Photochemistry and Photobiology

Cover image for Vol. 87 Issue 4

July/August 2011

Volume 87, Issue 4

Pages 747–943

  1. Invited Review

    1. Top of page
    2. Invited Review
    3. Highlight Article
    4. Research Articles
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      The Action Spectrum of Photochemical Damage to the Retina: A Review of Monochromatic Threshold Data (pages 747–753)

      Dirk van Norren and Theo G.M.F. Gorgels

      Version of Record online: 12 APR 2011 | DOI: 10.1111/j.1751-1097.2011.00921.x

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      In 1966 Noell published his landmark study on photochemical damage of the retina. The action spectrum (in rat) was identical to the absorption spectrum of rhodopsin. Ten years later Ham published a different action spectrum (in monkey) with highest susceptibility in the blue rather than the green. This spectrum was later also found in rat. In an attempt to find the unique conditions for each spectrum we gathered all monochromatic threshold data from the literature. Two sources adhered to the Noell type, 16 to the Ham type. An analysis of the conditions did not yield unique ones.

  2. Highlight Article

    1. Top of page
    2. Invited Review
    3. Highlight Article
    4. Research Articles
    1. Antimicrobial Photodynamic Therapy in the Colon: Delivering a Light Punch to the Guts? (pages 754–756)

      Mark Wainwright, Tianhong Dai and Michael R. Hamblin

      Version of Record online: 12 APR 2011 | DOI: 10.1111/j.1751-1097.2011.00925.x

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      A paper in this issue by Cassidy et al. describes the use of a sophisticated drug delivery vehicle prepared by the hot melt extrusion process to deliver photosensitizers and an oxygen releasing compound to the colon. The smart vehicle protects its cargo through the acidic environment of the stomach but releases the active photosensitizers in the higher pH and anaerobic environment of the colon. The goal is to use photodynamic therapy to destroy pathogenic microorganisms such as Clostridium difficile that can cause disease when they grow out of control in the colon.

  3. Research Articles

    1. Top of page
    2. Invited Review
    3. Highlight Article
    4. Research Articles
    1. Novel Photofunctional Multicomponent Rare Earth (Eu3+, Tb3+, Sm3+ and Dy3+) Hybrids with Double Cross-linking Siloxane Covalently Bonding SiO2/ZnS Nanocomposite (pages 757–765)

      Bing Yan, Yan Zhao and Ya-Juan Li

      Version of Record online: 6 APR 2011 | DOI: 10.1111/j.1751-1097.2011.00920.x

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      Zinc sulfide (ZnS) quantum dot is modified with 3-mercaptopropyltrimethoxysilane (MPTMS) to obtain MPTMS functionalized SiO2/ZnS nanocomposite. Novel rare earth/inorganic/organic hybrid materials are prepared by using 3-(triethoxysilyl)-propyl isocyanate (TESPIC) as an organic bridge molecule that can both coordinate to rare earth ions (Eu3+, Tb3+, Sm3+ and Dy3+) and form an inorganic Si–O–Si network with SiO2/ZnS nanocomposite after cohydrolysis and copolycondensation through a sol-gel process. These multicomponent hybrids with double cross-linking siloxane (TESPIC-MPTMS) covalently bonding SiO2/ZnS and assistant ligands (Phen = 1,10-phenanthroline, Bipy = 2,2′-bipyridyl) are characterized and especially the photoluminescence properties of them are studied in detail.

    2. Excited-State Double Proton Transfer of 7-Azaindole Dimers in a Low-Temperature Organic Glass (pages 766–771)

      Hyeongtaek Lim, Sun-Young Park and Du-Jeon Jang

      Version of Record online: 12 APR 2011 | DOI: 10.1111/j.1751-1097.2011.00923.x

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      The excited-state double proton transfer of model DNA base pairs, 7-azaindole dimers (7AI), is explored in a low-temperature organic glass of n-dodecane using picosecond time-resolved fluorescence spectroscopy. Reaction mechanisms are found to depend on the conformations of 7AI dimers at the moment of excitation; whereas planar conformers tautomerize rapidly, twisted conformers undergo double proton transfer to form tautomeric dimers on the time scale of 250 ps at 8 K. Precursor-configurational optimization is found to determine the overall rate of excited-state double proton transfer at cryogenic temperatures, showing a kinetic isotope effect to be as small as unity.

    3. Enhancement of Palladium-Porphyrin Room Temperature Phosphorescence by Alkaline Earth Metal in Deoxycholate Aggregates Solution (pages 772–778)

      Ying-Te Wang, Xiang-Wei Wang and Yong Zhang

      Version of Record online: 28 APR 2011 | DOI: 10.1111/j.1751-1097.2011.00927.x

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      Room temperature phosphorescence (RTP) of palladium-meso-tetrakis (4-carboxyphenyl) porphyrin (Pd-TCPP) was obviously enhanced in sodium deoxycholate (NaDC) aggregates mediated by alkaline earth metal (AEM). Under the same experimental conditions, Ca2+, Ba2+ and Mg2+ induced 200, 90 and 24 times greater enhancement in RTP of Pd-TCPP, respectively. It is ascribed to form the complex of NaDC-aggregate/AEM/Pd-TCPP in the system. Pd-TCPP is confined in rigid NaDC-aggregates/AEM system by the coordination which decreases the probability of collision between phosphor and quenchers such as dissolved oxygen then prolong the lifetime of the phosphor on the triplet state.

    4. Thermogravimetric Analysis of Photodegraded Acrylic Coated Lime Wood (pages 779–785)

      Carmen-Mihaela Popescu, Carmen Mihaela Tibirna and Cornelia Vasile

      Version of Record online: 12 APR 2011 | DOI: 10.1111/j.1751-1097.2011.00924.x

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      Photodegradation of the Paraloid B72 films and Paraloid B72 treated lime wood (Tilia cordata Mill.) samples was evaluated by thermogravimetry throughout the irradiation period up to 600 h. The shifting of the DTG maxima to lower temperatures and the decrease of weight loss indicates a decrease in the stability of copolymer during photodegradation. Even the surface of wood was covered with a thin layer of acrylic resin, some photodegradation reactions of the wood surface occurred. The modifications in wood structure may be influenced by the newly formed structures from acrylic resin photodegradation.

    5. Luminescent Lanthanide (Eu3+, Tb3+) Hybrids with 4-Vinylbenzeneboronic Acid Functionalized Si-O Bridges and Beta-Diketones (pages 786–794)

      Bing Yan, Min Guo and Xiao-Fei Qiao

      Version of Record online: 3 MAY 2011 | DOI: 10.1111/j.1751-1097.2011.00928.x

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      Eight binary and ternary lanthanide (Eu3+, Tb3+) hybrids with two linkages VPBA-TEPIC (VPBA-TMPMA) and beta-diketones (TTA, ACAC) have been constructed, whose photoluminescence properties are studied deeply and suggest that the ternary hybrids show favorable characteristic luminescent properties (longer lifetime and higher quantum efficiency).

    6. Enhanced Photocatalytic Degradation of C.I. Basic Violet 2 Using TiO2–SiO2 Composite Nanoparticles (pages 795–801)

      Ali Mahyar, Mohammad Ali Behnajady and Naser Modirshahla

      Version of Record online: 3 MAY 2011 | DOI: 10.1111/j.1751-1097.2011.00930.x

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      In this report, TiO2–SiO2 composite nanoparticles were prepared by the thermal hydrolysis method. The photocatalytic activity of TiO2–SiO2 composite nanoparticles in the photodegradation of C.I. Basic Violet 2 was investigated. The photodegradation rate of Basic Violet 2 using TiO2–40% SiO2 nanoparticles calcined at 600°C was much faster than that using pure TiO2 and Degussa P25 TiO2 by 10.9 and 4.3 times, respectively. The higher photoactivity of the TiO2–SiO2 composite nanoparticles was attributed to their higher surface area, larger pore volume, greater band-gap energy and smaller crystallite size as compared with pure TiO2.

    7. The (5-4) and (6-4) Adducts of 1-Methylthymine and Their Dewar Valence Isomers (pages 802–817)

      Martin D. Shetlar and Janet Chung

      Version of Record online: 9 MAY 2011 | DOI: 10.1111/j.1751-1097.2011.00932.x

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      Irradiation of 1-methylthymine (center) at 254 nm in frozen aqueous solution produces, in addition to cyclobutane dimers, both a (6-4) adduct (left) and a (5-4) adduct (right). The initially formed (5-4) adduct is unstable toward thermal conversion to another isomeric (5-4) adduct. Irradiation of each of these adducts in fluid solution with UVB results in the formation of two Dewar valence isomers. Similarly, irradiation of thymidine, frozen in ice at −78.5°C, produces a diastereomeric pair of (5-4) adducts, along with a corresponding pair of previously known (6-4) adducts.

    8. Opened-Ring Adducts of 5-Methylcytosine and 1,5-Dimethylcytosine with Amines and Water and Evidence for an Opened-Ring Hydrate of 2′-Deoxycytidine (pages 818–832)

      Martin D. Shetlar and Janet Chung

      Version of Record online: 15 JUN 2011 | DOI: 10.1111/j.1751-1097.2011.00936.x

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      The nucleobase 5-methylcytosine (m5C) reacts photochemically with ammonia to form an opened-ring adduct (IVa); similar reactions occur with 1,5-dimethylcytosine and with methylamine. Subjection of such adducts to hydrolysis in dilute acid (e.g. 0.1% trifluoracetic acid) produces opened-ring hydrates of m5C (Va) and DMC. Photoreaction of the nucleoside 2′-deoxycytidine in water results in formation of closed-ring hydrates that equilibrate thermally with a compound that has the UV spectral properties expected for an adduct similar in nature to Va.

    9. Control of Singlet Oxygen Generation Photosensitized by meso-Anthrylporphyrin through Interaction with DNA (pages 833–839)

      Kazutaka Hirakawa, Toru Hirano, Yoshinobu Nishimura, Tatsuo Arai and Yoshio Nosaka

      Version of Record online: 3 MAY 2011 | DOI: 10.1111/j.1751-1097.2011.00929.x

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      To control the activity of photosensitized singlet oxygen generation, the electron donor-connecting porphyrin was designed and synthesized. The photoexcited state of the porphyrin ring was effectively deactivated by intramolecular electron transfer from the anthracene moiety, the electron donor. The deactivation was suppressed by the interaction with a DNA, resulting in the elongation of the lifetime of the porphyrin excited state and the enhancement of the fluorescence intensity. Furthermore, it was confirmed that the interaction enabled the photoexcited porphyrin to generate singlet oxygen.

    10. Photodegradation of Folate Sensitized by Riboflavin (pages 840–845)

      Regina S. Scurachio, Leif H. Skibsted, Gustavo Metzker and Daniel R. Cardoso

      Version of Record online: 6 APR 2011 | DOI: 10.1111/j.1751-1097.2011.00916.x

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      Folate reacts with triplet-excited riboflavin with 3kq = 4.8 × 108 L mol−1 s−1 in aqueous solution by one-electron transfer from folate to triplet-excited riboflavin. The reaction quantum yield of φ = 0.32 confirms an efficient photodecomposition of folate sensitized by riboflavin producing mainly pterin-6-carboxylic acid, p-aminobenzoyl-l-glutamic and an oxaziridine derived from folate.

    11. Quantum Yields and Quantitative Spectra of Firefly Bioluminescence with Various Bivalent Metal Ions (pages 846–852)

      Yu Wang, Hidehiro Kubota, Nobuyuki Yamada, Tsutomu Irie and Hidefumi Akiyama

      Version of Record online: 9 MAY 2011 | DOI: 10.1111/j.1751-1097.2011.00931.x

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      Spectra of firefly (Photinus pyralis) bioluminescence were quantitatively measured and analyzed in the presence of Zn2+ and other bivalent metal ions. Adding various amounts of Mg2+, Mn2+ and Ca2+ produced virtually no change in the quantum yields or the spectra, while increasing concentrations of Zn2+ and some other ions decreased quantum yields and induced color shift. The sensitivities of the quantum yield and spectrum to metal ions were put as Hg2+>Zn2+, Cd2+>Ni2+, Co2+, Fe2+≫Mg2+, Mn2+, Ca2+. The sensitivity of reaction rate had no correlation with those of the quantum yield and spectrum.

    12. Photobleaching Kinetics of Verteporfin and Lemuteporfin in Cells and Optically Trapped Multilamellar Vesicles Using Two-photon Excitation (pages 853–861)

      Amy D. Tekrony, Nicole M. Kelly, B. Alexander Fage and David T. Cramb

      Version of Record online: 9 MAY 2011 | DOI: 10.1111/j.1751-1097.2011.00933.x

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      Verteporfin and Lemuteporfin are compared to examine the effect of their functional groups in two-photon excitation photodynamic therapy. Singlet oxygen-related photobleaching of the sensitizers is used to assess TPE-induced singlet oxygen generation in multilamellar vesicles (MLVs) and U343 glioma cells under a variety of conditions. This figure depicts an optically trapped vesicle with a resulting photobleaching decay curve. The magnitude of the rate constant obtained from this curve can give valuable information pertaining to the efficacy of the photosensitizers for use in photodynamic therapy.

    13. Photodynamic Effects of Pterin on HeLa Cells (pages 862–866)

      M. Paula Denofrio, Carolina Lorente, Thomas Breitenbach, Sonja Hatz, Franco M. Cabrerizo, Andrés H. Thomas and Peter R. Ogilby

      Version of Record online: 12 APR 2011 | DOI: 10.1111/j.1751-1097.2011.00922.x

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      Pterins are heterocyclic compounds widespread in biological systems. We ascertained that 2-aminopteridin-4(3H)-one, the naturally occurring parent pterin, readily associates with cervical cancer cells (HeLa) and that these cells die upon UV-A irradiation of the pterin. The data suggest that events related to mitochondrial failure precede those associated with the failure of the cell membrane.

    14. Development of Novel Oral Formulations Prepared via Hot Melt Extrusion for Targeted Delivery of Photosensitizer to the Colon (pages 867–876)

      Corona M. Cassidy, Michael M. Tunney, Deborah L. Caldwell, Gavin P. Andrews and Ryan F. Donnelly

      Version of Record online: 6 APR 2011 | DOI: 10.1111/j.1751-1097.2011.00915.x

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      In this study, a Eudragit®-based drug delivery system was formulated, via hot melt extrusion, for targeting colonic release of photosensitizer. Susceptibility of the colon pathogens Enterococcus faecalis and Bacteroides fragilis to photodynamic antimicrobial chemotherapy (PACT) was assessed. Up to 50% of photosensitizer used was released over a 6 h period. Over 7 log reductions in viable count of bacteria exposed to PACT were achieved. With these formulations, photosensitizer release could be targeted to the colon, and colon-residing pathogens killed by PACT. An oxygen-releasing compound such as tetrachlorodecaoxide, used in this study, could augment the PACT effect in the clinic.

    15. Enhanced Self-cleaning, Antibacterial and UV Protection Properties of Nano TiO2 Treated Textile through Enzymatic Pretreatment (pages 877–883)

      Majid Montazer and Samira Seifollahzadeh

      Version of Record online: 6 APR 2011 | DOI: 10.1111/j.1751-1097.2011.00917.x

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      Enzymatic pretreatment of textile can improve the absorbency and activity toward certain chemicals and nanoparticles. Polyester/wool fabric can be modified with protease and lipase to enhance surface activity. Application of nano TiO2 along with a cross-linking agent to the enzyme-pretreated polyester/wool fabric led to a higher adsorption and stabilization of nanoparticles on the fabric surface. Enhanced self-cleaning, antibacterial and UV protection properties can be obtained on the enzyme-pretreated fabric.

    16. Effects of Metal and the Phytyl Chain on Chlorophyll Derivatives: Physicochemical Evaluation for Photodynamic Inactivation of Microorganisms (pages 884–894)

      Adriana P. Gerola, Amanda Santana, Polyana B. França, Tayana M. Tsubone, Hueder P. M. de Oliveira, Wilker Caetano, Elza Kimura and Noboru Hioka

      Version of Record online: 27 MAY 2011 | DOI: 10.1111/j.1751-1097.2011.00935.x

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      Chlorophyll derivatives were investigated as photosensitizer in photodynamic inactivation of microorganisms (PDI). The Mg-chlorophyll (Mg-Chl), Zn-chlorophyll (Zn-Chl), Zn-chlorophyllide (Zn-Chlde), Cu-chlorophyll (Cu-Chl), pheophytin (Pheo) and pheophorbide (Pheid) were used. The generation of singlet oxygen is discussed and related to the photosensitizer photobleaching and the efficiency in death of S. aureus, E. coli, C. albicans, and A. salina. The PDI using chlorophylls with the phytyl chain was limited by the self-aggregation phenomenon in water at high concentrations, even in micellar systems. The physicochemical properties, allied to results in the bioassays, indicated Mg-Chl, Pheo, Zn-Chl, and Pheid as candidates for PDI.

    17. Investigation of the Photodynamic Effects of Curcumin Against Candida albicans (pages 895–903)

      Lívia N. Dovigo, Ana Cláudia Pavarina, Ana Paula D. Ribeiro, Iguatemy L. Brunetti, Carlos Alberto de S. Costa, Denis P. Jacomassi, Vanderlei S. Bagnato and Cristina Kurachi

      Version of Record online: 13 JUN 2011 | DOI: 10.1111/j.1751-1097.2011.00937.x

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      This study describes the association of curcumin with LED light for the inactivation of Candida albicans. A statistically significant reduction in C. albicans viability was observed after photodynamic therapy (PDT) (P < 0.05), for both planktonic and biofilm cultures. Photodynamic effect was greatly increased with the presence of curcumin in the surrounding media and the preirradiation time of 20 min improved PDT effectiveness against biofilms. Although PDT was phototoxic to macrophages, the therapy was more effective in inactivating the yeast cell than the defense cell.

    18. Photodynamic Therapy with Pc 4 Induces Apoptosis of Candida albicans (pages 904–909)

      Minh Lam, Paul C. Jou, Ali A. Lattif, Yoojin Lee, Christi L. Malbasa, Pranab K. Mukherjee, Nancy L. Oleinick, Mahmoud A. Ghannoum, Kevin D. Cooper and Elma D. Baron

      Version of Record online: 13 JUN 2011 | DOI: 10.1111/j.1751-1097.2011.00938.x

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      For photodynamic therapy (PDT) to be effective against yeast-like fungi, the photosensitizing drug must be able to permeate through the cell wall. Our confocal data confirmed that the phthalocyanine Pc 4 photosensitizer localizes to cytosolic organelles, including mitochondria. The current study suggests that PDT, sensitized by Pc 4, induces apoptosis in C. albicans, exhibiting many similarities with mammalian cells undergoing mitochondrion-mediated programmed cell death.

    19. Aminolevulinic Acid-Photodynamic Therapy Combined with Topically Applied Vascular Disrupting Agent Vadimezan Leads to Enhanced Antitumor Responses (pages 910–919)

      Allison Marrero, Theresa Becker, Ulas Sunar, Janet Morgan and David Bellnier

      Version of Record online: 13 JUN 2011 | DOI: 10.1111/j.1751-1097.2011.00943.x

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      Topical application of tumor vascular-disrupting agent vadimezan (5,6-dimethylxanthenone-4-acetic acid, DMXAA) potentiates the antitumor activity of photodynamic therapy (PDT) when combined with locally applied photosensitizer precursor aminolevulinic acid (ALA). A significant decrease in tumor size was observed after the combined treatment in a murine model of nodular lesions. This combined localized approach targeting blood vessels could be useful in the clinical treatment of dermatologic lesions.

    20. Photoprotective Effects of Methoxycinnamidopropyl Polysilsesquioxane (pages 920–924)

      Dae-Kyoung Choi, Taek Kyu Jung, Tae-Yeon Lim, Tae-Heung Kim, Young Baek Kim, Jeung-Hoon Lee, Kyung-Sup Yoon and Tae-Jin Yoon

      Version of Record online: 13 JUN 2011 | DOI: 10.1111/j.1751-1097.2011.00940.x

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      The chemical structure of the organic/inorganic hybrid compound, methoxycinnamidopropyl polysilsesquioxane (MCP-PSQ) and its spherical morphology photographed by the scanning electron microscope. This new sunscreen ingredient has been developed synthetically and evaluated using in vitro and in vivo approaches. We found that MCP-PSQ compound has good photoprotective effects for human fibroblasts, and for hairless mouse and human skin. Also we demonstrated the high SPF value for human skin. Further, there were no side effects such as erythema, edema, itch or tingling, suggesting that MCP-PSQ is a good sunscreen agent.

    21. Occupational Exposures to Solar Ultraviolet Radiation of Vineyard Workers in Tuscany (Italy) (pages 925–934)

      Anna Maria Siani, Giuseppe R. Casale, Renata Sisto, Alfredo Colosimo, Carolyn A. Lang and Michael G. Kimlin

      Version of Record online: 13 JUN 2011 | DOI: 10.1111/j.1751-1097.2011.00934.x

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      The study took place in Tuscany (Italy) to quantify the UV exposure of vineyard workers using polysulphone dosimetry and covering three different stages of the vine’s growth. It was found that during spring backs receive between 53% and 87% of ambient exposure and arms between 30% and 60%. During summer, the workers received on the back between 36% and 77% of ambient exposure and between 19% and 43% of ambient exposure on the arm. The comparison with the occupational UV exposure limit showed that all subjects received UV exposures in excess of the limit.

    22. Vitamin D Status of Adults from Tropical Australia Determined Using Two Different Laboratory Assays: Implications for Public Health Messages (pages 935–943)

      Madeleine Nowak, Simone L. Harrison, Petra G. Buettner, Michael Kimlin, David Porter, Lee Kennedy and Rick Speare

      Version of Record online: 13 JUN 2011 | DOI: 10.1111/j.1751-1097.2011.00941.x

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      Serum 25 hydroxyvitamin D [25(OH)D] levels of 145 ambulatory tropical Australian adults (19.16°S) were measured in late winter. Mean levels were 68.3 (DiaSorin Radioimmunoassay) and 83.0 (DiaSorin Liaison® one). No participants were 25(OH)D deficient (<25 nmol L−1); nine (6.2%) had levels between 25 and 50 nmol L−1 (insufficient), by both methods; 28 (19.3%) had one result in the insufficient range and the other in the adequate range. Thus most had adequate levels. Agreement was poor between the two assays. It appears appropriate to continue promoting sun-safe messages to the ambulatory Caucasian adult population of North Queensland, where skin cancer incidence is extremely high.