• Title/Summary/Keyword: cationic porphyrin

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Effect of Cationic and Anionic Porphyrins on the Structure and Activity of Adenosine Deaminase

  • Ajloo, Davood;Hajipour, Samaneh;Saboury, Ali Akbar;Zakavi, Saeed
    • Bulletin of the Korean Chemical Society
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    • v.32 no.9
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    • pp.3411-3420
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    • 2011
  • Kinetic and structural studies have been carried out on the effects of meso-tetrakis(4-sulfonatophenyl)-porphyrin ($H_2TPPS_4$) as an anionic and meso-tetrakis(3-N-methyl-pyridyl)porphyrin ($H_2TMPYP$) as a cationic porphyrin with adenosine deaminase (ADA) in 25 mM citrate/phosphate buffer, pH = 4-8, at $37^{\circ}C$ using UVvis spectrophotometry, circular dichroism (CD), fluorescence spectrophotometry as well as molecular dynamics (MD) and molecular docking. Kinetic results showed that the two porphyrins are non-competitive inhibitors. Increasing pH, increases $K_I$ and cationic porphyrin has a higher $K_I$ and lower binding constant ($K_b$) at all pH ranges. Analyzing the secondary structure revealed that both ligands decrease the secondary structure and that the anionic porphyrin is more effective.

Solution properties of sodium n-dodecyl sulfate in the presence of meso-tetrakis (N-methylpyridinium-4-yl) porphyrin (Meso-tetrakis (N-methylpyridinium-4-yl) porphyrin 존재 하에서 sodium n-dodecyl sulfate 용액 성질)

  • Hassanpour, Azin;Azani, Mohammad-Reza;Bordbar, Abdol-Khalegh
    • Journal of the Korean Chemical Society
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    • v.55 no.3
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    • pp.335-340
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    • 2011
  • The solution properties of sodium n-dodecyl sulfate, as an anionic surfactant in the presence of a cationic watersoluble 5, 10, 15, 20-tetrakis (N-methylpyridinium-4-yl) porphyrin (TMPyP) has been comprehensively studied by means of conductometry, UV-vis and resonance light scattering (RLS) spectroscopies. The results represent the decreasing of critical micelle concentration of SDS solution due to increasing of TMPyP concentration. The stabilization of SDS micelle is due to neutralization of negative charge at the micelle surface. The presence of three different species of TMPyP in SDS solution has been unequivocally demonstrated: free porphyrin monomers, porphyrin monomers or aggregates bound to the micelles, and nonmicellar porphyrin/surfactant aggregates. Our results show SDS induced an aggregation in TMPyP. In fact two kinds of J-aggregations were observed: one of them for porphyrin monomers or aggregates bound to the micelles and the other for nonmicellar porphyrin/surfactant aggregates. However, the results represent the electrostatic interaction of TMPyP with SDS anion below the cmc.

Photosensitized oxidative damage of human serum albumin by water-soluble dichlorophosphorus(V) tetraphenylporphyrin

  • Ouyang, Dongyan;Hirakawa, Kazutaka
    • Rapid Communication in Photoscience
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    • v.4 no.2
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    • pp.41-44
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    • 2015
  • Biomolecular photo-damaging activity of a water-soluble cationic porphyrin was examined using human serum albumin (HSA), a water-soluble protein as a target biomolecule model by a fluorometry. Dichlorophosphorus(V) tetraphenylporphyrin ($Cl_2P(V)TPP$), was synthesized and used as a photosensitizer. This porphyrin could bind to HSA and cause the photosensitized oxidation of HSA through the singlet oxygen generation and the oxidative photo-induced electron transfer (ET). Near infrared emission spectroscopy demonstrated the photosensitized singlet oxygen generation by this porphyrin. Decrement of the fluorescence lifetime of $Cl_2P(V)TPP$ by HSA supported the ET mechanism. Furthermore, the estimated Gibb's energy indicated that the ET mechanism is possible in the terms of energy. Because oxygen concentration in cancer cell is relatively low, ET mechanism is considered to be advantageous for photosensitizer of photodynamic therapy.

NMR Study on Binding Interactions of Cationic Porphyrin Derivatives with double helical $d(CGCGAATTCGCG)_2$

  • Huh, Sungho;Hong, Seokjoo
    • Journal of the Korean Magnetic Resonance Society
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    • v.5 no.2
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    • pp.118-129
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    • 2001
  • Binding interactions of cationic porphyrins, T4MPyP and TMAP with DNA oligomer d(CGCGAATTCGCG), were studied with NMR spectroscopy, W and CD spectroscopic method. Two porphyrins showed significant differences in NMR, UV and CD data upon binding to DNA. T4MPyP was considered to position more closely to DNA bases through partial intercalation as well as ionic intercalation between the positive charges of porphyrin and phosphate group of DNA at 5’-GC-3’steps. Contrast to this, TMAP was thought to bind to phosphate of DNA more or less outside of the groove.

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An Isothermal Titration Microcalorimetric Study on the Interaction of Three Water-Soluble Porphyrins with Histone H2B

  • Bordbar, A.K.;Ghaderi, A.R.;Safaei, E.;Tangestaninejad, S.;Eslami, A.;Saboury, A.A.;Moosavi Movahedi, A.A.
    • Bulletin of the Korean Chemical Society
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    • v.24 no.5
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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.

Energy Transfer from Ethidium to Cationic Porphyrins Mediated by DNA and Synthetic Polynucleotides at Low Binding Densities

  • Jung, Jin-A;Jeon, Sun-Hee;Han, Sung-Wook;Lee, Gil-Jun;Bae, In-Ho;Kim, Seog-K.
    • Bulletin of the Korean Chemical Society
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    • v.32 no.8
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    • pp.2599-2606
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    • 2011
  • The fluorescence of ethidium bound to DNA, poly[d(A-T)$_2$], and poly[d(G-C)$_2$] at a [ethidium]/[DNA] ratio of 0.005 was quenched by porphyrins when both ethidium and the porphyrins simultaneously bound to the same polynucleotide. The quenching was tested using the "inner sphere" and the "Forster resonance energy transfer" (FRET) models, with the latter found to contribute, at least in part, to the quenching. Meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP) exhibited a higher quenching and FRET efficiency than cis-bis(N-methylpyridinium-4-yl)porphyrin (BMPyP) for all of the tested DNA and polynucleotides, demonstrating that energy transfer efficiency is affected by the number of positive charges of porphyrins.

DNA Mediated Energy Transfer from 4',6-Diamidino-2-phenylindole to tetra- and bis-cationic Porphyrins at Low Binding Densities

  • Gong, Lindan;Ryu, Jae-Ki;Kim, Bok-Jo;Jang, Yoon-Jung
    • Bulletin of the Korean Chemical Society
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    • v.33 no.2
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    • pp.529-534
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    • 2012
  • The fluorescence of 4',6-diamidino-2-phenylindole (DAPI) bound to DNA at a [DAPI]/[DNA base] ratio of 0.005 was quenched by meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP) or cis-bis(N-methylpyridinium-4-yl)porphyrin (BMPyP) when both DAPI and either porphyrin spontaneously bound to the same DNA strand. The quenching was investigated using the "one-dimensional inner sphere" and the "F$\ddot{o}$rster resonance energy transfer" (FRET) models. Total quenching occurred when DAPI and TMPyP were up to 19.3 base pairs or $66\AA$ apart. BMPyP could quench the fluorescence up to 13.9 base pairs or $47\AA$. TMPyP, which intercalated between the DNA base-pairs, appeared to be a better acceptor than BMPyP, which stacked along the DNA stem. The higher quenching and higher resonance energy transfer efficiency of TMPyP was due to the larger overlap integral between its absorption spectrum and the emission spectrum of DNA-bound DAPI.

Extraction of Water-Soluble Porphyrin and Metalloporphyrins into Acetonitrile by Salting-out

  • Tabata, Masaaki;Kumamoto, Midori
    • Analytical Science and Technology
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    • v.8 no.4
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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.

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