title: Small angle X-ray scattering study of meso-tetrakis (4-sulfonatophenyl) porphyrin in aqueous solution: a self-aggregation model.
abstract: The aggregate morphology of meso-tetrakis(4-sulfonatophenyl) porphyrin (TPPS(4)) in aqueous solution is investigated by using small angle x-ray scattering (SAXS) technique. Measurements were performed at pH 4.0 and 9.0 to monitor the pH influence on the structural parameters of the aggregates. Radii of gyration were obtained from distance distribution functions p(r) analysis. The experimental data of TPPS(4) at pH 4.0 showed well-defined oscillations characteristic of large aggregates in contrast to the SAXS curve of 5 mM TPPS(4) at pH 9.0, where both a significant decrease in the intensity and the disappearance of the oscillation peaks suggest the dissociation of the aggregate. A 340-A long "hollow" cylinder with shell thickness of 20 A, compatible to the porphyrin molecule dimension, represents well the scattering curve of the aggregates at pH 4.0. According to the fitting parameters, 26 porphyrin molecules self-associate into a ringlike configuration in the plane of the cylinder cross-section. The total number of porphyrin molecules in the whole aggregate was also estimated as approximately 3000. The model compatible to SAXS data of a hollow cylinder with J-aggregation in the cross-section and H-aggregation (columnar stacking) between the cylinder layers is consistent with optical absorption spectroscopic data both in the literature and obtained in this work.
authors.affiliation: Instituto de Química de São Carlos, Universidade de São Paulo, São Paulo, Brazil.
authors.forename: S C M
authors.initials: SC
authors.lastname: Gandini
authors.forename: E L
authors.initials: EL
authors.lastname: Gelamo
authors.forename: R
authors.initials: R
authors.lastname: Itri
authors.forename: M
authors.initials: M
authors.lastname: Tabak
mesh_terms: D003198:Computer Simulation; D003460:Crystallization / Q000379:methods*; D018360:Crystallography, X-Ray / Q000379:methods*; D006863:Hydrogen-Ion Concentration; D046911:Macromolecular Substances; D008958:Models, Molecular; D008968:Molecular Conformation; D011108:Polymers / Q000138:chemical synthesis; D011166:Porphyrins / Q000138:chemical synthesis / Q000737:chemistry*; D012996:Solutions; D014867:Water / Q000737:chemistry*
chemical_list: D046911:Macromolecular Substances; D011108:Polymers; D011166:Porphyrins; D012996:Solutions; D014867:Water; C016136:tetraphenylporphine sulfonate