• 한국수소및신에너지학회논문집
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• 제2권1호
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• pp.7-13
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• 1990

광합성계를 모방한 인공물의 광분해기에는 광증감제, 전자공여체 및 전자수용체가 필요하다. 광합성계에서는 Mn-tetramer가 물의 산화를 담당하는 종이라는 것이 알려져 있으니 Mn 화합물의 반응성을 아는 것이 중요하다. 이 Mn-tetramer의 모델이 될 수 있는 지용성 및 수용성 Mn(III) porphyrin을 새로이 합성하였다. 지용성 Mn(III) porphyrin은 porphyrin 자체에 금속화하는 방법과 porphyrin 고리 자체를 합성 할 때 긴 탄소사슬을 넣는 방법을 이용하였다. 지용성이나 수용성 Mn(III) Porphyrin은 계면에서 거동이 다를 것으로 생각되기 때문에 그 합성에 의의가 있다고 하겠다. 이 합성된 Mn(III) porphyrin 유도체들은 아민이나 알코올이 존재하는데서 광환원된다는 사실을 알게 되었다. 이 사실은 광증감제와 더불어 이중으로 여기시킬 수 있다는 점에서 큰 의의가 있다.

• Bulletin of the Korean Chemical Society
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• 제22권12호
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• pp.1316-1322
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• 2001

Transition metal complexes of novel mono- and di-ferrocene-substituted porphyrins have been synthesized and characterized by structural and electrochemical methods. The X-ray structures of Mn(FPTTP)Cl and Mn(DFTTP)Cl showed the distorted square pyramidal coordination geometry with syn configuration of chloride and ferrocenyl substituents. The electrochemistry of ferrocene-substituted porphyrins and their metal complexes has been determined to elucidate the ${\pi}-conjugation$ effect of the porphyrin ring. The ferrocenyl group of H2FPTTP underwent a reversible one-electron transfer process at 0.30 V, indicating the good electron donating effect of the phorphyrin ring to the ferrocene substituent. The redox potential of the ferrocenyl subunit and porphyrin ring was affected by the central metal ions of the metalloporphyrins, that is, Zn(II) and Ni(II) made the oxidation of ferrocene much easier and Mn(III) made it harder. The ferrocene subunits of H2DFTTP interacted electrochemically with each other with peak splitting of 0.21 V. The strength of the electrochemical interactions between the two ferrocenyl substituents can be controlled by central metal ions of metalloporphyrins.

• 한국응용과학기술학회지
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• 제19권3호
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• pp.206-212
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• 2002

The catalytic activities of several metalloporphyrin, wherein the porphyrins are TPP(5,lO,l5,20-Tetraphenyl-21H,23H-porphyrin) and (p-X)TPP (X =$CH_{3}O$, $CH_{3}$, F, Cl), are reported for the oxidation of styrene and it's derivatives. The electronic effects of substrates and porphyrins on the catalytic activity of metalloporphyrin containing the transition metal ion such as Mn(III) was discussed. Investigating the correlation between the Michaelis-Menten's rate parameters and the substituent constants, we are going to analyze the influences on the changes of catalytic activity or rate determining step during the processes of the formation and the dissociation of the M-oxo-olefin.

• 환경생물
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• 제23권4호
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• pp.379-382
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• 2005

The new cationic meso-substituted N-quarternized 4-pyridylporphyrins and their metal derivatives were synthesized as novel chemotherapeutics. The level of DNA damage induced by porphyrins TOBut4PyP, TOBut4PyP, TOEt4PyPMn and TOBut4PyPMn and its dependence on the chemical structure of compounds were analyzed by the Comet-assay. On the base of data obtained, the investigated porphyrins may be arranged by their genotoxic activity in the following order: TOEt4PyP>TOEt4PyPMn>TOBut4PyP>TOBut4PyPMn. Thus, i) the genotoxicity of the Mn-derivatives of TOEt4PyP and TOBut4PyP is higher than the original porphyrins and ii) the genotoxicity of TOEt4PyP and TOEt4PyPMn is increased after substitution of a butyl radical for ethyl one. The applied Comet-assay permits to reveal the dependence of DNA damage induction on the chemical structure of porphyrins.

• Bulletin of the Korean Chemical Society
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• 제24권5호
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• pp.547-551
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• 2003

In the present work, the interaction of three water soluble porphyrins, tetra(p-trimethyle) ammonium phenyl porphyrin iodide (TAPP) as a cationic porphyrin, tetra sodium meso-tetrakis (p-sulphonato phenyle) porphyrin (TSPP) as an anionic porphyrin and manganese tetrakis (p-sulphonato phenyl) porphinato acetate (MnTSPP) as a metal porphyrin, with histone H₂B have been studied by isothermal titration microcalorimetry at 8 mM phosphate buffer, pH 6.8 and 27 °C. The values of binding constant, entropy, enthalpy and Gibbs free energy changes for binding of the first MnTSPP, and first and second TSPP and TAPP molecules were estimated from microcalorimetric data analysis. The results represent that the process is both entropy and enthalpy driven and histone induces self-aggregation of the porphyrins. The results indicate that both columbic and hydrophobic interactions act as self-aggregation driving forces for the formation of aggregates around histone.

• Bulletin of the Korean Chemical Society
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• 제11권4호
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• pp.286-290
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• 1990

The surface enhanced Raman scatterings of Zn(Ⅱ) tetrakis (4-N-methyl pyridyl) porphyrins were studied in silver sol. Zn(Ⅱ) tetrakis (4-N-methyl pyridyl) porphyrin was found to be adsorbed on silver surface via flat-on geometry with some inhomogeneous distribution in the orientation of pyridyl groups. Both the selective enhancement of Raman modes depending on the mode character and the theoretical arguments of SERS are utilized to support the above conclusion. The surface induced substitution reaction of Mn(Ⅲ) tetrakis (4-N-methyl pyridyl) porphyrin chloride to Ag(Ⅱ) tetrakis (4-N-methyl pyridyl) porphyrin was detected via surface enhanced Raman spectrum.

• Bulletin of the Korean Chemical Society
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• 제29권4호
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• pp.866-868
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• 2008

• 한국응용과학기술학회지
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• 제15권2호
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• pp.41-48
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• 1998

The catalytic oxidations of several cycloolefins in $CH_2Cl_2$ were been investigated using Mn(III)-, Fe(III)-porphyrin complexes as a catalyst and sodium hypochlorite as a terminal oxidant. Porphyrins were $(p-CH_3O)TTP,\;(p-CH_3)TTP,$ TPP, (p-F)TPP, (p-Cl)TPP and $(F_{20})TPP$ (TPP = tetraphenylporphyrin), and olefins were cyclopentene, cyclohexene and cycloheptene. The substrate conversion yield was discussed according to the substituent effects of metalloporphyrin. The conversion yield of substrate by changing the substituent of TPP increased in the order of $p-CH_3O$ < $p-CH_3$ < H < p-F < p-Cl, which was consistent with the sequence of $4{\sigma}$ values of TPP. The conversion of cycloalkene followed the order of $C_5\;<\;C_6\;<\;C_7$.

• Bulletin of the Korean Chemical Society
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• 제25권10호
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• pp.1484-1488
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• 2004

The thiocyanate-selective PVC membrane electrodes based on 5,10,15,20-tetrakis(2,4,6-trimethylphenyl)-porphyrinatomanganese(III) chloride [Mn(TMP)Cl] and 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinatomanganese(III) chloride $[Mn(Cl_8TPP)Cl]$ as ion carriers were investigated. The effect of ionophores, membrane compositions, plasticizers, and solution pHs on the response characteristics were studied. The Mn(TMP)Cl as an ionophore shows the best potentiometric sensitivity with a slope of -58.7 mV/decade and a detection limit of $log[SCN^-]$ = -6.90, and selectivity for thiocyanate over strong hydrophobic interfering anions such as ${ClO_4}^-$ and salicylate. The potentiometric response is affected by the electronic effect of the substituents and solution pHs. The presence of substituents with electron donating and more liphophilic characters around the ligated metal center produces an improved response toward $SCN^-$.

• 분석과학
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• 제8권4호
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• pp.511-517
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• 1995

A cationic water soluble porphyrin (5,10,15,20-tetrakis (l-methyl-pyridinium-4-yl)porphyrin, $H_2tmpyp^{4+}$) and its metalloporphyrins (MP) were easily extracted into acetonitrile separated by addition of sodium chloride ($4mol\;dm^{-3}$) in the presence of sodium perchlorate, where M denotes $Zn^{2+}$, $Cu^{2+}$, $Co^{3+}$, $Fe^{3+}$, and $Mn^{3+}$ and $P^{2-}$ is porphyrinate ion. The extracted ion-pair complexes were completely dissociated to $[MP(ClO_4)_3]^+$, and $[MP(ClO_4)_2]^{2+}$. The extraction and the dissociation constants were determined by taking into account of the partition constant of sodium perchlorate ($K_D=1.82{\pm}0.01$). The chemical properties of the separated acetonitrile phase as $E_{T(30)}$ and $D_{II,I}$ were determined and compared with other water miscible solvents (acetone, actonitrile, 1,4-dioxane, tetrahydrofuran, 1-propanol and 2-propanol). Furthermore, a sensitive and selective method was proposed for the determination of a subnanogram amount of copper(II) in natural water samples by using the present salting-out method and the porphyrins.