Leszek Czuchajowski

A series of meso-tris (N-methyl-pyridiniumyl)-(4-alkylamidophenyl) porphyrins: synthesis, interaction with DNA and antibacterial activity.

A series of meso-5,10,15-tris(N-methyl-4-pyridiniumyl)-20-(4-alkylamidophen yl) porphyrins were synthesized by derivatizing the amino group on the phenyl ring with the following hydrophobic groups: -C(O)C7F15, -C(O)CH=CH2, C(O)CH3, -C(O)C7H15, and -C(O)C15H31. The cationic tris-pyridiumyl porphyrin core serves as a DNA binding motif and a photosensitizer to photomodify DNA molecules. The changes of the UV-Vis absorption spectra during the titration of these porphyrins with calf thymus DNA revealed a large bathochromic shift (up to 14 nm) and a hypochromicity (up to 55%) of the porphyrins Soret bands, usually considered as proof of porphyrin intercalation into DNA. Association constants (K) calculated according to the McGhee and von Hippel model, were in the range of 10(6)-10(7) M(-1). An increase in hydrophobicity of the substituents at the 20-meso-position produced higher binding affinity. These porphyrins caused photomodification of the supercoiled plasmid DNA when a green laser beam at 532 nm was applied. Those with higher surface activity acted more efficiently as DNA photomodifiers. The porphyrin with a perfluorinated alkyl chain (-COC7F15) at the meso-20-position inhibited the growth of gram-positive bacteria (S. aureus, or S. epidermidis). Other porphyrins exhibited moderate activity against both gram-negative and gram-positive organisms.

Porphyrinyl-uridines as the first water soluble porphyrinyl-nucleosides

Abstract Meso-derivatives of porphine containing N-methyl-4-pyridinium and 5′-0-p-phenylene-2′,3′-0-protected-uridine substituents were obtained as the first representatives of water soluble porphyrinyl-nucleosides.

First representatives of porphyrinylnucleosides

Abstract 5′-0-(5-p-Phenylene-10,15,20-tri-p-tolylporphyrin)uridine and similarly substituted(2′,3′-0-isopropylidene)adenosine were obtained as first representatives of nucleosides containing covalently bonded porphyrin.

Conductive polymeric films of meso-tetrakis[2,2]-para-cyclophanyl-metalloporphyrins — spectroelectrochemistry an and catalytic properties

Abstract New thin ffilms of meso -tetrakis[2,2]- para -cyclophanyl metalloporphyrin ccomplexes with Mn(II), Fe(II), Co(II) and Ni(II) were studied using electrochemical methods and UV-Vis thin-layer spectroehemistry. These polymeric films are if interest both for their significant electrical conductivity and as electrode coating materials that exhibit new patterns of catalytic reactivity in the reduction of oxygen. All of the films show a catalytic effect in the reduction of oxygen in acidic as well an basic media. Electroreduction of oxygen on the new polymeric porphyrins promotes the four-electron reduction directly to water.

Ribofuranosides N-substituted with meso-porphyrin as nucleoside-like compounds

Abstract Meso-tri(4-pyridyl)porphyrin-p-phenylene-1′-amino-D-ribose and the respective D-2-deoxyribose derivative were synthesized as first representatives of porphyrinyl-N-glycosides.

Porphyrinyl-nucleosides containing fluorinated nucleobases

Abstract Porphyrins were synthesized in which a meso-p-phenylene-O- bridge joins the porphine core with 5′-C of 5-flourouidine(protected), 5-CF 3 -thymidine or 2-N-trifluoroacetamidato-6-O pentafluorophenyl-2′-deoxyguanosine.

Transannular interactions insyn- andanti- [2.2](1,4) napthalenophanes andsyn- andanti- [2.2](1,4) anthracenophanes

The UV spectra of the title compounds were interpreted as a result ofPPP-CI-1 calculations of excitation energies and oscillator strengths for the singlet—singlet transitions. A good agreement of the theoretical transitions with the experimental spectrum was found. A strong transannular effect was characteristic for thesyn isomers, the effect decreased in the order:syn-ring anthracenophane,syn-ring naphtalenophane,anti-ring naphthalenophane,anti-ring anthracenophane. Also the influence of a pseudo-substituent effect was found and discussed.ZusammenfassungDie UV-Spektren der Titelverbindungen wurden mittelsPPP-CI-1-Rechnungen interpretiert; dabei wurde eine gute Übereinstimmung der theoretischen Übergänge mit den experimentellen Spektren gefunden. Für diesyn-Isomeren wurde ein starker transannularer Effekt festgestellt, dessen Einfluß in der Reihesyn-Ring Anthracenophan,syn-Ring Napthalenophan,anti-Ring Naphthalenophan,anti-Ring Anthracenophan abnimmt. Ebenso wurde ein pseudo-Substituenten-Effekt gefunden und in die Diskussion miteinbezogen.

The Synthesis of Isomeric Dithymidyl-phosphorus(V)-meso-tetraphenylporphyrins

The synthesis of three novel axial dinucleosides was successfully accomplished. The compounds are 5″-O, 5″-O-dithymidylphosphorus(V)-meso-tetraphenylporphyrin, 5″-O, 3″-O-dithymi-dylphosphorus(V)-meso-tetraphenylporphyrin, and 3″-O, 3″-O-dithymidylphosphorus(V)tetraphenylporo-phyrin. These compounds could provide a lead toward the synthesis of an oligo-porphyrinyl DNA analogue that represents a system containing phosphorus(V)porphine units axially connected through the 5″-O-thymidine-3″-O bridges.

A novel meso-[2.2]paracyclophanyltriphenylporphyrin; electrochemical oxidation and conductive polymeric film formation

The electrochemical oxidation, conductive film formation, and electrocatalytic properties of meso-[2.2]paracyclophanyltriphenylporphyrin were investigated.

Phosphorus (V) porphyrin diaxially substituted with Leu-enkephalin

Synthesis of the first phosphorus (V) porphyrin-peptide conjugate was successfully accomplished. A biologically active peptide, leucine enkephalin, was constructed on the phosphorus atom of the 5,10,15,20-meso-tetraphenylporphinato dichlorophosphorus (V) chloride. The method involved solution phase peptide synthesis. The first C-terminal amino acid in the sequence of the peptide was axially attached to the porphyrin through a linker, 3-aminopropanol, and the remainder of leucine enkephalin was synthesized by subsequent additions of amino acids. Leucine enkephalin-P(V) porphyrin conjugate represents a new group of compounds, and its synthesis broadens potential applications of P(V) porphyrine, e.g. in photodynamic therapy.