Biopolym. Cell. 2006; 22(3):231-235.
http://dx.doi.org/10.7124/bc.000735
Molecular Biophysics
Possible electronic mechanisms of generation and quenching of luminescence of singlet oxygen in the course of photodynamic therapy: ab initio study
1Minaev B. F., 1Yashchuk L. B.
  1. B. Khmelnyckyy Cherkasy National University
    81, Shevchenko Blvd., Cherkassy, Ukraine, 18031

Abstract

On the basis of ab initio quantum chemical calculations the strong enhancement of the 1(a1Δg·S0)→ 1(X3Σg– ·T) transition in collision complex between O2 and organic dye is predicted, where T is the triplet excited state of the dye and S0 is its ground singlet state. The collision-induced electric dipole transition moment depends on polarizability of the dye and can be used for the estimation of energy transfer rate constant. Quantum chemical calculations can predict the most efficient dye sensibilizer for photodynamic therapy of cancer, instead of the difficult experimental search. Some new ideas are proposed for additional laser simulated mechanisms of active oxygen generation.
Keywords: singlet, triplet, complex of collision, transition moment, spin-orbit coupling
Full text: (PDF, in English)

References

[1] Schweitzer C, Schmidt R. Physical mechanisms of generation and deactivation of singlet oxygen. Chem Rev. 2003;103(5):1685-757.
[2] Datta D, Vaidehi N, Xu X, Goddard WA 3rd. Mechanism for antibody catalysis of the oxidation of water by singlet dioxygen. Proc Natl Acad Sci U S A. 2002;99(5):2636-41.
[3] Redmond RW, Gamlin JN. A compilation of singlet oxygen yields from biologically relevant molecules. Photochem Photobiol. 1999;70(4):391-475.
[4] Krasnovski? AA. [Photosensitized luminescence of singlet oxygen in solution]. Biofizika. 1976;21(4):748-9.
[5] Krasnovsky A. Quantum yield of photosensitized luminescence and radiative lifetime of singlet (1?g) molecular oxygen in solutions. Chem Phys Lett. 1981;81(3):443–5.
[6] Egorov SY, Kamalov VF, Koroteev NI, Krasnovsky AA, Toleutaev BN, Zinukov SV. Rise and decay kinetics of photosensitized singlet oxygen luminescence in water. Measurements with nanosecond time-correlated single photon counting technique. Chem Phys Lett. 1989;163(4-5):421–4.
[7] Minaev B. F. USSR-All-Union School on Quantum Chemistry: Abstracts. Karaganda, 1982.
[8] Minaev BF. Theoretical analysis and prognostication of spin-orbit coupling effects in molecular spectroscopy and che­ mical kinetics. Dr. Sc. Thesis. N. N. Semenov. Institute of Chemical Physics. Moscow, 1983.
[9] Sveshnikova EB, Minaev BF. Mechanism of nonradiative quenching of singlet oxygen in solution. Opt Spectrosc. 1983; 54: 320-3.
[10] Becker AC, Schurath U, Dubost H, Galaup JP. Luminescence of metastable 16O2 (18O2) in solid argon: Relaxation and energy transfer. Chem Phys. 1988;125(2-3):321–36.
[11] Minaev BF. Intensity of singlet-triplet transitions in the oxygen molecule and selective effect of an external heave atom . Opt Spectrosc. 1978; 45: 936-42.
[12] Klotz R, Peyerimhoff SD. Theoretical study of the intensity of the spin- or dipole forbidden transitions between the c 1?-u, A?3?u, A3?+u and X3?-g, a1?g, b1?+ g states in O2 . Mol Phys. 1986;57(3):573–94.
[13] Minaev BF, ?gren H. Collision-induced b1?g+–a1 ?g, b1?g+–X3 ?g- and a1?g–X3?g - transition probabilities in molecular oxygen. Faraday Trans. 1997;93(13):2231–9.
[14] Minaev BF. Quantum-chemical investigation of the mechanisms of the photosensitization, luminescence, and quenching of singlet1?g oxygen in solutions. J Appl Spectrosc. 1985;42(5):518–23.
[15] Minaev BF. The theory of solvent influence on radiative transition al?g probability in molecular oxygen. Opt Spectrosc. 1985; 58: 1238-46.
[16] Minaev BF. Ab initio study of the ground state properties of molecular oxygen. Spectrochim Acta A Mol Biomol Spectrosc. 2004;60(5):1027-41.
[17] Minaev BF. Oxygen absorption below and near the Herzberg I continuum. Ab initio calculation of the transitions probability from metastable states. Chem Phys. 2000;252(1-2):25–46.
[18] Minaev BF, Minaeva VA. MCSCF response calculations of the excited states properties of the O2 molecule and a part of its spectrum. Phys Chem Chem Phys. 2001;3(5):720–9.
[19] Minaev BF. The singlet oxygen absorption to the upper state of the Schumann–Runge system: the B 3?u-?a 1?g and B 3?u-?b 1?g+ transitions intensity calculation. Physical Chemistry Chem Phys. 1999;1(15):3403–13.
[20] Minaev BF, Kobzev GI. Response calculations of electronic and vibrational transitions in molecular oxygen induced by interaction with noble gases. Spectrochim Acta A Mol Biomol Spectrosc. 2003;59(14):3387–410.
[21] Minaev BF, Mambeterzina GK. Oxygen complexes with naphthalene and decapenthaene studied by configuration inter­ action method. Photoprocesses in atomic and molecular systems. Karaganda: KGU, 1984: 35-41.
[22] Schmidt R. Comment on “Analysis of mixed solvent effects on the properties of singlet oxygen (1?g)” . Chem Phys. 2004;304(3):315–6.