Self-assembly in water of the sodium salts of meso-sulfonatophenyl substituted porphyrins

Rubires, Raimon; Crusats, Joaquim; El‐Hachemi, Zoubir; Jaramillo, Tatiana; López, Marta; Valls, Elisabet; Farrera, Joan‐Anton; Ribó, Josep M.

doi:10.1039/a808943d

Cited by 137 publications

(150 citation statements)

References 39 publications

(3 reference statements)

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“…This relationship may indicate that axial ligands have undesirable steric interactions with the biological target. Some TPPS4 derivatives stack significantly in solution (9,32,35). To determine whether the monomeric form of the porphyrin was important for the activity, the selfstacking of these derivatives was evaluated by measuring the optical spectrum of each of the metallo-TPPS4 derivatives as a function of added NaCl.…”

Section: Resultsmentioning

confidence: 99%

Inactivation of Human Immunodeficiency Virus Type 1 by Porphyrins

Vzorov¹,

Dixon

Trommel

et al. 2002

Antimicrob Agents Chemother

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We have evaluated the anti-human immunodeficiency virus (HIV) activity of a series of natural and synthetic porphyrins to identify compounds that could potentially be used as microbicides to provide a defense against infection by sexually transmitted virus. For assays we used an epithelial HeLa-CD4 cell line with an integrated long terminal repeat-␤-galactosidase gene. For structure-activity analysis, we divided the porphyrins tested into three classes: (i) natural porphyrins, (ii) metallo-tetraphenylporphyrin tetrasulfonate (metallo-TPPS4) derivatives, and (iii) sulfonated tetra-arylporphyrin derivatives. None of the natural porphyrins studied reduced infection by more than 80% at a concentration of 5 g/ml in these assays. Some metal chelates of TPPS4 were more active, and a number of sulfonated tetra-aryl derivatives showed significantly higher activity. Some of the most active compounds were the sulfonated tetranaphthyl porphyrin (TNapPS), sulfonated tetra-anthracenyl porphyrin (TAnthPS), and sulfonated 2,6-difluoro-meso-tetraphenylporphine [TPP(2,6-F2)S] and its copper chelate [TPP(2,6-F2)S,Cu], which reduced infection by 99, 96, 94, and 96%, respectively. Our observations indicate that at least some of these compounds are virucidal, i.e., that they render the virus noninfectious. The active compounds were found to inhibit binding of the HIV type 1 gp120 to CD4 and also to completely inhibit the ability of Env proteins expressed from recombinant vectors to induce cell fusion with receptor-bearing target cells. These results support the conclusion that modified porphyrins exhibit substantial activity against HIV and that their target is the HIV Env protein.

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Section: Resultsmentioning

confidence: 99%

Inactivation of Human Immunodeficiency Virus Type 1 by Porphyrins

Vzorov¹,

Dixon

Trommel

et al. 2002

Antimicrob Agents Chemother

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“…An optical and topographic resolution of about 100 and 160 nm, respectively, with an optical contrast C ) 18% is derived. sulfonatophenyl)porphine (TPPS), [24][25][26][27][28] which under strong acidic conditions form extended J-aggregates. Several investigators have pointed out that coplanarity is a prerequisite for the initial dimerization step, together with the presence of negatively charged groups on the periphery.…”

Section: Discussionmentioning

confidence: 99%

Aggregation Behavior of Protoporphyrin IX in Aqueous Solutions: Clear Evidence of Vesicle Formation

et al. 2002

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The aggregation behavior of protoporphyrin IX in aqueous solution, as a function of pH and ionic strength, has been studied by means of UV/vis, fluorescence emission spectroscopy, and resonant light scattering (RLS) techniques. Our experimental results agree with previous literature assignments: (i) protoporphyrin IX is a monomer in the pH range 0-3, (ii) a dimer is present for pH > 8, and (iii) higher aggregates are present in the pH range 3-7. Addition of sodium chloride up to 0.3 M to a porphyrin solution at pH 12 gives a process resembling a phase transition, whereas it has little effect on acidic or neutral solutions. The apparent split Soret band observed in the intermediate pH range has been explained using a model in which dimers of porphyrins (with a slip angle R ) 38°or 52°, as derived from depolarized RLS measurements) are the basic units and they interact axially through π-π stacking and laterally by edge-to-edge hydrophobic contacts. The half neutralization of the carboxylic acid side chains is responsible for the occurrence of a network of intermolecular hydrogen bonds, which contribute to a better stabilization of the supramolecular assembly. Evaporation on a glass surface of solutions containing protoporphyrin IX aggregates from samples at intermediate pH leads to aggregates stable enough to be investigated for the first time through scanning electron (SEM) and scanning near-field optical microscopy (SNOM). These species evidence a prolate shape with an average size of 200-500 nm and a medium height of 60 nm, which is in agreement with the hydrodynamic radii as measured in solution by dynamic light scattering. On consideration of the amphiphilic character of protoporphyrin IX, these observations suggest the formation of multilamellar or onion-like vesicles. The analysis of the SNOM images points to the presence of regions in which the aggregation process resulted in a thin film covering the vesicles. An analysis of SEM experiments reveals also the contemporary presence of large regions in which the vesicles collapse in a continuum layered structure.

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“…This characteristic causes their aggregation in water, resulting in formation of supramolecular structures. Self-assembly of porphyrins can be easily modulated by varying pH: as an example, the well-known class of meso-benzylsulfonated derivatives forms H-and J-aggregates at pH < 3 (pK a = 4.8) [9][10][11][12][13][14]. Of course, self-aggregation is mainly driven by protonation of the porphyrin core, but also the protonation of the substituents covalently bonded to the macrocycle [15] or the presence of a metal in the porphyrin core [16,17] strongly influences their aggregartion pathway.…”

Section: Introductionmentioning

confidence: 99%

ZnTPPS demetalation: Role of polyelectrolytes on aggregation after protonation in acid

Gaeta

Randazzo

Cristaldi

et al. 2017

J. Porphyrins Phthalocyanines

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Acid-base properties of tetra-anionic zinc meso-5,10,15,20-tetrakis-(4-sulfonatophenyl) porphyrin (ZnTPPS) in presence of cationic and anionic polyelectrolytes are studied by UV-visible spectroscopy. In fact, spectral modifications related to the out-of-plane deformation of porphyrins after protonation allow for an easy probing of the protonation event that, in presence of a metal derivative, requires a deprotonation step. Interactions with poly-D-glutamate and poly-L-lysine, modulated by system electrostatics and by the presence of an axially-coordinated central metal ion, trigger both protonation occurrences as well as porphyrin self-aggregation. The crucial role of electrostatic interactions experienced by the metalated inner core in strong acid solution, probed by UV-visible spectroscopy, are discussed.

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Self-assembly in water of the sodium salts of meso-sulfonatophenyl substituted porphyrins

Cited by 137 publications

References 39 publications

Inactivation of Human Immunodeficiency Virus Type 1 by Porphyrins

Inactivation of Human Immunodeficiency Virus Type 1 by Porphyrins

Aggregation Behavior of Protoporphyrin IX in Aqueous Solutions: Clear Evidence of Vesicle Formation

ZnTPPS demetalation: Role of polyelectrolytes on aggregation after protonation in acid

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