Photochemistry and Photobiology

Cover image for Vol. 90 Issue 4

July'August 2014

Volume 90, Issue 4

Pages 727–956

  1. Research Articles

    1. Top of page
    2. Research Articles
    3. Research Note
    1. Photoexcited States of UV Absorbers, Benzophenone Derivatives (pages 727–733)

      Ryo Kumasaka, Azusa Kikuchi and Mikio Yagi

      Article first published online: 7 MAR 2014 | DOI: 10.1111/php.12257

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      The energy levels and lifetimes of the lowest excited triplet states of benzophenone (BP) derivatives, BP-2, BP-3, BP-6, BP-7 and BP-12, used as organic UV absorbers in cosmetic sunscreens were determined in rigid solutions at 77 K. The time-resolved near-IR emission spectrum of singlet oxygen generated by photosensitization with BP-7 was observed in acetonitrile at room temperature. BP-2, BP-3, BP-6 and BP-12 show photoinduced phosphorescence enhancement in ethanol at 77 K.

    2. Photophysics of a Coumarin in Different Solvents: Use of Different Solvatochromic Models (pages 734–746)

      Banibrata Maity, Aninda Chatterjee and Debabrata Seth

      Article first published online: 18 MAR 2014 | DOI: 10.1111/php.12258

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      This study demonstrated the photophysics of 7-(diethylamino)coumarin-3-carboxylic acid N-succinimidyl ester (7-DCCAE) in the presence of different neat solvents. Different empirical solvatochromic models were used to analyze the solvatochromic shift of 7-DCCAE in different solvents.

    3. Influences of Acid on Molecular Forms of Fluorescein and Photoinduced Electron Transfer in Fluorescein-Dispersing Sol–Gel Titania Films (pages 747–759)

      Hiromasa Nishikiori, Rudi Agus Setiawan, Kyohei Miyashita, Katsuya Teshima and Tsuneo Fujii

      Article first published online: 23 FEB 2014 | DOI: 10.1111/php.12254

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      Fluorescein-dispersing titania gel films were prepared by the acid-catalyzed sol–gel reaction using a titanium alkoxide solution containing fluorescein. The titanium species were coordinated to the carboxylate and phenolate-like groups of the fluorescein species. The quantum efficiencies of the fluorescence quenching and photoelectric conversion were higher upon excitation of the dianion species interacting with the titania, i.e. the dye–titania complex. Using nitric acid as the catalyst, the titania surface bonded to the fluorescein instead of the adsorbed nitrate ion during the steam treatment. The complex formation played an important role in the electron injection from the dye to the titania.

    4. Photodecomposition of Chloroform Catalyzed by Unmodified MCM-41 Mesoporous Silica (pages 760–766)

      Laura A. Peña, Alissa M. Chan, Larissa R. Cohen, Karen Hou, Brent M. Harvey and Patrick E. Hoggard

      Article first published online: 15 FEB 2014 | DOI: 10.1111/php.12245

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      Unmodified MCM-41 silica catalyzes the photodecomposition of chloroform under near-UV irradiation. It is proposed that decomposition is initiated through hydrogen abstraction from chloroform at a photoactive SiO2 defect site.

    5. The Number of Accumulated Photons and the Quality of Stimulated Emission Depletion Lifetime Images (pages 767–772)

      Aleem Syed, Michael D. Lesoine, Ujjal Bhattacharjee, Jacob W. Petrich and Emily A. Smith

      Article first published online: 3 MAR 2014 | DOI: 10.1111/php.12248

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      Photon counts in the peak channel of stimulated emission depletion fluorescence lifetime decay curves are increased by time binning without affecting the spatial resolution of the measurements. The fluorescence lifetime of Alexa Fluor 594 phalloidin bound to F-actin is probed in cultured cells at a spatial resolution 10-fold better compared to confocal imaging. Pixel-by-pixel fluorescence lifetime measurements and error analysis show that an average of 40 ± 30 counts in the peak channel with a signal-to-noise ratio of 20 is enough to calculate a reliable fluorescence lifetime from a single exponential fluorescence decay.

    6. Bistable Retinal Schiff Base Photodynamics of Histidine Kinase Rhodopsin HKR1 from Chlamydomonas reinhardtii (pages 773–785)

      Alfons Penzkofer, Meike Luck, Tilo Mathes and Peter Hegemann

      Article first published online: 8 MAR 2014 | DOI: 10.1111/php.12246

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      In HKR1 two thermally stable retinal Schiff base (RSB) forms RetA and RetB exist. RetA is deprotonated 13-cis, 15-anti RSB absorbing in the UV. RetB is protonated all-trans 15-anti and 15-syn RSB absorbing blue light. RetB is blue-light convertible to RetA with quantum efficiency of 0.4. RetA is UVA light convertible to RetB with quantum efficiency of 0.1.

    7. Tyrosine 263 in Cyanobacterial Phytochrome Cph1 Optimizes Photochemistry at the prelumi-R[RIGHTWARDS ARROW]lumi-R Step (pages 786–795)

      Vitaly Sineshchekov, Joel Mailliet, Georgios Psakis, Kathleen Feilke, Jakub Kopycki, Mathias Zeidler, Lars-Oliver Essen and Jon Hughes

      Article first published online: 28 MAR 2014 | DOI: 10.1111/php.12263

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      Y263 in Cph1 is perfectly conserved among phytochromes, even though mutations at that site seemed to be innocuous. Here we show that, on the contrary, tyrosine is important in optimizing photochemistry toward lumi-R at the of S0/S1 conical intersection (prelumi-R). A possible structure of the prelumi-R phantom state is shown here.

    8. The Effect of Photodynamic Action on Leakage of Ions Through Liposomal Membranes that Contain Oxidatively Modified Lipids (pages 796–800)

      Shany Ytzhak and Benjamin Ehrenberg

      Article first published online: 25 MAR 2014 | DOI: 10.1111/php.12266

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      We measured the integrity of the liposomal membrane when it includes oxidatively modified lipids and when it is exposed to photodynamic action by photosensitization with hematoporphyrin. We demonstrate that the photodynamic process, in which unsaturated lipids of natural lecithin are damaged, is not causing the lipid bilayer to leak, but it strongly accelerates the leakage of ions if a very small fraction of the natural lipids are replaced by the modified lipids.

    9. Membrane Damage Efficiency of Phenothiazinium Photosensitizers (pages 801–813)

      Isabel O. L. Bacellar, Christiane Pavani, Elisa M. Sales, Rosangela Itri, Mark Wainwright and Mauricio S. Baptista

      Article first published online: 26 MAR 2014 | DOI: 10.1111/php.12264

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      Structure–activity relationships were investigated for a series of phenothiazinium photosensitizers (methylene blue, toluidine blue O, 1,9-dimethyl methylene blue and DO15). We compared the ability of these compounds to damage membranes by quantifying the efficiency of liposome permeabilization, which was correlated with singlet-oxygen generation within the membranes, membrane/solution partition and tendency of aggregation of the photosensitizers. We concluded that membrane-based protocols can provide a better understanding on the photodynamic efficiency of the photosensitizer.

    10. Antioxidative Activities of Algal Keto Carotenoids Acting as Antioxidative Protectants in the Chloroplast (pages 814–819)

      Michael Dambeck and Gerhard Sandmann

      Article first published online: 26 FEB 2014 | DOI: 10.1111/php.12249

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      Carotenoids and especially their keto derivatives are known for their antioxidative potential. Therefore the keto carotenoids peridinin, siphonaxanthin, fucoxanthin and astaxanthin mono fatty acid ester were isolated from different algae. They were assayed for their antioxidative properties as quenchers of singlet oxygen and oxo radicals and their potential was determined to protect against singlet oxygen- or radical-mediated peroxidation reactions.

    11. Analysis of Photoexcitation Energy Dependence in the Photoluminescence of Firefly Luciferin (pages 820–828)

      Miyabi Hiyama, Hidefumi Akiyama, Toshimitsu Mochizuki, Kenta Yamada and Nobuaki Koga

      Article first published online: 15 FEB 2014 | DOI: 10.1111/php.12243

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      By considering protonation/deprotonation, the whole pathways for photoluminescence of firefly luciferin in aqueous solutions of different pH values with different photoexcitation energies were theoretically investigated.

    12. Quantitative and in situ Detection of Oxidatively Generated DNA Damage 8,5′-Cyclo-2′-Deoxyadenosine Using an Immunoassay with a Novel Monoclonal Antibody (pages 829–836)

      Takaaki Iwamoto, Philip J. Brooks, Tomohisa Nishiwaki, Kazuki Nishimura, Nobuhiko Kobayashi, Shigeki Sugiura and Toshio Mori

      Article first published online: 23 FEB 2014 | DOI: 10.1111/php.12239

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      Xeroderma pigmentosum (XP) is a genetic disorder associated with defects in nucleotide excision repair, which eliminates a wide variety of helix-distorting DNA damage including sunlight-induced pyrimidine dimers. In addition to skin disease, approximately 30% of XP patients develop progressive neurological disease, which has been hypothesized to be associated with the accumulation of oxidatively generated DNA damage called purine cyclonucleosides. In this study, we generated a novel monoclonal antibody (CdA-1) specific for purine cyclonucleosides in DNA that recognizes 8,5′-cyclo-2′-deoxyadenosine (cyclo-dA). An immunofluorescent analysis using CdA-1 enabled the visualization of cyclo-dA (green dots) in human osteosarcoma cells, which had been transfected with oligonucleotides containing 5′S-cyclo-dA.

    13. Bystander Effect Induced by UVC Radiation in Chinese hamster V79 cells (pages 837–844)

      Shengwen Wu, Cuihong Jin, Xiaobo Lu, Jinghua Yang, Qiufang Liu, Ming Qi, Shuai Lu, Lifeng Zhang and Yuan Cai

      Article first published online: 5 MAR 2014 | DOI: 10.1111/php.12255

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      This study showed that UVC radiation induced some damage in irradiated V79 cells, which might initiate apoptosis progress when damage couldn't be repaired. The UVC-irradiated apoptotic cells released gradually some soluble factors into irradiated conditioned medium (ICMs) which finally induced bystander effect in unirradiated V79 cells.

    14. Phosphorylation of Histone H2AX Generated by Linear Alkylbenzene Sulfonates and its Suppression by UVB Exposure (pages 845–852)

      Toru Kubota, Tatsushi Toyooka, Xiaoxu Zhao and Yuko Ibuki

      Article first published online: 26 MAR 2014 | DOI: 10.1111/php.12268

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      Linear alkylbenzene sulfonates (LAS), general anion surfactants, generated DNA double-strand breaks (DSBs) with phosphorylation of histone H2AX (γ-H2AX). The ability to generate γ-H2AX was markedly reduced in LAS exposed to UVB. HPLC analysis revealed that UVB evenly decreased all peaks of LAS, without migration of peaks to other retention times, which indicated that UVB may degrade the benzene ring of LAS, but did not shorten the alkyl chains. UVB is an important environmental factor in the degradation of LAS exhibiting the ability to induce DSBs, the most serious type of DNA damage.

    15. Effects of white light-emitting diode (LED) light exposure with different Correlated Color Temperatures (CCTs) on human lens epithelial cells in culture (pages 853–859)

      Chen Xie, Xiuyi Li, Jianping Tong, Yangshun Gu and Ye Shen

      Article first published online: 25 FEB 2014 | DOI: 10.1111/php.12250

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      Oxidative stress on the lens epithelial cells (hLECs) is the most important factor in cataract formation. Cumulative light exposure from widely used light-emitting diodes (LEDs) may pose a potential oxidative threat to the lens epithelium, due to the high-energy blue light component in the white-light emission from diodes. LED light having a CCT of 7378 K caused overproduction of intracellular ROS and severe cellular damage, which indicate that white LEDs with a high CCT could cause significant photobiological damage to hLECs and detailed industrial standards for this new artificial light source should be determined for the sake of ocular safety.

    16. Dimerization of Resveratrol Induced by Red Light and Its Synergistic Analgesic Effects with Cobra Neurotoxin (pages 860–866)

      Yong Ye, Fei Fang and Yue Li

      Article first published online: 15 MAR 2014 | DOI: 10.1111/php.12262

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      A new synthetic method is designed for resveratrol dimer, which is induced by the excitation of photosensitizer pheophorbide at red light of 630 nm, the mechanism is illustrated. The dimer interacts with cobra neurotoxin and forms a complex substance, which shows significant synergistic analgesic effects after combined administration to mice. The dimer has multiple targets, and its combination with cobra neurotoxin may make up for their deficiencies in analgesic effects suggesting good prospects in clinical use.

    17. Hypericin as a Marker for Determination of Myocardial Viability in a Rat Model of Myocardial Infarction (pages 867–872)

      Cuihua Jiang, Yue Li, Xiao Jiang, Nan Yao, Meng Gao, Xueli Zhang, Junying Wang, Xiaoning Wang, Ziping Sun, Jian Zhang and Yicheng Ni

      Article first published online: 26 FEB 2014 | DOI: 10.1111/php.12247

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      The aim of this study was to investigate the necrosis avid agent hypericin as a potential indicator for determination of myocardial infarction. Animals were challenged with different doses of hypericin (0, 1, 2, and 5 mg kg−1) after an experimental myocardial infarction. Infarct-to-normal contrast ratio and relative infarct size were evaluated by fluorescence macroscopy in colocalization with triphenyltetrazoliumchloride and histomorphology. Results confirm that hypericin specifically labeled necrosis, and enhanced the imaging contrast between the infarcted and normal myocardium, suggesting its potential applications for the assessment of myocardial viability.

    18. Efficacy of Low-Dose Ultraviolet A-1 Phototherapy for Parapsoriasis/Early-Stage Mycosis Fungoides (pages 873–877)

      Kenan Aydogan, Serkan Yazici, Saduman Balaban Adim, Isil Tilki Gunay, Ferah Budak, Hayriye Saricaoglu, Sukran Tunali and Emel Bulbul Baskan

      Article first published online: 5 MAR 2014 | DOI: 10.1111/php.12253

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      Skin-directed therapies are currently available treatment options for plaque type PP/early-stage MF with some limitations, and management of the diseases is still challenging. Ultraviolet A-1 (340–400 nm) phototherapy was first described in 1978 and it has became a valuable treatment for sclerotic and T-cell mediated diseases, more deeply penetrates than UVB. This study showed that Low-dose UVA-1 therapy seems to be a safe and effective alternative to other therapeutic options in patients with PP/early-stage MF who do not tolerate or respond to PUVA and UVB therapy, without systemic effect.

    19. Measurement of Intracellular Oxygen Concentration During Photodynamic Therapy in vitro (pages 878–888)

      Mark A. Weston and Michael S. Patterson

      Article first published online: 14 MAR 2014 | DOI: 10.1111/php.12256

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      A novel technique is described that measures the intracellular ground state oxygen concentration ([3O2]) during photodynamic therapy of cell monolayers and cell suspensions. The photosensitizer Pd(II) meso-tetra(4-carboxyphenyl)porphine (PdT790) is used to deplete the cells of 3O2 by photodynamic action while simultaneously monitoring the intracellular [3O2]. The intracellular [3O2] is calculated using the steady-state phosphorescence signal emitted by PdT790 during treatment. It was found that cells remain well oxygenated during PDT of cell suspensions, while for monolayer treatments intracellular [3O2] is rapidly reduced.

    20. Enhanced Efficacy of Photodynamic Therapy via a Sequential Targeting Protocol (pages 889–895)

      David Kessel and John J. Reiners Jr

      Article first published online: 1 APR 2014 | DOI: 10.1111/php.12270

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      Testing for iron translocation using fluorescent probes: red = RhoNox-1 (Ferrous iron); green = LysoTracker Green (A) or MitoTracker Green (B–D). Iron is initially localized in lysosomes (A), not mitochondria (B). Treatment with Bafilomycin results in substantial translocalization to mitochondria (C), whereas a low level of lysosomal photodamage does not (D). Either effect can markedly promote the efficacy of subsequent mitochondrial photodamage but via different mechanisms.

    21. Topical Photodynamic Therapy Using Different Porphyrin Precursors Leads to Differences in Vascular Photosensitization and Vascular Damage in Normal Mouse Skin (pages 896–902)

      Tom A. Middelburg, Hannah C. de Vijlder, Henriette S. de Bruijn, Angélique van der Ploeg-van den Heuvel, H. A. Martino Neumann, Ellen R. M. de Haas and Dominic J. Robinson

      Article first published online: 7 APR 2014 | DOI: 10.1111/php.12271

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      The ability of the vasculature to synthesize PpIX and be damaged by PDT was compared between HAL, ALA and MAL in mouse skin using confocal microscopy and fluorescent CD31 and CD144 antibodies. Colocalization of CD31 and PpIX (left images) was calculated to measure endothelial PpIX synthesis. Vascular damage was scored as loss of normal CD144 staining (right images). Both PpIX synthesis and vascular damage were highest for HAL, then ALA, then MAL. This illustrates that superficial blood vessels synthesize biologically relevant amounts of PpIX. Vascular responses can limit oxygen supply during or after PDT and are expected to influence outcome.

    22. Autonomous Portable Solar Ultraviolet Spectroradiometer (APSUS) – a New CCD Spectrometer System for Localized, Real-Time Solar Ultraviolet (280–400 nm) Radiation Measurement (pages 903–910)

      Rebecca Hooke, Andy Pearson and John O'Hagan

      Article first published online: 10 MAR 2014 | DOI: 10.1111/php.12251

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      A new prototype portable CCD (charge-coupled device) spectrometer-based instrument called APSUS (Autonomous Portable Solar Ultraviolet Spectroradiometer) has been developed which monitors spectral UV (280–400 nm) radiation levels at the earth's surface. The APSUS system enables the UV index to be calculated and disseminated to the public in real time. The APSUS unit incorporates an Ocean Optics QE65000 spectrometer contained within a robust environmental housing. It can gather reliable data from approximately April to October inclusive (depending on ambient temperature) in the UK. In this study the new APSUS unit and APSUS system are presented.

    23. Occupational UV Exposure of Environmental Agents in Valencia, Spain (pages 911–918)

      María-Antonia Serrano, Javier Cañada, Juan Carlos Moreno, Gonzalo Gurrea and Members of the Valencia Solar Radiation Research Group

      Article first published online: 26 FEB 2014 | DOI: 10.1111/php.12252

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      The aim of this paper is to measure UV exposure of environmental agents in their occupational schedules in summer in Valencia province (Spain) using VioSpor personal dosimeters attached to several parts of their bodies. Due to its geographical situation, Valencia receives large UVR doses throughout the year, and the work of environmental agents is directly related to the protection, care, and custody of natural, often in mountainous areas. Comparison with the occupational UV exposure limit showed that the agents received an erythemal UV dose in excess of occupational guidelines, indicating that protective measures against this risk are highly advisable.

    24. Measuring Exposure to Solar Ultraviolet Radiation Using a Dosimetric Technique: Understanding Participant Compliance Issues (pages 919–924)

      Jiandong Sun, Robyn M. Lucas, Simone L. Harrison, Ingrid van der Mei, David C. Whiteman, Rebecca Mason, Madeleine Nowak, Alison M. Brodie and Michael G. Kimlin

      Article first published online: 24 MAR 2014 | DOI: 10.1111/php.12265

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      Among 10 020 polysulphone UV dosimeters distributed in the AusD Study, the majority (89%) were returned with no reported issues, but 3% were not returned or used and 8% were returned with self-reported usage errors such as “missing some time,” “covered by clothing,” or “dosimeter got wet” that may potentially compromise the measurement quality. We found these noncompliance issues were more frequently reported on the first day of measurement; weekend days or rainy days; and among females; younger people; more educated participants or those with predominantly outdoor occupations. These factors should be considered when designing future UV dosimetry studies.

    25. Quantification of Ocular Biologically Effective UV Exposure for Different Rotation Angle Ranges Based on Data from a Manikin (pages 925–934)

      Liwen Hu, Fang Wang, Nan-Ning Ou-Yang, Na Gao, Qian Gao, Tiantian Ge, Yanyan Gao, Guangcong Liu, Yang Zheng and Yang Liu

      Article first published online: 24 MAR 2014 | DOI: 10.1111/php.12267

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      To improve the understanding of solar UV and the biologically effective UV exposure at eye (UVBE), this study monitored the ocular UV exposure at different rotation angles using a rotating manikin in clear skies during July 2010 in Sanya, China. The rotation angle ranges were the ranges of the eye facing the sun or facing away from the sun; for example, the 60° rotation angle range facing the sun was the rotation angle of 330° to 30°, and the 180° rotation angle range facing away from the sun included the rotation angles between 90° and 270°.

    26. Measurements of Pilots’ Occupational Solar UV Exposure (pages 935–940)

      Adrian Chorley, Michael Higlett, Katarzyna Baczynska, Robert Hunter and Marina Khazova

      Article first published online: 2 JUL 2014 | DOI: 10.1111/php.12269

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      It is known that UVR increases by 10–12% every 1000 m altitude; UVR at the 10 000 m of typical cruise altitude for commercial aircraft may be 2–3 times higher than at ground level. Information on the levels of solar UV exposures is essential for the assessment of the occupational risk of pilots developing sun-related eye disorders and skin cancers. The aim of the study was to investigate how UV hazard exposures can be measured during flights. It was successfully tested for a number of aircraft and helicopter flights during 2012–2013, illustrated in this paper for a Gatwick-Alicante flight.

    27. Two Methods for Retrieving UV Index for All Cloud Conditions from Sky Imager Products or Total SW Radiation Measurements (pages 941–951)

      Jordi Badosa, Josep Calbó, Richard Mckenzie, Ben Liley, Josep-Abel González, Bruce Forgan and Charles N. Long

      Article first published online: 17 APR 2014 | DOI: 10.1111/php.12272

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      Cloud effects on UV Index (UVI) and total solar radiation (TR) are assessed. The role of cloud cover and sunny conditions (from sky images) and of solar zenith angle is investigated. The analyses are undertaken for a southern-hemisphere mid-latitude site where a 10-years dataset is available. It is confirmed that clouds affect TR more than UVI, both in reducing and enhancing the cloud-free radiation. From the analyses, two methods to estimate UVI are developed: (1) from sky imaging cloud cover and sunny conditions, and (2) from TR measurements. Methods' estimations are compared with measurements.

  2. Research Note

    1. Top of page
    2. Research Articles
    3. Research Note
    1. Preparation and Characterization of Uniform Near IR Polystyrene Nanoparticles (pages 952–956)

      Michal Pellach and Shlomo Margel

      Article first published online: 20 FEB 2014 | DOI: 10.1111/php.12244

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      In vivo fluorescence imaging requires the use of near IR fluorescent imaging agents, to avoid the absorbance and autofluorescence of endogenous tissues that occur at visible wavelengths. Near IR dye was encapsulated into polystyrene nanoparticles via a swelling process. The dye encapsulation process was performed for a series of differently sized nanoparticles, without affecting the relatively uniform size distribution of each size. The method used was found to be appropriate for nanoparticles averaging approximately 20–100 nm in size. The resulting nanoparticles were highly fluorescent and highly photostable, and with appropriate surface modification, have potential for biological and in vivo imaging applications.