Poly porphyrin

Sarkar T, Srinives S, Sarkar S, Haddon RC, Mulchandani A. Single-walled carbon nano-tube-poly(porphyrin) hybrid for volatile organic compounds detection. J Phys Chem C 2014 118 1602-10. 

It is not surprising then that the first reported surface mediated reaction made use of vicinal dihalides. In addition to poly-p-nitrostyrene immobilized metallo-porphyrins and viologens were found to be catalytically active. Recently,... 

A poly(L-lysine) dendrimer 23 which carries 16 free-base porphyrins in one hemisphere and 16 Zn porphyrins in the other has been synthesized and studied in dimethylformamide solution [54]. In such a dendrimer, energy transfer from the Zn porphyrins to the free-base units can occur with 43% efficiency. When the 32 free base and zinc porphyrins were placed in a scrambled fashion, the efficiency of energy transfer was estimated to be 83% [55]. Very efficient (98%) energy transfer from Zn to free-base porphyrins was also observed in a rigid, snowflake-shaped structure in which three Zn porphyrin units alternate with three free-base porphyrin units [56]. 

That dendrimers are unique when compared with other architectures is confirmed by an investigation on porphyrin core dendrimers and their isomeric linear analogues [63]. The isomers displayed dramatically different hydrodynamic properties, crystallinity, and solubility characteristics when compared to those of their dendritic analogues, and photophysical studies showed that energy transfer from the poly(benzylether) backbone to the core was more efficient in the dendrimer because of the shorter distance between the donor units and the acceptor core. 

Tetra(o-aminophenyl)porphyrin, H-Co-Nl TPP, can for the purpose of electrochemical polymerization be simplistically viewed as four aniline molecules with a common porphyrin substituent, and one expects that their oxidation should form a "poly(aniline)" matrix with embedded porphyrin sites. The pattern of cyclic voltammetric oxidative ECP (1) of this functionalized metal complex is shown in Fig. 2A. The growing current-potential envelope represents accumulation of a polymer film that is electroactive and conducts electrons at the potentials needed to continuously oxidize fresh monomer that diffuses in from the bulk solution. If the film were not fully electroactive at this potential, since the film is a dense membrane barrier that prevents monomer from reaching the electrode, film growth would soon cease and the electrode would become passified. This was the case for the phenolically substituted porphyrin in Fig. 1. 

Fig. 2. Curve A Eleotropolymerization of ImH H2(o-NH2)TPP in 0.1M Et NClO /CH CN by sweeping potential at 200mV/s on Pt electrode. Numbers represent scan number. Curve B Cyclic voltammogram of an electropolymerized film of poly-[H2(o-NH2)TPP] on a Pt electrode, in 0.1M Et NClO /CH CN at 200 mV/s. Integration of the charge under the wave shows that coverage is 3.5X10 9 mol/cm of the porphyrin sites. Curve C Rotated disk electrode voltammetry of the Os(lII,Il) reaction for 0.2 mM...

The reduced poly-[Fe(II)TPP] porphyrin site now finds itself next to a fresh poly-[Fe(III)TPP(X)] site one polymer lattice unit further into the polymer. An electron hopping - or self exchange - reaction can then ensue, repeatedly, in successive layers and sites ... 

Figure 4 shows the application (6) of potentials to the Pt and Au electrodes of the sandwich (vs. a reference electrode elsewhere in the contacting electrolyte solution) so that they span the E° of the poly-[Co(II/I)TPP] couple (Fig. 4B). There is a consequent redistribution of the concentrations of the sites in the two oxidation states to achieve the steady state linear gradients shown in the inset. Figure 4C represents surface profilometry of a different film sample in order to determine the film thickness from that the actual porphyrin site concentration (0.85M). The flow of self exchange-supported current is experimentally parameterized by applying Fick s first law to the concentration-distance diagram in Fig. 4B ...

The decay of zinc tetrakis(A -methylpyridinium-4-yl(porphyrin 7r-radical cations in the presence of poly(styrenesulfonate) and IrIV oxides or [Ir(OI I )r,]2 has been studied at high pH.46 The hexahydroxide species was found to be very reactive. 

Other supramolecular structures such as dendrimers have also been synthesized with zinc-containing porphyrins. Sixteen free base and sixteen zinc porphyrin units were added at the fifth generation of dendritic poly(L-lysine) and intramolecular fluorescence energy transfer was observed.823 Assembly of supramolecular arrays in the solid state has been achieved with the incorporation of an amide group for hydrogen bonding. Zinc meso-tetra(4-amidophenyl)porphyrin... 

Most helicates have linear axes, though a few helicates with circular axes are known - indeed the chiral (D4) molecular squares formed from Zn2+ and 2,5 -bis(2,2 -bipyridin- 6 -yl)pyrazine, 22, may be regarded as circular helicates (450). The formation of circular or linear forms seems to depend on balances between kinetic and thermodynamic control iron(II)-poly-2,2/-diimine systems with their substitutionally-inert metal centers provide useful systems for disentangling thermodynamic and kinetic contributions. The mechanism of formation of circular helicates of this type is believed to entail a kinetically favored triple helicate intermediate (484). Self-assembly of chiral-twisted iron(III)-porphyrin dimers into extended polynuclear species takes place through the intermediacy... 

T. Yirgili, D. Lidzey, and D.D.C. Bradley, Efficient energy transfer from blue to red in tetra-porphyrin-doped poly(9,9-dioctylfluorene) light-emitting diodes, Adv. Mater., 12 58-62, 2000. 

The method consists of the retention by sorption of the porphyrins on poly (vinyl alcohol) (PVA) hydrogels. Poly (vinyl alcohol) (PVA) is selected as the polymer of choice for the purification of industrial and medical wastewaters due to its capacity to form physically crosslinked hydrogels with the advantages of non-toxic, non-carcinogenic and biodegradable properties. 

Some authors consider that poly(vinyl alcohol) hydrogels represent an efficient and environmentally viable alternative advanced purification method for porphyrin-containing medical wastewaters. 

S. Varga, S. Patachia, R. Ion. The application of poly(vinyl alcohol) based hydrogels for the decontamination of porphyrins-containing medical waste waters. Endvedu-2007 International Conference, Brasov, Romania, Book of Abstracts Bulletin of the Transilvania University of Brasov, 2007. In press. 

Figure 13.13 Poly(aryl ether) dendrimers with a porphyrin core and dendritic imidazoles...

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