Photooxidation of Alkaloids: Considerable Quantum Yield Enhancement by Rose Bengal‐sensitized Singlet Molecular Oxygen Generation

The photooxidation of sanguinarine, coralyne and berberine was studied in oxygenated alkaline methanol solutions. Rose bengal as photosensitizer significantly accelerates the process, indicating the importance of singlet molecular oxygen in the reaction mechanism. The quantum yield of sensitized oxidation was found to increase significantly with pH and reaches 0.4 for berberine at pH 13.8. The direct oxidation of alkaloids is less efficient, the quantum yield does not exceed 0.01 even in oxygen‐saturated solutions. The photoinduced electron ejection does not play a role in the oxidation. The uncharged pseudobase forms, which are present in alkaline medium, are oxidized much more easily than the alkaloid cations.

[1]  Zsombor Miskolczy,et al.  Photoreduction and Ketone‐sensitized Reduction of Alkaloids , 2011, Photochemistry and photobiology.

[2]  G. Tárkányi,et al.  Inclusion complex formation of sanguinarine alkaloid with cucurbit[7]uril: inhibition of nucleophilic attack and photooxidation. , 2011, Organic & biomolecular chemistry.

[3]  J. Mattay,et al.  Direct photooxidation and xanthene-sensitized oxidation of naphthols: quantum yields and mechanism. , 2011, The journal of physical chemistry. A.

[4]  M. Wolszczak,et al.  Radiolysis of berberine or palmatine in aqueous solution , 2011 .

[5]  Andrés H. Thomas,et al.  Mechanism of photooxidation of folic acid sensitized by unconjugated pterins. , 2010, Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology.

[6]  J. Ulrichová,et al.  Fluorescence of sanguinarine: spectral changes on interaction with amino acids. , 2010, Physical chemistry chemical physics : PCCP.

[7]  Liang Shen,et al.  The mechanisms of ROS-photogeneration by berberine, a natural isoquinoline alkaloid. , 2010, Journal of photochemistry and photobiology. B, Biology.

[8]  Mei Wang,et al.  Characterization of the transient species generated by the photoionization of Berberine: a laser flash photolysis study. , 2009, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[9]  J. Ulrichová,et al.  Fluorescence of sanguinarine: fundamental characteristics and analysis of interconversion between various forms , 2009, Analytical and bioanalytical chemistry.

[10]  Mei Wang,et al.  The examination of berberine excited state by laser flash photolysis. , 2009, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[11]  E. Oliveros,et al.  Oxidation of 2'-deoxyguanosine 5'-monophosphate photoinduced by pterin: type I versus type II mechanism. , 2008, Journal of the American Chemical Society.

[12]  K. Hirakawa,et al.  The Microenvironment of DNA Switches the Activity of Singlet Oxygen Generation Photosensitized by Berberine and Palmatine , 2007, Photochemistry and photobiology.

[13]  R. Sik,et al.  Photochemistry and Photocytotoxicity of Alkaloids from Goldenseal (Hydrastis canadensis L.) 3: Effect on Human Lens and Retinal Pigment Epithelial Cells , 2007, Photochemistry and photobiology.

[14]  E. Oliveros,et al.  Singlet Oxygen (O 2 ( 1 ? g )) Quenching by Dihydropterins , 2007 .

[15]  E. Oliveros,et al.  Reactivity of Conjugated and Unconjugated Pterins with Singlet Oxygen (O2(1Δg)): Physical Quenching and Chemical Reaction † , 2007, Photochemistry and photobiology.

[16]  Lenka Gryčová,et al.  Quaternary protoberberine alkaloids. , 2007, Phytochemistry.

[17]  H. Ihmels,et al.  Efficient Photoinduced DNA Damage by Coralyne , 2006, Photochemistry and photobiology.

[18]  R. Sik,et al.  Photochemistry and photocytotoxicity of alkaloids from Goldenseal (Hydrastis canadensis L.). 2. Palmatine, hydrastine, canadine, and hydrastinine. , 2006, Chemical research in toxicology.

[19]  S. Kawanishi,et al.  The mechanism of guanine specific photooxidation in the presence of berberine and palmatine: activation of photosensitized singlet oxygen generation through DNA-binding interaction. , 2005, Chemical research in toxicology.

[20]  M. Iesce,et al.  Photooxygenation of Heterocycles , 2005 .

[21]  R. Dommisse,et al.  Berberine and coptisine free bases , 2004 .

[22]  C. Baiocchi,et al.  Photochemical Behavior of Folic Acid in Alkaline Aqueous Solutions and Evolution of Its Photoproducts , 2002 .

[23]  C. Chignell,et al.  Photochemistry and photocytotoxicity of alkaloids from Goldenseal (Hydrastis canadensis L.) 1. Berberine. , 2001, Chemical research in toxicology.

[24]  M. Jung,et al.  Antiphotooxidative activity of protoberberines derived from Coptis japonica makino in the chlorophyll-sensitized photooxidation of oil. , 2000, Journal of agricultural and food chemistry.

[25]  R. Suau,et al.  Hydroxymethylation of protoberberine alkaloids by photoinduced SET. The total synthesis of (±)-solidaline , 1999 .

[26]  C. Ferroud,et al.  SINGLET OXYGEN MEDIATED ALKALOID TERTIARY AMINES OXIDATION BY SINGLE ELECTRON TRANSFER , 1998 .

[27]  M. Maiti,et al.  Photochemical conversion of sanguinarine to oxysanguinarine , 1997 .

[28]  D. Cortes,et al.  Cerasodine and cerasonine: new oxoprotoberberine alkaloids from Polyalthia cerasoides , 1997 .

[29]  I. Kochevar,et al.  Does Rose Bengal Triplet Generate Superoxide Anion , 1996 .

[30]  M. K. Maiti,et al.  PRODUCTION OF SINGLET OXYGEN BY SANGUINARINE AND BERBERINE , 1995 .

[31]  R. Nandi,et al.  PHOTOPHYSICAL PROPERTY OF SANGUINARINE IN THE EXCITED SINGLET STATE , 1992 .

[32]  J. Scaiano,et al.  PHOTOTOXIC AND PHOTOCHEMICAL PROPERTIES OF SANGUINARINE * , 1992, Photochemistry and photobiology.

[33]  E. Oliveros,et al.  Kinetic parameters of the reactivity of dihydroxy naphthalenes with singlet oxygen , 1990 .

[34]  M. Berenbaum,et al.  SANGUINARINE, A PHOTOTOXIC H2O2‐PRODUCING ALKALOID , 1989, Photochemistry and photobiology.

[35]  J. Langan,et al.  Photochromic heterocyclic fulgides. Part 3. The use of (E)-α-(2,5-dimethyl-3-furylethylidene)(isopropylidene)succinic anhydride as a simple convenient chemical actinometer , 1981 .

[36]  S. Singh,et al.  Photochemistry of alkaloids , 1980 .

[37]  V. Šimánek,et al.  The pseudobase formation in some isoquinoline alkaloids , 1976 .

[38]  T. Higuchi,et al.  Solubilization and stabilization of the cytotoxic agent coralyne. , 1975, Journal of pharmaceutical sciences.