Chiral micellar porphyrin fibers with 2-aminoglycosamide head groups

Fuhrhop, Jürgen‐Hinrich; Demoulin, Corinna; Boettcher, Christoph; Koening, Juergen; Siggel, Ulrich

doi:10.1021/ja00037a018

Cited by 167 publications

(123 citation statements)

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“…Other authors reported just the presence of a shoulder at 460 nm under neutral pH conditions, while rapid precipitation occurs on decreasing pH. 4 Results similar to those of Inamura et al were obtained only by using water/dimethyl sulfoxide mixtures (1:20 in molar ratio) as solvent. Anyway, the instability and low reproducibility of the experimental results prevented further investigations.…”

Section: Introductionsupporting

confidence: 62%

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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Section: Introductionsupporting

confidence: 62%

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

et al. 2002

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“…All dimerized in aqueous solutions with the dimers stability dependent upon the substitution pattern. The diglycosylated derivative 115 was the most stable dimer with an offset stacked geometry similar to that reported for the dimer of an aminoglucosamide protoporphyrin in solution [31,187] . The fluorescence of all dimers was quenched, except for the 5,10-diglycosylated derivative 115.…”

Section: Unsymmetrically Substituted Glycoporphyrinssupporting

confidence: 75%

“…Various methods of linking carbohydrates to porphyrin scaffolds, for example by direct glycosylation to the porphyrin [30] , amide [31] , or triazole linkages [32] are available. The number and regiochemical arrangement of the sugar units gives scope for fine-tuning the hydrophobicity and hydrophilicity.…”

Section: Carbohydratesmentioning

confidence: 99%

“…The substitution of the glycosyl group on the ortho position of the meso phenyl caused steric hindrance to metallation by zinc [160] . In extension of this work Maillard et al synthesized a range of tetraglycosylated TPP's containing glucopyranosyl, galactopyranosyl, maltosyl, and glucosaminosyl residues Olinked at the para position under Lindsey condensation conditions (29)(30)(31)(32)(33)(34)(35)(36) [162] . Similar compounds were prepared to determine the effect the glycosyl unit had on the singlet oxygen production for possible application in asymmetric photooxygenation.…”

Section: A 4 -Type Porphyrinsmentioning

confidence: 99%

“…Another example is the use of glycosylated protoporphyrin IX derivatives as micellular fibers [31] . The amphiphilic glycosylated porphyrins 652-655 were synthesized from the porphyrin-formic acid mixed anhydride (651a) and the acetyl-2-deoxy-2-aminopyranosides which on subsequent deprotection afforded the desired amphiphilic compounds.…”

Section: Membrane and Protein Interactionsmentioning

confidence: 99%

See 2 more Smart Citations

Chemical Synthesis and Medicinal Applications of Glycoporphyrins

Moylan¹,

Scanlan²,

Senge

2015

CMC

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Abstract:This review presents an in-depth overview of the modification of porphyrins with bioconjugates and their applications in medicine today. Porphyrin bioconjugates ranging from nucleotides to steroids are under active scrutiny. However, carbohydrates have been at the forefront of such research in recent years and offer significant potential. This is attributed to their own selectivity to lectins on the surface of cancer cells and their influence on the amphiphilicity of the porphyrin macrocycle. These characteristics and the tendency of porphyrin photosensitizers to accumulate in tumor tissues make glycoporphyrins promising candidates for use as photosensitizers. Thus, a detailed overview of the synthesis and biological evaluation of glycoporphyrins is given with a particular focus on their applications in photodynamic therapy and their future prospects as drug candidates have been reported.

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Molecular environment effect onO₂binding to lipidporphyrinatoiron(II) complexes in aqueous media

Tsuchida

Komatsu

Yanagimoto

2000

J. Porphyrins Phthalocyanines

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Lipidporphyrinatoiron(II) complexes are tetrakis(o-substituted)phenylporphinatoiron(II) derivatives which can be easily dispersed in water by molecular assembling. The most remarkable aspect of lipidporphyrinatoiron(II) assemblies is their reversible binding of dioxygen under physiological conditions (in aqueous media, pH 7.3, 37 °C) like hemoglobin and myoglobin. In these structures the O 2-binding properties are largely influenced by the molecular environment around the coordination site. Tetrakis(o-pivalamido)phenylporphinatoiron(II) with a covalently linked axial imidazole (lipidporphyrinatoiron(II), 1) is incorporated into recombinant human serum albumin (rHSA), providing a totally synthetic O 2-carrying hemoprotein (rHSA–1). Electrospray ionization mass spectrometry revealed the molecular mass of this non-covalent albumin–porphyrin hybrid. The O 2 rebinding after laser flash photolysis represented a three-phase decay, suggesting that each porphyrin is embedded into different cavities in the albumin structure. On the other hand, amphiphilic lipidporphyrinatoiron(II) with four alkylphosphocholine chains (2) is self-organized in aqueous solution to produce bimolecular fibers with a uniform thickness of 10 nm. This fiber also gave a stable O 2 adduct, and the O 2 rebinding after laser flash irradiation showed monophasic kinetics. Up to 20 vol% of methanol, which is a critical concentration for fiber formation, the morphology was gradually dissociated into spherical micelles, and the stability of the dioxygenated species suddenly decreased to 10% of that of the fibers.

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Chiral micellar porphyrin fibers with 2-aminoglycosamide head groups

Cited by 167 publications

References 0 publications

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

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

Chemical Synthesis and Medicinal Applications of Glycoporphyrins

Molecular environment effect onO₂binding to lipidporphyrinatoiron(II) complexes in aqueous media

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Chiral micellar porphyrin fibers with 2-aminoglycosamide head groups

Cited by 167 publications

References 0 publications

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

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

Chemical Synthesis and Medicinal Applications of Glycoporphyrins

Molecular environment effect onO2binding to lipidporphyrinatoiron(II) complexes in aqueous media

Contact Info

Product

Resources

About

Molecular environment effect onO₂binding to lipidporphyrinatoiron(II) complexes in aqueous media