On the dynamics of the TPPS4 aggregation in aqueous solutions

Aggarwal, Lucimara Perpetua Ferreira; Borissevitch, Iouri

doi:10.1016/j.saa.2005.05.009

Cited by 84 publications

(76 citation statements)

References 26 publications

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“…Despite the strong anionic character with charge −4, the profile is very similar to that of the heme porphyrin [4], with charge −2. The hydrophobic character is responsible for porphyrin H-aggregation processes [15].…”

Section: −mentioning

confidence: 99%

Solvation of anionic water‐soluble porphyrins: A computational study

Cuya

Louro

Pascutti

et al. 2010

Int J of Quantum Chemistry

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Explicit solvent molecular dynamics simulations of meso-tetra[4-sulfonatophenyl] porphyrin (TPPS 4− ) in water were performed. The relation solute-solvent was examined through the radial distribution function g(r) of water molecules around different groups of the solute. The outcomes of the simulations show that, despite the presence of charged side groups in the particular case of TTPS 4− , it displays a global hydrophobic character. Moreover, the hydropathic pattern of the different groups of the solute (central ring and side chains) is also characterized. Additionally, we show that this heterogeneous hydropathicity profile remains basically unaltered by complexing TPPS 4− with Fe 2+ .

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Section: −mentioning

confidence: 99%

Solvation of anionic water‐soluble porphyrins: A computational study

Cuya

Louro

Pascutti

et al. 2010

Int J of Quantum Chemistry

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“…[24] The metal porphyrin absorption spectrum changes upon the decreasing pH from a typical monomer TPPS with the absorption maxima at 422 and 556 nm to the lightgreen solution which shows a gradual absorbance increase at 490 and 710 nm, characteristic for J-type aggregated species, with the decreasing extinction in the diprotonated monomeric bands at 434 and 590 nm ( Figure 2). The spectral changes observed in the long wavelength spectral region corresponding to J-aggregate formation without any electrolytes or surfactants require several hours to occur.…”

Section: Resultsmentioning

confidence: 99%

Photophysical Properties and Aggregation Behavior of Transition Metal Tetraphenylporphyrin Tetrasulfonate Complexes in Microheterogeneous Media

Gradova¹,

Лобанов²

2013

MHC

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This paper considers the influence of various surfactants and polyelectrolytes on the photophysical properties and the aggregation state of transition metal complexes of meso-5,10,15,20-tetrakis-(4-sulfonatophenyl) porphyrin (MeTPPS). Porphyrin transition metal complex aggregation stability in acidic medium is also compared for a number of metal cations. The mechanism of J-aggregate formation and the nature of porphyrin-surfactant interactions in microorganized systems are discussed in details.Keywords: Transition metal porphyrin complexes, ZnTPPS, J-aggregates, ionic associates. Фотофизические свойства и агрегационная устойчивость IntroductionPorphyrin based supramolecular assemblies in recent years have been considered as novel mesoscopic materials with tunable electronic and optical properties, useful as photosensitizers, optical switches, molecular sensors, artificial light-harvesting systems and photovoltaic device components. [1][2][3] Such smart materials can include either homoporphyrin aggregates (H-or J-type ones) or multiporphyrin assemblies, [4] as well as heteroaggregates [5] and ionic associates with various non-porphyrin compounds. [6] Since both photophysical and photochemical properties of various porphyrin derivatives strongly depend on the chromophore aggregation state determined predominantly by the medium acidity, ionic strength and the presence of template molecules, controlled reversible aggregation of porphyrin supramolecular assemblies is still of great research interest.To date among the known water-soluble porphyrin derivatives the most well-studied one is meso-5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrin (TPPS). During the past decade much work has been done on TPPS interactions with surfactants, [7][8][9][10][11] polyelectrolytes [12][13][14][15] and especially biomacromolecules. [16][17][18] The increasing research interest in porphyrin behavior within microorganized systems is due to their possible application as photosensitizers in photodynamic therapy (PDT), [19] since the microheterogeneous medium is known to favor supramolecular ionic associate and 341 Макрогетероциклы / Macroheterocycles 2013 6(4) 340-344 M. A. Gradova, A. V. Lobanov heteroaggregate formation, especially at low pH abundant in cancer cells. [20][21][22] Despite the large amount of available experimental data, we still lack a unified detailed description of the mechanism of porphyrin aggregate formation in microorganized biomembrane-mimetic media.The main aim of this work was to compare the photophysical properties and the aggregation state of water soluble transition metal complexes of tetraphenylporphyrin tetrasulfonate in various microheterogeneous systems, such as surfactant (SDS, CTAB, TX-100) and polyelectrolyte (PDDA, PVP, PEG) solutions with different surface charge. We especially focused on influence of the cation nature on the porphyrin metal complex stability in acidic medium, J-type aggregate formation and their morphology. ExperimentalTransition metal complexes of cobalt, nickel and zinc with a...

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“…At the same time a significant effect of the length of the aliphatic spacer and the metal nature on the liquid crystalline properties has been discovered. [11] In this work we have synthesized the structural analogs of the above mentioned cationic porphyrins -amphiphilic tetraalkoxyaryl porphyrins (1-5) and studied their mesomorphic properties. These compounds have long chain substituents in which the spacer methylene chains with a length of five or ten carbon atoms separate the carboxy or carboxymethyl groups from the porphyrin macrocycle.…”

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confidence: 99%