Porphyrins, labelled

O Riordan, T.C. Soini, A.E. Soini. J.T. Papkovsky, D.T. Performance evaluation of the phosphorescent porphyrin label Solid-phase immunoassay of a-fetoprotein. Anal. Chem. 2002, 74 (22). 5845-5850. 

Originally, 1,19-unsubstituted or 1,19-dicarboxylated biladienes-ac were prepared75 for the synthesis of corroles (See Section 1.6.), but by condensation with formaldehyde they give the corresponding porphyrins, e.g. 14. The method is especially valuable for the introduction of isotopic labels from the formaldehyde moiety.76... 

The chemical reactivity of the organoruthenium and -osmium porphyrin complexes varies considerably, with some complexes (M(Por)R2, M(Por)R and Os(OEP)(NO)R) at least moderately air stable, while most are light sensitive and Stability is improved by handling them in the dark. Chemical transformations directly involving the methyl group have been observed for Ru(TTP) NO)Me, which inserts SO2 to form Ru(TTP)(N0) 0S(0)Me and Ru(OEP)Me which undergoes H- atom abstraction reactions with the radical trap TEMPO in benzene solution to yield Ru(OEP)(CO)(TEMPO). Isotope labeling studies indicate that the carbonyl carbon atom is derived from the methyl carbon atom. "" Reaction of... 

The magnesium enolates are prepared by treatment of malonic acid half ester either with magnesium ethylate[24],[32] or with isopropylmagnesium bromide[24] or chloride.t26] Ref. [23] describes the synthesis of a 13C-labelled ethyl acetoacetate. Concerning the synthesis of porphyrin / -ketoesters,[3 1 it was noticed that the method via imidazolides is more efficient than the other approach via acid chlorides and sodiomalonic esters. 

Rakowsky, M. H., K. M. More et al. (1995). Time-domain electron paramagnetic resonance as a probe of electron-electron spin-spin interaction in spin-labeled low-spin iron porphyrins. J. Am. Chem. Soc. 117 2049-2057. 

A.R. Raitsimring and F.A. Walker, Porphyrin and ligand protons as internal labels for determination of ligand orientations in ESEEMS of low-spin d5 complexes in glassy media ESEEM studies of the orientation of the g tensor with respect to the planes of axial ligands and porphyrin nitrogens of low-spin ferriheme systems, J. Am. Chem. Soc., 1998, 120, 991. 

Like the palladium(II) complexes, the platinum(II) porphyrins show appreciable phosphorescence even in aqueous media at room temperature in one study,169 singlet oxygen quantum yields ranged from 0.1 to 0.9 and were strongly influenced by dimerization/aggregation. Platinum(II) 5,10,15,20-tetrakis(/>-carboxyphenyl)porphyrin and platinum(II)coproporphyrin-I ((36) for Pd read Pt) have been studied as phosphorescent labels of antibodies for use in time-resolved microscopy.189... 

Maehashi et al. (2007) used pyrene adsorption to make carbon nanotubes labeled with DNA aptamers and incorporated them into a field effect transistor constructed to produce a label-free biosensor. The biosensor could measure the concentration of IgE in samples down to 250 pM, as the antibody molecules bound to the aptamers on the nanotubes. Felekis and Tagmatarchis (2005) used a positively charged pyrene compound to prepare water-soluble SWNTs and then electrostatically adsorb porphyrin rings to study electron transfer interactions. Pyrene derivatives also have been used successfully to add a chromophore to carbon nanotubes using covalent coupling to an oxidized SWNT (Alvaro et al., 2004). In this case, the pyrene ring structure was not used to adsorb directly to the nanotube surface, but a side-chain functional group was used to link it covalently to modified SWNTs. 

Fig. 26. Structure of tetrakis[3,4-bis(carboxymethyleneoxy)phenyl porphyrin] indirectly labeled with "mTc.

Fig. 7 Cytochrome P450-mimic oxidation of fenvalerate (9) by iron(ffl) porphyrin. The values in parentheses are percent of the applied 14C (Asterisk labeled position) after 50 min...

Antisense and antigene oligonucleotides labeled with manga-nese(III) porphyrins can selectively cleave double-stranded DNA... 

Fig. 3.10. Calculated and experimental (FD-MS, cf. Chap. 8.5.4) isotopic pattern of a ruthenium carbonyl porphyrin complex. The isotopic pattern supports the presumed molecular composition. The label is attached to the peak corresponding to the ° Ru-contaming ion. Adapted fromRef. [17] with permission. IM Publications, 1997.

Fig. 2. The distinct steps in the oxidation of heme to biliverdin catalyzed by heme oxygenase. The substituted carbons of the porphyrin ring are labeled, as are the meso-positions. The oxygens introduced in the catalytic process are shown in bold t3rpe.

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