title: Self-assemblies of tricationic porphyrin on inorganic polyphosphate.
abstract: Self-assemblies formed by the new synthesized tricationic porphyrin derivative (TMPyP(3+)) on the polyanionic inorganic polyphosphate (PPS) in aqueous solution were studied using different spectroscopic techniques and DFT calculation method. From the fluorescence quenching of the bound TMPyP(3+) molecules and their Raman spectra we conclude that porphyrin chromophores form the stable π-π stacking-assemblies onto PPS polyanions. The transformation of the Soret band in absorption spectra at different PPS/TMPyP(3+)concentration ratios evidences that the assemblies are mixtures of J- and H-aggregates. Molecular modeling performed shows that the flexibility of PPS strand allows a realization of spiral or "face-to-face" one-dimensional structures formed by porphyrin molecules arranged in parallel and antiparallel modes. The peculiarity of PPS structure allows a formation of two porphyrin stacks on opposite sides of polymer strands that result in the appearance of higher-order aggregates. Their size was estimated from the light scattering data. Distinctions between TMPyP(3+) and TMPyP4 aggregation on PPS template are discussed.
authors: Department of Molecular Biophysics, B. Verkin Institute for Low Temperature Physics and Engineering, National Academy of Sciences of Ukraine, 47 Lenin ave, 61103 Kharkov, Ukraine.
authors: Victor N
authors: VN
authors: Zozulya
authors: Department of Molecular Biophysics, B. Verkin Institute for Low Temperature Physics and Engineering, National Academy of Sciences of Ukraine, 47 Lenin ave, 61103 Kharkov, Ukraine. Electronic address: ryazanova@ilt.kharkov.ua.
authors: Olga A
authors: OA
authors: Ryazanova
authors: Department of Molecular Biophysics, B. Verkin Institute for Low Temperature Physics and Engineering, National Academy of Sciences of Ukraine, 47 Lenin ave, 61103 Kharkov, Ukraine.
authors: Igor M
authors: IM
authors: Voloshin
authors: Department of Synthetic Bioregulators, Institute of Molecular Biology and Genetics, National Academy of Sciences of Ukraine, 150 Zabolotnogo str., 03680 Kyiv, Ukraine.
authors: Mykola M
authors: MM
authors: Ilchenko
authors: Department of Synthetic Bioregulators, Institute of Molecular Biology and Genetics, National Academy of Sciences of Ukraine, 150 Zabolotnogo str., 03680 Kyiv, Ukraine.
authors: Igor Ya
authors: IY
authors: Dubey
authors: Department of Molecular Biophysics, B. Verkin Institute for Low Temperature Physics and Engineering, National Academy of Sciences of Ukraine, 47 Lenin ave, 61103 Kharkov, Ukraine.
authors: Alexander Yu
authors: AY
authors: Glamazda
authors: Department of Molecular Biophysics, B. Verkin Institute for Low Temperature Physics and Engineering, National Academy of Sciences of Ukraine, 47 Lenin ave, 61103 Kharkov, Ukraine.
authors: Victor A
authors: VA
authors: Karachevtsev
mesh_terms: D005453:Fluorescence; D008027:Light; D008958:Models, Molecular; D000071228:Polyelectrolytes; D011108:Polymers / Q000737:chemistry; D011122:Polyphosphates / Q000737:chemistry*; D011166:Porphyrins / Q000737:chemistry*; D012542:Scattering, Radiation
chemical_list: D000071228:Polyelectrolytes; D011108:Polymers; D011122:Polyphosphates; D011166:Porphyrins; C057459:tetra(3-N-methylpyridyl)porphine
keywords: Absorption; Cationic meso-porphyrin; Light scattering; Polarized fluorescence; Polyphosphate; Porphyrin aggregation