• Title, Summary, Keyword: metalloporphyrin

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Syntheses of Metalloporphyrins and Polymer-bonded Metalloporphyrin and Their Catalytic Effects on Benzoquinone Photoreduction (Metalloporphyrins 와 Polymer-bonded Metalloporphyrin 의 합성 및 Benzoquinone 광환원반응의 촉매효과)

  • Kyu-Ja Whang;Hee-Kyung Lee;Yong-Keun Lee
    • Journal of the Korean Chemical Society
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    • v.35 no.5
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    • pp.569-574
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    • 1991
  • Six free base porphyrins were synthesized by reacting pyrrole with benzaldehyde or its derivatives and then reacted with metal chlorides to prepare corresponding metal complexes. In addition, polymer-bonded porphyrins were synthesized by treating chloromethylated styrene-divinyl benzene (1%) copolymer beads with meso-tetra (p-aminophenyl)porphyrin (TNPP) solution and then treated with cupric chloride to obtain Cu(Res-NH-TPP-$NH_2$). The porphyrin compounds were characterized by visible, inffrared and electron spin resonance spectral analyses. The metal contents of metalloporphyrins were determined by atomic adsorption spectrophotometry. The synthesized porphyrin compounds were subsequently examined for their catalytic strength and found the activity to increase in the following order: free base porphyrins; metalloporphyrins; polymer-bonded metalloporphyrin. Among metalloporphyrins, Cu-TNPP showed the greatest catalytic power.

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Interaction between Metalloporphyrins and Diazine Tautomers

  • Xu, Huiying;Wang, Wei;Zhu, Jianqing;Xu, Xiaolu;Zhang, Deyong
    • Bulletin of the Korean Chemical Society
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    • v.34 no.12
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    • pp.3727-3732
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    • 2013
  • The interaction between metalloporphyrins and diazine tautomers was investigated using quantum chemistry method. The results showed that the metal atom in the metalloporphyrin was not coplanar with porphin ring, and zinc porphyrin has the most extent of its non-coplanar nature. The most stable complex in nine complexes was iron porphyrin. NBO analysis indicated that the interaction between the lone pair of electrons on the nitrogen atom and the unoccupied lone pair orbital of metal contributes significantly to the stability of the complexes. Through the conceptual DFT parameter and Fukui dual descriptor, the thermodynamic stability and reactivity of complexes were analyzed. The density difference function (DDF) analyzes were performed to explore the rearrangement of electronic density after the coordination interaction. NICS calculation indicated that metalloporphyrin aromaticity was reduced after the coordination interaction, and aromaticity of diazine tautomer was increased along direction vector of the coordination interaction force.

Oxidative Decomposition of 2, 4, 6-Trichlorophenol Catalyzed by Polymer Supported Metalloporphyins (고분자결합 금속포르피린을 촉매로 한 2, 4, 6-트리클로로페놀의 산화 분해반응)

  • Park, Hye-Ok;Lee, Bo-Young;Rhee Paeng, Insook
    • Analytical Science and Technology
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    • v.14 no.1
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    • pp.72-79
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    • 2001
  • Oxidative decomposition of 2, 4, 6-trichlorophenol(TCP) was studied in aqueous solution. Iron and manganese protoporphyrin [or tetrakis(p-carboxyphenylporphyrin)] and their polymer supported derivatives were used as catalysts, and $KHSO_5$ and tert-butyldroperoxide(TBHP) as oxidants. Metalloporphyrin itself shows very poor catalytic activity in oxidative decomposition of TCP with oxidant. However, very high catalytic activity was observed when metalloporphyrin was chemically bound to newly synthesized polymers or XAD2 resin. Additionally, it revealed much higher catalytic activity in the presence of water-soluble polymers having a electron-donating axial ligand such as pyridine and immidazole. Maleic acid and chloromaleic acid were found in the resulting solution by ESI-MS. Especially, XAD2-supported metalloporphyrins can be reused as catalysts due to insolubility to solvent, and stability against oxidant.

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Study for the Preparation of Deodorizing Fiber (I) - Preparations of Deodorizing Fibers using Metalloporphyrines - (소취 섬유의 제조에 관한 연구 (I ) - 금속 포르피린을 이용한 소취 섬유의 제조 -)

  • 오선화;전숙경;박수민
    • Textile Coloration and Finishing
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    • v.13 no.6
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    • pp.367-373
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    • 2001
  • The preparations of deodorizing fibers using metalloporphyrines hove been investigated. The three metalloporphyrin derivatives(MTCPP, M=Mn, Zn, Sn) were prepared in modest to good yields. The metalloporphyrin derivative as a deodorant material was Introduced to fibers by a dyeing method. The deodorant activity(D.A.) of these deodorizing fibers was measured by chromogenic gas detector tubes. In comparison with untreated fiber, these deodorizing fibers was remarkably effective against $NH_3$ and $CH_3$SH$. More than 98% of ammonia can be removed within 20 min.. The D.A.(%) of fiber adsorbed MTCPP was more than 80% after 90min..

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Kinetic Investigation of Styrene Derivatives Oxidation Mechanism by Mn(III)-porphyrin (Mn(III)-porphyrin에 의한 Styrene 유도체의 산화반응 메카니즘 연구)

  • Na, Hun-Gil
    • Journal of the Korean Applied Science and Technology
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    • v.19 no.3
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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.

Gadolinium-Chlorin is Potentially a New Tumor Specific MRI Contrast Agent

  • Kim Jong-Ki;Kim Dong-Myung;Kang Min-Suk;Kim Hae-Kyung;Kim Jeong-Sook;Yu Eun-Kyung;Jeong Jin-Hyun
    • Archives of Pharmacal Research
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    • v.29 no.3
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    • pp.188-190
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    • 2006
  • In this study, a newly-synthesized metalloporphyrin, Gd-chlorin (PB Chlorin), was investigated by using a simple tissue phantom to test its efficacy as an MRI contrast agent. This study demonstrated the potential activity of Gd-chlorin as not only a MRI contrast agent, but also as a PDT photosensitizer by using a simple tissue phantom and conducting a very brief MRI experiment.

Cycloolefins Oxidation Reaction Catalyzed by Ga(III)-, In(III)- and TI(III)-Porphyrin Derivatives (Ga(III)-, In(III)-, TI(III)-porphyrin 유도체를 촉매제로 한 고리성 올레핀의 산화반응)

  • Na, Hun-Gil
    • Journal of the Korean Applied Science and Technology
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    • v.21 no.1
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    • pp.76-88
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    • 2004
  • The catalytic oxidation reaction of several cycloolefins in $CH_2Cl_2$ have been investigated using non-redox metalloporphyrin(M = Ga(III), In(III) and TI(III) complexes as a catalyst and sodium hypochlorite as a terminal oxidant. Porphyrins were $(p-CH_3O)$TPP, $(p-CH_3)$TPP, TPP, (p-F)TPP, (p-Cl)TPP and $(F_{20})$TPP (TPP=5,10,15,20-tetraphenyl-21H,23H-porphyrin) and olefins were cyclopentene, cyclohexene, cycloheptene and cyclooctene, The substrate conversion yield(%) was investigated according to the radius effect of non-redox metal ion, substituent effect and hindrance effect of metalloporphyrin. The conversion yield of cycloolefin was in the following order : $C_5$ < $C_6$ < $C_7$ = $C_8$.

Kinetics of the Formation of Metalloporphyrins and the Catalytic Effect of Lead Ions and Hydrogen Ions

  • Qi, Yong;Pan, Ji Gang
    • Bulletin of the Korean Chemical Society
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    • v.35 no.11
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    • pp.3313-3318
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    • 2014
  • The reaction mechanism of Lead ions catalyzing complexation reactions between TIPP and metal ions was investigated by researching the kinetics of the formation of metalloporphyrins by UV/Vis-spectra, and verified by exploring the formation of metalloporphyrins catalyzed by acetic acid. Kinetics studies suggested that the fluctuations of reaction rate indicated the formation of metalloporphyrin was step-wise, including the pre-equilibrium step (the coordination of the pyrrolenine nitrogens to $Mn^+$) and the rate-controlling step (the deprotonation of the pyrrole proton). In the pre-equalization step, a sitting-atop (SAT) structure formed first with the complexation between larger radius of $Pb^{2+}$ and TIPP, changed the activation, then $Pb^{2+}$ left with the smaller radius of metal ions attacking from the back of the porphyrin ring center. In the rate-controlling step, two pyrrole protons dissociated to restore a stable structure. This was verified by adding acetic acid at different reaction times.