Anionic porphyrin

Fig.1. Structures of porphyrin 1, chlorophyll 2, and phthalocyanine 3. In the presence of metal salts M"+X (M=metal, X=counter anion, n=oxidation state or number of counter anions), porphyrins produce chelate complexes. Some metal chelates of the porphyrins, such as ZnPor, form further coordination bonds with other ligands such as pyridines...

Fig. 11a,b. Binding affinities of IgG, IgM, and the antibody dendrimer (Gl) with the cationic porphyrin (TMPyP) (a) and those with the anionic porphyrin (TCPP) (b) estimated by ELISA... 

Fig. 12a,b. The sensorgrams for the binding of the antibody dendrimer (a) or IgG (b) to the anionic porphyrin immobilized onto the surface of the sensor chip. Phosphate borate buffer (0.1 M, pH 9.0) was used. TCPP was immobilized via hexamethylenediamine spacer onto the sensor chip and then a solution of IgG or the dendrimer was injected to the flow cell. After 60 s from the injection of the antibody solutions, flow ceU was filled with buffer... 

Fig. 67. Schematic representation of three types of anionic porphyrins in a cast multibilayer film of 34. The overall bilayer organization is assumed to be the same as that of Fig. 64. For clarity, counterions are not shown and the bilayer units are separated from each other. The spacer portion is also not shown in Stereogram . Type I porphyrins (Fig. 66) are inserted into the bilayer along the molecular axis of the spacer chain. Type II porphyrins are randomly placed on the bilayer surface. Type III porphyrins lie flat on the bilayer [445]...

Photoinduced Hydrogen Evolution with Water-soluble Viologen-linked Anionic Porphyrin and Hydrogenase... 

Fig. 18.9 Chemical structures of water-soluble viologen-linked anionic porphyrins (TPPSC V).

Several anionic porphyrins, for example, can transfer electrons... 

Figure 5.56 Schematic illustrating the self-assembled multilayers of sodium 3-mercaptoethane-sulfonate (layer 1 ), hexacationic homooxacalix[3]arene-fullerene (2 1) complex (layer 2 ), with either the anionic porphyrin polymer ( 3 ) or its zinc porphyrin analogue ( 4 ) forming the third layer. Reprinted with permission from A. Ikeda, T. Hatano, S. Shinkai, T. Akiyama and S. Yamada, /. Am. Chem. Soc., 123,4855 (2001). Copyright (2001) American Chemical Society...

Fig. 17 Structure of the anionic porphyrin cis- and trans-DPPS and of the A— and A— enantiomers of [Ru(phen)3]2+. Modified from [50, 51]...

Moreover, fluorescence characterization of these systems indicated, as previously hypothesized, that ruthenium(II) cationic complexes are able to activate energy transfer processes towards the anionic porphyrins [50]. 

The behaviour of the systems presented above is, however, even more complex and richer than what we have shown until now. In particular, a deeper study of the tetra-anionic porphyrin Ru-complexes system has revealed that, using proper experimental conditions, not only the porphyrin J-aggregates show the chiral memory phenomenon, but also that the chiral information can be cyclically erased and rewritten, switching on and off the porphyrin ICD signal by pH variations [51]. 

H2TPPS and [Ru(phen)3]2+. Interaction is indicated by variation in the absorption spectra (Fig. 22) and, especially, by the appearance of an induced circular dichro-ism (Fig. 23) band in the absorption region of the achiral porphyrin. The relationship between chirality of the cationic metal complex and that transferred to the anionic porphyrins is straightforward because interactions of H2TPPS with the A- and A-[Ru(phen)3]2+ lead to mirror-image ICD signals (Fig. 23) [51]. 

D Urso A, Mammana A, Balaz M et al (2009) Interactions of a tetra-anionic porphyrin with DNA from a Z-DNA sensor to a versatile supramolecular device. J Am Chem Soc 131 2046-2047... 

Jiang S, Zhang L, Liu M (2009) Photo-triggered J-aggregation and chiral symmetry breaking of an anionic porphyrin (TPPS) in mixed organic solvent. Chem Commun 41 6252-6254... 

Ojadi E, Selzer R, Linschitz H (1985) Properties of porphyrin dimers, formed by pairing cationic and anionic porphyrins. J Am Chem Soc 107 7783-7784... 

Randazzo R, Lauceri R, Mammana A et al (2009) Interactions of A and A enantiomers of ruthenium(II) cationic complexes with achiral anionic porphyrins. Chirality 21 92-96... 

Randazzo R, Mammana A, D Urso A et al (2008) Reversible chiral memory in ruthenium tris(phenanthroline)-anionic porphyrin complexes. Angew Chem Int Ed Engl 47 9879-9882... 

Cationic amphiphilic CDs, heptakis[2-co-amino-0-oligo(ethylene oxide] hexyl-thio-ji-CD nanoparticles, have encapsulated anionic porphyrins (TPPS) by entangling these molecules within the aliphatic chains aligning both faces of the cationic amphiphilic CD. These nanoparticles were demonstrated to preserve the photodynamic properties of the entrapped photoactive agent. The photodynamic efficacy of the carrier/sensitizer nanoparticles was proven by in vitro studies on tumor HeLa cells showing significant cell death upon illumination with visible light [88]. 

Mazzaglia, A., Angelini, N., Darcy, R., Donohue, R., Lombardo, D., Micali, N., Sciortino, M.T., Villari,V.,and Scolaro,L.M. (2003), Novel heterotropic colloids of anionic porphyrins entangled in cationic amphiphilic cyclodextrins Spectroscopic investigation and intracellular delivery, Chem. Eur. 1,9,5762-5769. 

Sortino, S., Mazzagha, A., Scolaro, L. M., Merlo, F. M., Volveri, V., and Sciortino, M. T. (2006), Nanoparticles of cationic amphiphilic cyclodextrins entangling anionic porphyrins as carrier-sensitizer system in photodynamic cancer therapy, Biomaterials, 27, 4256-4265. 

Ion-association adsorption of water-soluble porphyrin was studied using time-resolved TIR fluorometry. Interfacial adsorption of anionic or cationic surfactants succeeded in attracting the oppositely charged porphyrin from the mixture of cationic and anionic porphyrins in the aqueous phase, tetrakis(sulphonatophenyl)porphyiin (TPPS) adsorbed with the hexadecyltrimethylammonium ion and tetrakis(iV-methylpyridyl)porphyrin (TMPyP) with the hexadecanesulfonate [44], In addition, it was found that the application of an external electric field across the interface enabled to control the interfacial ion-association adsorption of ionic porphyrin [45]. Furthermore, TIR Raman microspectroscopy revealed the interfacial concentration of meso-tetrakis(A -methylpyridyl) porphyrinato-manganese(III) (Mn(tmpyp) +) adsorbed with dihexadecyl hydrogenphosphate (DHP) at the toluene/water interface and also revealed that the orientation of the tilt angle was 65° from the interface normal [46]. 

Recently, we have also used VCD and a combination of VCD and ECD to study the non-covalent interactions between two groups of important biomolecules, i.e. biopolymers - polypeptide and DNA - and cationic and anionic porphyrins [34-36]. 

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