으로 측정하고, 몇가지 열력학함수를 계산했으며 결합에너지가 대개 -1∼-4 kcal/몰임을 알았다. 한편 용매의 영향을 검토하여 착물의 안정도가 용매의 극성은 물론 염기도에 크게 의존함을 알았다.

• Rapid Communication in Photoscience
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• 제4권3호
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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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• 제10권2호
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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.