Singlet molecular oxygen, 02(’Ag) , has been intensively investigated over the last few decades, primarily in relation to photosensitization reactions. In combination with the increasing awareness and interest in singlet oxygen has been the development of various methodologies for the detection and quantification of singlet oxygen production. A large body of literature now exists concerning the singlet oxygengenerating abilities of a large variety of endogenous and exogenous compounds that can be photoactivated in the UV and visible regions of the electromagnetic spectrum. The purpose of this review was to compile data from many different sources to provide a convenient resource for biological scientists with interest in this area. This compilation is essentially an updated subset of the excellent comprehensive review on singlet oxygen yields by Wilkinson et af. (l), which, unlike this compilation, was not limited to biological molecules. The data are current up to the early months of 1999. The following tables include various related parameters in addition to the central parameter of the quantum yield of singlet oxygen generation (QA) for a given photosensitizer. The methodology or technique used to measure the QA value for each entry is given and ranges from direct detection of the luminescence produced on relaxation of singlet oxygen (time-resolved [TRILIT or steady-state [SSIL]), calorimetric

https://onlinelibrary.wiley.com/doi/pdf/10.1111/j.1751-1097.1999.tb08240.x

A Compilation of Singlet Oxygen Yields from Biologically Relevant Molecules

Metal Complexes as Photo- and Radiosensitizers

The singlet oxygen luminescence method and the photochemical methods using 1,3-diphenylisobenzofuran (DPBF) or bilirubin ditaurate (BDT) as chemical quenchers were employed to determine the single oxygen quantum yields (ΦΔ) of different phthalocyanines and tris(2,2″-bipyridyl)ruthenium(II) dichloride in dimethylformamide (DMF) or aqueous micellar solution of 0.1 M CTAC (cetyltrimethylammonium chloride). Additionally, a perylenetetracarboxylic acid diimide derivative was examined in DMF. In a series of tetrasulfonated phthalocyanines (PTS) the following order was found: ZnPTS > GaPTS > AlPTS ≈ H2PTS > CoPTS. In general, the singlet oxygen quantum yields are higher in DMF than in 0.1 M CTAC/H2O. The results obtained with the photochemical systems are comparable with those obtained by the photophysical method. The photochemical DPBF method results in absolute values of ΦΔ. However, in micellar solution, chain reactions occur when DPBF is used as chemical quencher in the photo-oxidative process. This problem ...

Singlet Oxygen Quantum Yields of Different Photosensitizers in Polar Solvents and Micellar Solutions

Photobleaching of sensitisers used in photodynamic therapy

Synthetic pathways to water-soluble phthalocyanines and close analogs

Unsymmetrical zinc(II) complexes of benzonaphthoporphyrazines 5a-12a bearing between one and eight pyridyloxy substituents are synthesized by statistical tetramerization of 6-(1,1-dimethylethyl)-2,3-naphthalenedicarbonitrile (1) with 4-(3-pyridyloxy)- or 4,5-bis-(3-pyridyloxy)-1,2-benzenedicarbonitrile (2, 3). Methylation of 5a-12a leads to the catianic pyridyloxybenzonaphthoporphyrazines 5b-12b having between one to eight positive charges. The Q-band transition in the visible spectra exhibits a bathochromic shift from 680 to 760 nm dependent upon the number of annelated naphthalene rings. The singlet oxygen quantum yields of the benzonaphthoporphyrazines determined by the dye-sensitized photooxidation of 1,3-diphenylisobenzofurane is surprisingly high (in the range of zinc phthalocyanine). The photooxidative stabilities of the photosensitizers described quantitatively by first-order kinetics decrease with the number of annelated naphtho groups. A linear correlation between the logarithm of the decomposition rate constant and the position of the highest occupied molecular orbital (HOMO)-level of the photosensitizers is found. Destabilization of the HOMO leads to a decrease of the photostability. Due to their adjustable long wavelength absorption, their intramolecular polarity axis and their different hydrophilic/hydrophobic character, these novel compounds may be suitable photosensitizers for the photodynamic therapy of cancer.

Unsymmetrically substituted benzonaphthoporphyrazines: a new class of cationic photosensitizers for the photodynamic therapy of cancer.

A new method for coatings of polymeric phthalocyanines and for comparison also of low molecular weight phthalocyanine metal complexes (W, Cr, Mo, Co) on quartz and titanium dioxide was developed by the reaction of metal carbonyls adsorbed on the carriers with tetracarbonitriles or phthalonitrile. By UV-vis or IR spectra the formation of structural uniform polymeric phthalocyanines on the carriers is established. The compounds are used then to compare their catalytic and photocatalytic activities in the oxidation of sulfide as test reaction.

Synthesis of polymeric and low molecular weight phthalocyanines from nitriles and metal carbonyls on SiO2 and TiO2 and catalytic activities in the sulfide oxidation

Porphyrins and Phthalocyanines in Macromolecules

For the application of photosensitizers in PDT attention must be given to the stability of these compounds. For various substituted and annelated tetraazaporphyrins zinc complexes the experimentally determined first order rate constant of the photo-oxidative decomposition in DMF were compared with the calculated values of the HOMO energy level. The method described allows one to predict the photo-oxidative stability by calculating their HOMO levels which is important for the use of macrocyclic metal complexes in the photodynamic therapy of cancer. To high photo-oxidative stability leads to risks in healthy tissues and reduces photodynamic effects in tumor tissues. To low photo-oxidative stability cause problems in preparation, purification and in vivo persistency of photosensitizers for tumor treatment.© (1997) COPYRIGHT SPIE--The International Society for Optical Engineering. Downloading of the abstract is permitted for personal use only.

Guenter Schnurpfeil

Papers

Unsymmetrically substituted benzonaphthoporphyrazines: a new class of cationic photosensitizers for the photodynamic therapy of cancer.

Synthesis of polymeric and low molecular weight phthalocyanines from nitriles and metal carbonyls on SiO2 and TiO2 and catalytic activities in the sulfide oxidation

Porphyrins and Phthalocyanines in Macromolecules

Photo-oxidative stability of various tetra-azaporphyrin derivatives in solution and correlation with semiempirical MO calculations

Chapter 3. Fluorinated Phthalocyanines as Molecular Semiconductor Thin Films