New Porphyrin-Nucleobase Hybrid Compounds and Their Interaction with Nucleosides and Nucleic Acids

Abstract

Four new porphyrin derivatives are described: one (1) with a methoxyphenyl group and three pyridinium units (for comparison only), and three others with either adenine (2, 3) or thymine (4) bases. The synthetic strategies vary from known literature procedures in that the methylation of pyridinium subunits takes place before the formation of the hybrid molecule, beginning with simultaneous condensation of pyridinealdehyde and 3-(propionyloxy)benzaldehyde, with subsequent chromatography under improved conditions. The thymine derivative 4 is obtained from trimethylated tetrapyridylporphyrin T4PyP by treatment with a suitable thyminealkyl bromide. Dilution experiments in water show the absence of intermolecular porphyrin associations under the experimental conditions used. UV and NMR spectroscopic data indicate strong intramolecular self-stacking between the porphyrin moiety and the covalently attached nucleobases. This results in smaller affinities of porphyrin-nucleobase conjugates towards added nucleosides than observed with the reference compounds tris-or tetrakis-pyridinium porphyrin (1 and TMPyP, respectively). Compounds 2−4 displayed no significant discrimination between A and T based on complementarity of nucleobases, which is explained by the strong competition from bulk water with Watson−Crick hydrogen bonds. Interactions of ligands 1−4 with ct DNA and

Porphyrinoid biohybrid materials as an emerging toolbox for biomedical light management

“…192 Moreover, adenine and thymine have been linked to H 2 Por, in order to study the interaction of the resulting hybrids with nucleic acids and nucleosides. 199 The authors concluded that self-aggregation, due to p-p stacking between the PS and nucleobases, has a big influence on the conjugates' binding properties.…”

Synthesis, Characterization and EPR Studies of Supramolecular Porphyrazines

“…In biological systems, cationic porphyrins can act as singlet oxygen generators in photodynamic therapy, inhibitors of human telomerases, receptors for peptides, DNA cleavers and specific probes of DNA structures [1][2][3][4][5][6][7][8][9][10][11]. As cationic porphyrins have planar structures with quaternized functional groups on the peripheral positions, their activity is different from conventional intercalators such as ethidium bromide, proflavin and daunomycin [8][9].…”

“…As cationic porphyrins have planar structures with quaternized functional groups on the peripheral positions, their activity is different from conventional intercalators such as ethidium bromide, proflavin and daunomycin [8][9]. Cry stall ographic analysis of a metaUoporphyrinoligonuclotide complex has shown that intercalation or binding of cationic porphyrin causes a distortion of the DNA molecule [1][2][3][4][5][6][7].…”

Synthesis of Porphyrins Di‐ and Tetra‐Functionalized with Nucleobases

“…For instance, the uracil‐functionalized porphyrins described by Drain et al ., [14] the water‐soluble NB‐porphyrins reported by Maiya et al [15] . and the NB‐porphyrin hybrid compounds described by Schneider et al [16] . were synthesized by an Adler synthesis, [17] alkylation reactions of NB's active amine sites and by a condensation reaction between corresponding NBs and porphyrin derivatives respectively.…”

“…[8,9] Other synthetic approaches were also used to introduce NBs to the porphyrin scaffold. For instance, the uracil-functionalized porphyrins described by Drain et al, [14] the water-soluble NB-porphyrins reported by Maiya et al [15] and the NB-porphyrin hybrid compounds described by Schneider et al [16] were synthesized by an Adler synthesis, [17] alkylation reactions of NB's active amine sites and by a condensation reaction between corresponding NBs and porphyrin derivatives respectively. Furthermore, the synthesis of porphyrins bearing nucleobases via ethoxy and acetyl linkers [18] or via amide linkers [19] was also reported.…”