Singlet oxygen fullerenes

Y. Mikata, S. Takagi, M. Tanahashi, S. Ishii, M. Obata, Y. Miyamoto, K. Wakita, T. Nishisaka, T. Hirano, T. Ito, M. Hoshino, C. Ohtsuki, et al., Detection of 1270 nm emission from singlet oxygen and photocytotoxic property of sugar-pendant [60]fullerene, Bioorg. Med. Chem. Lett., 13 (2003) 3289-3292. 

Of all the fullerene forms, the nearly spherical properties of C o have attracted the greatest attention, especially in the field of bioconjugation. In addition to its physical properties, C o fullerenes have unique photo-optical and electro-chemical properties, which make them useful as carriers for biomedical research applications. For instance, upon exposure to light C o will generate singlet oxygen, which can be used in vivo to cleave biological molecules, particularly DNA and RNA. Studies indicate that irradiation of Cgo in solution can be used to destroy virus contamination (Kasermann and Kempf, 1997). Solutions of Buckminsterfullerene are a deep purple color, whereas other sizes of fullerenes display a variety of other colors. 

In other cases fullerene antibacterial action takes place after photoirradiation of fulleropyrrolidinium salts. It is not yet clear if the photodynamic action implies the participation of superoxide and hydroxyl radicals (type I mechanism) or singlet oxygen (type II mechanism) but the efficacy is really interesting with the death of more than 99.9% of bacterial and fungal cells and a special selectivity for microbes over mammalian cells (Tegos et al., 2005). Also a sulfobutyl fullerene derivative is able to inhibit environmental bacteria after photoirradiation and it exerts its action on E. coli even if incorporated in coated polymer (Yu et al., 2005). 

The cytotoxic and photocytotoxic effects of two water-soluble fullerene derivatives, a dendritic CL mono-adduct and the malonic acid CL tris-adduct were tested on Jurkat cells when irradiated with UVA or UVB light (Rancan et al., 2002). The cell death was mainly caused by membrane damage and it was UV dose-dependent. Tris-malonic acid fullerene was found to be more phototoxic than the dendritic derivative. This result is in contrast to the singlet oxygen quantum yields determined for the two compounds. 

Sera N, Tokiwa H, Miyata N (1996) Mutagenicity of the fullerene C60-generated singlet oxygen dependent formation of lipid peroxides. Carcinogenesis 17 2163-2169. 

The course of viral photodynamic inactivation in allantoic fluid is probably directed by the following process the initial period of induction is a result of the quenching of singlet oxygen (or other reactive forms of oxygen) by natural antioxidants present in the fluid (Kolb, 1991). Subsequently, a dramatic drop in the viral titer was observed. This then reached a plateau due to the consumption of the active fraction of the fullerene. This may be indirectly confirmed by the results of viral titration after the addition of a new portion of fullerene when the process of inactivation was observed again. 

So, fullerenes C60 and their derivatives may be potential damaging agents of biologic systems upon PDT, because upon irradiation C60 molecule is able to generate singlet oxygen, selectively penetrate tumor cells, and be accumulated there and could be easily removed from biologic medium. 

Boutorine AS, Tokuyama H, Takasugi M et al. (1994) Singlet oxygen production from fullerene derivatives. Angew Chem Int Ed. 33 2462-2465. 

Hamano T, Okuda K, Mashino T, et al. (1997) Singlet oxygen production from fullerene derivatives effect of sequential functionalization of the fullerene core. Chem Commun. 1 21-22. 

Prat F, Stackow R, Bernstein R et al. (1999) Triplet-state properties and singlet oxygen generation in a homologous series of functionalized fullerene derivatives. J Phys Chem. 103 7230-7235. 

Danilov OB, Belousova IM, Mak AA, Belousov VP, Grenishin AS, Kiselev VM, Kris ko AV, Ponomarev AN, Sosnov EN (2003) Generation of singlet oxygen with the use of optically excited fullerenes and fullerene-like nanoparticles. Optics and Spectroscopy 95 833-842. 

Scheme 11.4 Photochemical reaction of 14 with singlet oxygen, leading to the cluster opened fullerene 19. (i) O2 hv, benzene (II) [2+2] cycloreversion, keto-enol tautomerization.

Observations Although singlet oxygen was previously prepared by milling fullerene... 

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