Two-photon excitation studies of hypocrellins for photodynamic therapy.

The photophysical and photochemical properties of hypocrellins (HA and HB) are examined with two-photon excitations at 800 nm using femtosecond pulses from a Ti:sapphire laser. The two-photon excited fluorescence spectra of HA and HB are very similar to those obtained by one-photon excitation, which may indicate that the two-photon induced photodynamic processes of hypocrellins are similar to one-photon induced photodynamic processes. The two-photon excitation cross sections of HA and HB are measured at 800 nm as about 34.8 x 10(-50) cm(4) s/photon and 21.3 x 10(-50) cm(4) s/photon, respectively. The large two-photon cross sections of both HA and HB, suggest that the hypocrellins can be potential two-photon phototherapeutic agents. As an example for two-photon photodynamic therapy of hypocrellins, we also further examine the cell-damaging effects of HA upon two-photon illumination. Our preliminary results of cell viability test indicate hypocrellins can effectively damage the Hela cells under two-photon illumination.

[1]  M. McCloskey,et al.  Light-Induced Acidification by the Antiviral Agent Hypericin , 1995 .

[2]  P. Shaw,et al.  A comparison of tetrazolium reduction and FDA hydrolysis with other measures of microbial activity , 1990 .

[3]  J. Ordonez,et al.  Estimation of cell survival by flow cytometric quantification of fluorescein diacetate/propidium iodide viable cell number. , 1989, Cancer research.

[4]  Zhenjun Diwu,et al.  Photosensitization by anticancer agents 12. Perylene quinonoid pigments, a novel type of singlet oxygen sensitizer , 1992 .

[5]  Zhang Manhua,et al.  ELECTRONIC SPECTRA OF HYPOCRELLIN A, B AND THEIR DERIVATIVES , 1990 .

[6]  M. Olivo,et al.  Hypericin and hypocrellin induced apoptosis in human mucosal carcinoma cells. , 2001, Journal of photochemistry and photobiology. B, Biology.

[7]  Jacob W. Petrich,et al.  Excited-State Processes in Polycyclic Quinones: The Light-Induced Antiviral Agent, Hypocrellin, and a Comparison with Hypericin , 1996 .

[8]  Jacob W. Petrich,et al.  Picosecond Linear Dichroism and Absorption Anisotropy of Hypocrellin: Toward a Unified Picture of the Photophysics of Hypericin and Hypocrellin , 1998 .

[9]  Yuying He,et al.  Photoreactions of hypocrellin B with thiol compounds , 1998 .

[10]  K. Ikuta,et al.  Photoinactivation of Virus Infectivity by Hypocrellin A , 1997, Photochemistry and photobiology.

[11]  Robert R. Birge,et al.  Two-photon spectroscopy of protein-bound chromophores , 1986 .

[12]  Yuying He,et al.  Synthesis of a new water-soluble phototherapeutic sensitizer from hypocrellin B with enhanced red absorption , 1999 .

[13]  J. Bhawalkar,et al.  Two-photon photodynamic therapy. , 1997, Journal of clinical laser medicine & surgery.

[14]  J. An,et al.  Spectroscopic study on the photoreduction of hypocrellin A: generation of semiquinone radical anion and hydroquinone , 1995 .

[15]  J. Demas,et al.  Measurement of photoluminescence quantum yields. Review , 1971 .

[16]  J. Lijin,et al.  Glycoconjugated hypocrellin: photosensitized generation of free radicals (O2*-, *OH, and GHB*-) and singlet oxygen (1O2). , 1999, Free radical biology & medicine.

[17]  W. Webb,et al.  Measurement of two-photon excitation cross sections of molecular fluorophores with data from 690 to 1050 nm , 1996 .

[18]  T. Dougherty,et al.  HOW DOES PHOTODYNAMIC THERAPY WORK? , 1992, Photochemistry and photobiology.

[19]  E. A. Wachter,et al.  Simultaneous Two‐Photon Activation of Type‐I Photodynamic Therapy Agents , 1997, Photochemistry and photobiology.

[20]  Jianquan Shen,et al.  Active oxygen species (1O2, O2*-) generation in the system of TiO2 colloid sensitized by hypocrellin B. , 2002, Journal of photochemistry and photobiology. B, Biology.

[21]  Yuying He,et al.  pH Effect on the spectroscopic behavior and photoinduced generation of semiquinone anion radical of hypocrellin B , 1999 .

[22]  S. Boxer,et al.  Two‐Photon Excitation of 4'‐Hydroxymethyl‐4,5',8‐Trimethylpsoralen , 1997, Photochemistry and photobiology.

[23]  D. Cramb,et al.  Near‐Infrared Two‐Photon Excitation of Protoporphyrin IX: Photodynamics and Photoproduct Generation ¶ , 2000, Photochemistry and photobiology.

[24]  L. Mátyus,et al.  Flow cytometric analysis of viability of bull sperm cells. , 1984, Acta biochimica et biophysica; Academiae Scientiarum Hungaricae.

[25]  J. Lown,,et al.  Photosensitization with anticancer agents 13. The production of singlet oxygen by halogenated and metal-ion-chelated perylenequinones , 1992 .

[26]  W. Webb,et al.  Two-Photon Fluorescence Excitation Cross Sections of Biomolecular Probes from 690 to 960 nm. , 1998, Applied optics.

[27]  Li-jin Jiang,et al.  Characteristics of the reaction between semiquinone radical anion of hypocrellin A and oxygen in aprotic media , 1996 .

[28]  George A. Kraus,et al.  Excited-State Photophysics of Hypericin and Its Hexamethoxy Analog: Intramolecular Proton Transfer as a Nonradiative Process in Hypericin , 1997 .

[29]  J. Hudson,et al.  HYPOCRELLIN, FROM HYPOCRELLA BAMBUASE, IS PHOTOTOXIC TO HUMAN IMMUNODEFICIENCY VIRUS , 1994, Photochemistry and photobiology.

[30]  W. Denk,et al.  Two-photon laser scanning fluorescence microscopy. , 1990, Science.

[31]  George A. Kraus,et al.  Hypericin, Hypocrellin, and Model Compounds: Steady-State and Time-Resolved Fluorescence Anisotropies , 1998 .

[32]  Yuying He,et al.  Photodynamic action of a water-soluble hypocrellin derivative with enhanced absorptivity in the phototherapeutic window I: ESR and UV-Vis studies on the photogeneration of the semiquinone anion radical and hydroquinone , 1998 .

[33]  Man-hua Zhang,et al.  Photobleaching of Hypocrellin B and its Butylamino-substituted Derivative in Solutions , 2001 .

[34]  J. An,et al.  EPR and spectrophotometric studies on free radicals (O2.-, Cysa-HB.-) and singlet oxygen (1O2) generated by irradiation of cysteamine substituted hypocrellin B. , 1998, International journal of radiation biology.

[35]  Tao Shen,et al.  Photodynamic action of amino substituted hypocrellins: EPR studies on the photogenerations of active oxygen and free radical species. , 2000, Journal of photochemistry and photobiology. B, Biology.

[36]  S. Carpenter,et al.  The role of oxygen in the photoinduced antiviral activity of hypericin , 1994 .

[37]  N. Turro Modern Molecular Photochemistry , 1978 .

[38]  Xiaoming Shang,et al.  Optical nonlinearities of hypocrellin A with the excitation of nanosecond pulses , 1998 .

[39]  R. Haugland,et al.  Antiviral Activities of Photoactive Perylenequinones , 1997, Photochemistry and photobiology.

[40]  Seth R. Marder,et al.  Two-photon polymerization initiators for three-dimensional optical data storage and microfabrication , 1999, Nature.

[41]  Zhao Kai,et al.  Conversion of Hypocrellin A in Alkaline and Neutral Media , 1989 .

[42]  George A. Kraus,et al.  Hypericin, Hypocrellin, and Model Compounds: Primary Photoprocesses of Light-Induced Antiviral Agents , 1997 .

[43]  F. Gai,et al.  OBSERVATION OF EXCITED-STATE TAUTOMERIZATION IN THE ANTIVIRAL AGENT HYPERICIN AND IDENTIFICATION OF ITS FLUORESCENT SPECIES , 1994 .

[44]  J. An,et al.  Reactivity of semiquinone radical anions of hydroxyperylenequinone with oxygen , 1996 .

[45]  S. Carpenter,et al.  Roles of oxygen and photoinduced acidification in the light-dependent antiviral activity of hypocrellin A. , 1995, Biochemistry.