DNA interactions and photocatalytic strand cleavage by artificial nucleases based on water-soluble gold(III) porphyrins.
The novel gold porphyrin complex (5,10,15-tris(N-methylpyridinium-4-yl)-20-(1-pyrenyl)-porphyrinato)gold(III) chloride, [Au(III)(TMPy3Pyr1P)]Cl4, was prepared and characterized by optical spectroscopy, high-resolution nuclear magnetic resonance (NMR), and electrospray mass spectrometry. This cationic multichromophore compound exhibits excellent water solubility and does not form aggregates under physiological conditions. Binding interactions of this complex and related model compounds with nucleic acid substrates have been studied and characterized by NMR and circular dichroism spectroscopy. The photoreactivity of [Au(III)(TMPy3Pyr1P)]Cl4 was investigated under anaerobic and aerobic conditions in the presence of an excess of purine nucleoside, guanosine, and plasmid DNA. Photocatalytic oxidative degradation of guanosine and the change from supercoiled to circular plasmid DNA upon monochromatic irradiation and polychromatic blue-light exposure with a maximum at 420 nm was explored. The potential of the novel water-soluble cationic metallointercalator complex [Au(III)(TMPy3Pyr1P)]Cl4 to serve as a catalytic photonuclease for the cleavage of DNA has been demonstrated.
Haeubl
Martin
M
Institut für Organische Chemie, Johannes Kepler Universität Linz (JKU), Altenberger Str. 69, 4040 Linz, Austria.
Reith
Lorenz Michael
LM
Gruber
Bernadette
B
Karner
Uwe
U
Müller
Norbert
N
Knör
Günther
G
Schoefberger
Wolfgang
W
D000970:Antineoplastic Agents / Q000138:chemical synthesis / Q000737:chemistry*; D002384:Catalysis; D002942:Circular Dichroism; D004247:DNA / Q000737:chemistry* / Q000528:radiation effects; D053903:DNA Breaks, Double-Stranded; D003848:Deoxyguanine Nucleotides / Q000737:chemistry / Q000528:radiation effects; D055664:Electrochemical Techniques; D006046:Gold / Q000737:chemistry*; D006151:Guanosine / Q000737:chemistry / Q000528:radiation effects; D008027:Light; D009682:Magnetic Resonance Spectroscopy; D008665:Metalloporphyrins / Q000138:chemical synthesis / Q000737:chemistry*; D050607:Organogold Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010782:Photolysis; D017319:Photosensitizing Agents / Q000138:chemical synthesis / Q000737:chemistry*; D011166:Porphyrins / Q000737:chemistry; D026082:Singlet Oxygen / Q000737:chemistry; D012995:Solubility; D013050:Spectrometry, Fluorescence; D021241:Spectrometry, Mass, Electrospray Ionization; D013056:Spectrophotometry, Ultraviolet; D044366:Transition Temperature
C545834:(5,10,15-tris(N-methylpyridinium-4-yl)-20-(1-pyrenyl)-porphyrinato)gold(III); D000970:Antineoplastic Agents; D003848:Deoxyguanine Nucleotides; D008665:Metalloporphyrins; D050607:Organogold Compounds; D017319:Photosensitizing Agents; D011166:Porphyrins; C545835:porphyrin 5,10,15-tris(N-methylpyridinium-4-yl)-20-(1-pyrenyl)-21H,23H-porphyrin; D006151:Guanosine; D026082:Singlet Oxygen; D006046:Gold; C007257:2'-deoxyguanosine 5'-phosphate; D004247:DNA