• Bulletin of the Korean Chemical Society
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• v.16 no.3
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• pp.202-204
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• 1995

The ultraviolet photochemistry of N,N'-bis(salicylidene)ethylenediamine copper(II), Cu(sal)2en, was investigated with low pressure mercury lamp. Redution of Cu(Ⅱ) and formation of Cl- were shown on 254 nm irradiation both for aerated and deaerated chlorinated hydrocarbon solvent such as CH2Cl2, chloroform, and 1,2-dichloroethane. Relatively long lived $({\tau}=100{\mu}sec)$ intermediate was detected by flash photolysis. Overall photo-process can be described as the formation of Cl- and new copper complex, product(1) by chlorohydrocarbon mediation, photoinduced reduction by abstraction of halogen from solvent, followed by redox induced substitution of axial ligand with chlorine. Product(1) is possibly Cu(III) chlorosalicylaldeimido complex and cyclic -CH2CH2- moiety is absent in the structure. 247nm band of Cu(sal)2en should contain ligand to metal charge transfer character.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.08a
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• pp.68-69
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• 2011

The process of charge transfer at the interface between two semiconductors or between a metal and a semiconductor plays an important role in many areas of technology. The optimization of such devices requires a good theoretical description of the interfaces involved. This, in turn, has motivated detailed mechanistic studies of interfacial charge-transfer reactions at metal/organic, organic/organic, and organic/inorganic semiconductor heterojunctions. Charge recombination of photo-induced electron with redox species such as oxidized dyes or triiodide or cationic HTM (hole transporting materials) at the heterogeneous interface of $TiO_2$ is one of main loss factors in liquid junction DSSCs or solid-state DSSCs, respectively. Among the attempts to prevent recombination reactions such as insulating thin layer and lithium ions-doped hole transport materials and introduction of co-adsorbents, although co-adsorbents retard the recombination reactions as hydrophobic energy barriers, little attention has been focused on the anchoring processes. Molecular engineering of heterogeneous interfaces by employing several co-adsorbents with different properties altered the surface properties of $TiO_2$ electrodes, resulting to the improved power conversion efficiency and long-term stability of the DSSCs. In this talk, advantages of the coadsorbent-assisted sensitization of N719 in preparation of DSSCs will be discussed.

• Journal of the Korean Ceramic Society
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• v.47 no.2
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• pp.169-176
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• 2010

The Fe-treated CNT/$TiO_2$ photocatalysts mixed with anatase and rutile phase have been developed for the decomposition of non-biodegradable different organic dyes like methylene blue (MB), rhodamine B (Rh.B), and methyl orange (MO) in two conditions as ultraviolet and visible light respectively. The results indicate that all the Fe-CNT/$TiO_2$ composites proved to be more efficient photocatalysts since degradation of MB at higher reaction rates, tthe decomposition rate of different dyes increases with an increase of $Fe^{3+}$ concentration in composites the highest rate of decomposition of different dyes was noted under UV irradiation. These results can indicate that the large CNT network is facilitate the electron transfer and strongly adsorb dye molecules on the texted photocatalysts, iron is reactive in the photo-Fenton process resulting in high production of OH radicals and also high activity of the photocatalyst. And Fe particles can generate more photoinduced electrons to conduction band of $TiO_2$ under visible light irradiation. The composites of Fe-CNT/$TiO_2$ photocatalysts synthesized by a sol-gel method were characterized by BET, TEM, SEM, XRD and EDX.

• Korean Journal of Optics and Photonics
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• v.9 no.2
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• pp.104-110
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• 1998

The energy transfer between two incident beams in a photorefractive Cu-doped(0.04 wt. %) ${(K_{0.5}Na_{0.5})}_{0.2}{(Sr_{0.61}Ba_{0.39})}_{0.9}Nb_2O_6$ crystal is investigated at 632.8 nm laser wavelength. In addition, the coherent two-wave coupling properties of a photoinduced refractive-index grating in the presence of amplitude modulation on the signal beam or reference beam are also experimentally investigated. Some preliminary exprimental results are presented for use as a dynamic photorefracitive combiners and pulse shaping elements in coherent optical communication systems and in optical signal processing.

• Bulletin of the Korean Chemical Society
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• v.28 no.2
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• pp.271-275
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• 2007

γ -Glutamyl transpeptidase (EC 2.3.2.2) plays a key role in glutathione metabolism by catalyzing the transfer of the γ -glutamyl residue and hydrolysis of glutathione. The functional residues at the active site of the rat kidney γ -glutamyl transpeptidase were investigated by kinetic studies at various pH, the treatment of diethylpyrocarbonate (DEPC), and photooxidation in presence of methylene blue. An ionizable group affecting the enzymatic activity with an apparent pKa value of 7.1, which is in the range of pKa values for a histidine residue in protein, was obtained by examining the pH-dependence of kinetic parameters. The pH effect on the photoinduced inactivation rate of the enzyme corresponds to that expected for the photooxidation of the free histidine. The involvement of a histidine in the catalytic site of the enzyme was further supported by DEPC modification accompanied by an increase in absorbance at 240 nm, indicating the formation of Ncarbethoxyhistidine. The histidine located at the position of 382 in the precursor of the enzyme is primarily suspected based on the amino acid sequence alignment of the transpeptidases from various organisms.

• Bulletin of the Korean Chemical Society
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• v.22 no.7
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• pp.709-715
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• 2001

We have been studied photosensitization mechanism's additive effect, of perylene 3,4,9,10-tetracarboxyl-diimide and X-phthalocyanine (charge generation materials), using the photochemical and photoelectrochemical approach. It was found that the photoreceptor on the excited state reacts with metal oxide, which creates the charge transfer on the interface of SnO2/electrolyte. In the electrode (X5P1) made of five X-phthalocyanine and single perylene 3,4,9,10-tetracarboxyldiimide layers, the cathodic photocurrent of X-phthalocyanine in the 400-600 nm region was increased by the addition of perylene 3,4,9,10-tetracarboxyldiimide. The maximum wavelength of fluorescence of perylene 3,4,9,10-tetracarboxyldiimide showed no dependence on the temperature. The addition of 4-dibenzylamino-2-methylbenzaldehyde diphenylhydrazone known as charge transport material was represented as decreasing photocurrent for X-phthalocyanine and perylene 3,4,9,10-tetracarboxyldiimide, respectively. In the electrode (X1P1) made of single X-phthalocyanine and single perylene 3,4,9,10-tetracarboxyldiimide layers, an anodic photocurrent of about 10.5 nA was generated by addition of hydroquinone at 550 nm. And the characteristic of photoinduced discharge was shown to decrease by a factor of 5 and the speed of dark decay was increased by a factor of 1.2.

• Journal of the Korean Chemical Society
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• v.55 no.6
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• pp.932-935
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• 2011

Using tetrabutyl titanate as precursor, $Eu^{3+}$ doped $TiO_2$ nano-powder was prepared by sol-gel method, the nature of luminescence of nano-powder was studied. The interaction of chlorpyrifos with $Eu^{3+}$ doped $TiO_2$ was studied by absorption and fluorescence spectroscopy. The results indicated the fluorescence intensity of $Eu^{3+}$ doped $TiO_2$ was quenched by chlorpyrifos and the quenching rate constant ($k_q$) was $1.24{\times}10^{11}\;L/mol{\cdot}s$ according to the Stern-Volmer equation. The dynamics of photoinduced electron transfer from chlorpyrifos to conduction band of $TiO_2$ nanoparticle was observed and the mechanism of electron transfer had been confirmed by the calculation of free energy change (${\Delta}G_{et}$) by applying Rehm-Weller equation as well as energy level diagram. A new rapid method for detection of chlorpyrifos was established according to the fluorescence intensity of $Eu^{3+}$ doped $TiO_2$ was proportional to chlorpyrifos concentration. The range of detection was $5.0{\times}10^{-10}-2.5{\times}10^{-7}mol/L$ and the election limit ($3{\sigma}$) was $3.2{\times}10^{-11}$ mol/L.

• Bulletin of the Korean Chemical Society
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• v.24 no.4
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• pp.446-452
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• 2003

Some new nanohybrid materials have been synthesized by intercalating the oxotitanium(IV) meso-tetrakis(4- sulfonatophenyl) porphyrin$(O=Ti^{(IV)} TSPP)$ into the Zn/Al layered double hydroxides (LDHs), and their structures and photophysical properties have been investigated by various laser spectroscopic techniques. According to the XRD pattern of the synthesized nanohybrid materials, the macrocycle plane of $O=Ti^{(IV)}$ TSPP are grafted perpendicular to the LDH layers. The $O=Ti^{(IV)}$ TSPP-intercalated LDH exhibits band broadening of the absorption spectrum and a blue shift of Q-band as compared to that observed in solution. Resonance Raman spectral measurements demonstrate that the positively charged LDHs give rise to a slight decrease of the electronic density of the porphyrin ring accompanying a small change of the electronic distribution of the $O=Ti^{(IV)}$ TSPP. Consequently the LDH environment affects the energies of the two highest occupied molecular orbitals (HOMOs) of the $O=Ti^{(IV)}$) TSPP, $a_{1u}$ and $a_{2u}$, producing a mixed orbital character. Being consistent with these electronic structural changes of $O=Ti^{(IV)}$ TSPP in LDH, both the fluorescence spectral change and the fsdiffuse reflectance transient measurements imply that the photoexcitation of the $O=Ti^{(IV)}$ TSPP intercalated into LDH undergoes fast relaxation to the O=Ti(IV) $TSPP^+-LDH^- $charge transfer (CT) state within a few picoseconds, followed by a photoinduced electron transfer between the O=Ti(IV) TSPP and LDHs with a rate constant greater than %1×10^{10}S^{-1}$. No evidence is found for back electron transfer. In conclusion, the $O=Ti^{(IV)}$ TSPP intercalated LDH seems to be a possible candidate for an artificial reaction center for an efficient solar energy conversion system.

• Rapid Communication in Photoscience
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• v.3 no.4
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• pp.70-72
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• 2014

Visible-light irradiation of MeCN solution containing di(hydroxo)metallo(tetraphenyl)porphyrin complex $(tppM(OH)_2$: 1a; $M=Sb(V)^+Br^-$, 1b; $M=P(V)^+Cl^-$, 1c; M=Ge(IV)) and 2-mercaptoethanol (2-ME) as a substrate under aerated condition gave bis(2-hydroxyethyl)disulfide (2-HEDS) as an oxidative product of 2-ME. It is indicated that the oxidation of 2-ME should proceed with a photocatalytic process by 1, because the turn over number (TON) for the formation of 2-HEDS was over unit. The TON was determined to be 642 as a maximum value when 1a was used as a sensitizer. The formation of 2-HDES was extremely slow under argon atmosphere. The fluorescence of 1 was not quenched by 2-ME at all, and the free energy change (${\Delta}G$) with electron transfer (ET) from 2-ME to excited triplet state of $1(^31^*)$ was estimated as a negative value. The quenching rate constant ($k_r$) of $^31^*$ by 2-ME, obtained by the kinetics for the formation of 2-HEDS, strongly depends on ${\Delta}G$. These findings indicate that 1-sensitized oxidation was initiated by photoinduced ET from 2-ME to $^31^*$ to generate both radical cation of 2-ME ($2-ME^{+\bulle}$) and porphyrin radical anion ($1^{-\bulle}$), resulting that the formation of 2-HEDS can be proceeded by the dimerization of $2-ME^{+\bulle}$, and through a catalytic cycle due to returning to 1 by the ET from $1^{-\bulle}$ to molecular oxygen.

• Polymer(Korea)
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• v.30 no.5
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• pp.426-431
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• 2006

Novel azacrown ether containing blue -light emitting anthracene fluorophore, 9,10-bis [p-(1-aza-18-crown-6)methylphenyl] anthracene (3) and N,N-bis [9-(p-methylphenyl) anthracenyl-methyl] -1,6-diaza-18-crown-6 (4) were prepared by reacting anthracene derivatives 1 and 2 with mono- and diaza-18-crown-6, respectively Also, crown ether containing fluorophore copolymer (5) were prepared by reacting 1,6-diaza-18-crown-6 with 1. Their fluorescence emission spectral studies were investigated by binding group I, group II and various metal cations. The fluorophores showed an absorption at ${\lambda}_{max}$= 372 nm and an emission at ${\lambda}_{max}$= 430 nm. pH Dependency of fluorescence emission intensity were examined to determine the optimum pH for the fluorophores.