Photochemistry and Photobiology

Cover image for Vol. 91 Issue 6

November/December 2015

Volume 91, Issue 6

Pages 1251–1509

  1. Editorial

    1. Top of page
    2. Editorial
    3. Invited Reviews
    4. Research Articles
    1. Editorial (page 1251)

      Jean Cadet

      Article first published online: 3 NOV 2015 | DOI: 10.1111/php.12541

  2. Invited Reviews

    1. Top of page
    2. Editorial
    3. Invited Reviews
    4. Research Articles
    1. You have free access to this content
      Rethinking the Concepts of Fluence (UV Dose) and Fluence Rate: The Importance of Photon-based Units – A Systemic Review (pages 1252–1262)

      James R. Bolton, Ian Mayor-Smith and Karl G. Linden

      Article first published online: 24 SEP 2015 | DOI: 10.1111/php.12512

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      This diagram depicts the reactor that could be used to study photochemical or photobiological reactions in a collimated beam apparatus. The reactor is configured so that photons from the UV lamp that pass through the hole in the mask impinge directly on the surface of the solution, but no photons impinge on the walls of the dish. This diagram illustrates the fundamental concept in the paper, namely that photochemical and photobiological reactions should use photon-based terms, such as photon irradiance (einstein m−2 s−1), rather than power-based terms, such as irradiance (W m−2).

    2. You have free access to this content
      Photochemistry and Photobiology of the Spore Photoproduct: A 50-Year Journey (pages 1263–1290)

      Peter Setlow and Lei Li

      Article first published online: 20 SEP 2015 | DOI: 10.1111/php.12506

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      In 1965, a thymine dimer was discovered as the dominant DNA photolesion in UV-irradiated endospores, which was later named the spore photoproduct (SP). Formation of SP is due to the unique environment in central core of endospores surrounded by several spore-specific layers, in which the genomic DNA adopts an A-conformation supporting SP photochemistry. Spore photoproducts, if unrepaired, are toxic to germinated bacteria; developments on synthetic chemistry now make it possible to understand the molecular basis of SP toxicity. This review covers the SP research in the past 50 years, which indicates a rich SP biology existing beyond endospores.

    3. You have free access to this content
      More Than Just Light: Clinical Relevance of Light Perception in the Nosocomial Pathogen Acinetobacter baumannii and Other Members of the Genus Acinetobacter (pages 1291–1301)

      María Soledad Ramírez, Gabriela Leticia Müller, Jorgelina Fernanda Pérez, Adrián Ezequiel Golic and María Alejandra Mussi

      Article first published online: 24 OCT 2015 | DOI: 10.1111/php.12523

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      In Acinetobacter baumannii light modulates physiological aspects related to the success of the microorganism as a nosocomial pathogen. In the figure are outlined models for light perception and signal transduction in A. baumannii. (A) Light absorption induces a conformational change in the A. baumannii BLUF photoreceptor BlsA, now able to bind unknown partners that modulate the response, resulting ultimately in regulation of surface motility, biofilm formation and virulence against Candida albicans. (B) Light can also induce reduction in susceptibility to antibiotics in a photoreceptor-independent manner in A. baumannii and other clinically relevant pathogens. In this case, light application could result in the excitation of an unknown photosensitizer molecule with the concomitant production of ROS such as 1O2, leading ultimately to the induction of expression of antibiotic resistance genes such as those coding for the AdeABC pump. This results in reduction in susceptibility to the antibiotics MIN and TIG. All these phenotypes occur at 25°C.

  3. Research Articles

    1. Top of page
    2. Editorial
    3. Invited Reviews
    4. Research Articles
    1. Preparation of SnO2–TiO2/Fly Ash Cenospheres and its Application in Phenol Degradation (pages 1302–1308)

      Shaomin Liu, Jinglin Zhu, Qing Yang, Pengpeng Xu, Jianhua Ge and Xuetao Guo

      Article first published online: 17 OCT 2015 | DOI: 10.1111/php.12529

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      Under UV light irradiation, TiO2 and SnO2 are excited. The photo-generated electrons of TiO2 transfer from the valence band to the conduction band and then injected into the conduction band of SnO2. Thus, electrons could be trapped by the absorbed O2 to produce inline image on the catalyst surface and then react with phenol. The photo-generated holes are also transferred from the valence band of SnO2 to the valence band of TiO2; this transfer induces phenol degradation. The active species would decompose phenol to the final carbon dioxide or other intermediate products.

    2. The Synthesis and Photocatalytic Properties of TiO2 Nanotube Array by Starch-Modified Anodic Oxidation (pages 1309–1314)

      Fengjun Zhang, Zijian Liu, Wei Lu, Cong Lyu, Chuan Lyu and Xiansheng Wang

      Article first published online: 17 JUN 2015 | DOI: 10.1111/php.12471

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      The TiO2 nanotube arrays were prepared by anodization process with starch addition. With the starch addition, the viscosity of the electrolyte was controlled, which modified the prepared nanotubes grew completely. The as-prepared nanotubes possessed well uniformed and higher photodegradation responsive than the pure TiO2, and consequently enhancing the photochromic properties.

    3. Preparation of Silver Carbonate and its Application as Visible Light-driven Photocatalyst Without Sacrificial Reagent (pages 1315–1323)

      Wei Jiang, Ya Zeng, Xiaoyan Wang, Xiaoning Yue, Shaojun Yuan, Houfang Lu and Bin Liang

      Article first published online: 14 AUG 2015 | DOI: 10.1111/php.12495

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      As-prepared Ag2CO3 possessed high photocatalytic performance which can quickly decompose methyl orange and rhodamine B in less than 15 min under visible light irradiation. The calculated band gap of Ag2CO3 was 2.312 eV with VB edge potential of 2.685 eV and CB 0.373 eV. Photogenerated ozone anion radicals and holes are determined as the major active species in the oxidation–reduction degradation of dye with Ag2CO3. The generation of metallic silver resulted from photocorrosion slightly decayed the performance of Ag2CO3 after recycling. The simple preparation method and high photocatalytic performance of Ag2CO3 increases its prospect of application in future.

    4. Photoisomerization of Trans Ortho-, Meta-, Para-Nitro Diarylbutadienes: A Case of Regioselectivity (pages 1324–1331)

      Harsha Agnihotri, Mahalingavelar Paramasivam, Veerabhadraiah Palakollu and Sriram Kanvah

      Article first published online: 11 SEP 2015 | DOI: 10.1111/php.12504

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      Regioselective isomerization of o-nitrobutadiene derivatives.

    5. Selective Activation of C=C Bond in Sustainable Phenolic Compounds from Lignin via Photooxidation: Experiment and Density Functional Theory Calculations (pages 1332–1339)

      Morgan Zielinski (Goldberg), Luke A. Burke and Alexander Samokhvalov

      Article first published online: 15 SEP 2015 | DOI: 10.1111/php.12509

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      We report a selective photochemical and photocatalytic oxidative activation of C=C bond in sustainable phenolic compound from lignin, isoeugenol vs its isomer eugenol, as found for the first time. Photooxidation of isoeugenol to lignan dehydrodiisoeugenol (DHDIE) in solution has the following advantages vs chemical oxidation: 1) reaction proceeds only via internal C=C bond in isoeugenol, but not via terminal C=C bond in isomeric eugenol and 2) photooxidation of isoeugenol leads to fewer molecular products. We also report, for the first time, the density functional theory calculations of the stage-wise mechanism of oxidative “dimerization” of isoeugenol to DHDIE.

    6. Pulsed Laser-Driven Molecular Self-assembly of Cephalexin: Aggregation-Induced Fluorescence and Its Utility as a Mercury Ion Sensor (pages 1340–1347)

      Pradeep Kumar Singh, Asmita Prabhune and Satishchandra Ogale

      Article first published online: 14 OCT 2015 | DOI: 10.1111/php.12526

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      Pulsed UV laser irradiation of cephalexin solution in water makes aggregation-induced fluorescent mesostructures. These fluorescent structures can be used for mercury ion (Hg++) sensing in aqueous solution.

    7. Amino Acid–Porphyrin Conjugates: Synthesis and Study of their Photophysical and Metal Ion Recognition Properties (pages 1348–1355)

      Albish K. Paul, Suneesh C. Karunakaran, Joshy Joseph and Danaboyina Ramaiah

      Article first published online: 23 OCT 2015 | DOI: 10.1111/php.12527

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      Synthesis, photophysical properties and metal ion interactions of few proline/tryptophan-linked free-base and Zn-porphyrins are described. These porphyrins exhibit excellent triplet quantum yields and singlet oxygen generation efficiencies, making them desirable for PDT applications. Proline – Zn-porphyrin conjugates selectively interact with Cu2+ leading to significant changes in absorption properties and strong quenching of fluorescence.

    8. Biochemical Characterization of the DASH-Type Cryptochrome CryD From Fusarium fujikuroi (pages 1356–1367)

      Marta Castrillo, Adrian Bernhardt, Javier Ávalos, Alfred Batschauer and Richard Pokorny

      Article first published online: 11 SEP 2015 | DOI: 10.1111/php.12501

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      The study biochemically characterizes the heterologously expressed and purified DASH-type cryptochrome CryD that plays regulatory roles in Fusarium fujikuroi. As an example, CryD inhibits the light-induced accumulation of a red polyketide pigment bikaverin in F. fujikuroi mycelia. Colonies of F. fujikuroi wild-type strain (Wild type) and of a representative CryD null-mutant strain (ΔcryD) grown for 7 days at 30°C on a minimal medium with low nitrogen content in white light (Light) are colored differently whereas colonies of the two strains grown in darkness (Dark) show the same color.

    9. Thermal Effects and Structural Changes of Photosynthetic Reaction Centers Characterized by Wide Frequency Band Hydrophone: Effects of Carotenoids and Terbutryn (pages 1368–1375)

      László Nagy, Vladimir Kiss, Vlad Brumfeld, Károly Osvay, Ádám Börzsönyi, Melinda Magyar, Tibor Szabó, Márta Dorogi and Shmuel Malkin

      Article first published online: 25 SEP 2015 | DOI: 10.1111/php.12511

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      Photothermal characteristics and light induced structural (volume) changes of carotenoid containing and noncontaining photosynthetic reaction centers were investigated by wide frequency band hydrophone and compared. The presence of carotenoid either does not play considerable role in the light induced conformational movements or these rearrangements are slow enough for inducing the photoacoustic signal. Binding of terbutryne to the acceptor side of the RC contributes specifically to the overall RC dynamics. Our results do not confirm large displacements and volume changes induced by the charge relaxation processes existing in RCs in the microseconds time scale that accompanies the interquinone electron transfer.

    10. Photosynthetic Performance of the Red Alga Pyropia haitanensis During Emersion, With Special Reference to Effects of Solar UV Radiation, Dehydration and Elevated CO2 Concentration (pages 1376–1381)

      Juntian Xu and Kunshan Gao

      Article first published online: 17 OCT 2015 | DOI: 10.1111/php.12531

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      As one of the most economically important intertidal macroalga, Pyropia haitanensis experiences periodic exposures to air with tidal cycles either in its niche or on farming rafts. Subsequently, the alga often suffers from dehydration due to desiccation, especially during daytime under the sun with presence of UV radiation and heat stresses. During such exposures, CO2 is the only exogenous carbon source for its photosynthesis. Although increasing atmospheric CO2 can enhance the photosynthesis during the exposures, such benefit diminished with increased levels of water loss and in the presence of solar UV radiation.

    11. UV Sensitivity of Vegetative and Reproductive Tissues of Two Antarctic Brown Algae is Related to Differential Allocation of Phenolic Substances (pages 1382–1388)

      Pirjo Huovinen and Iván Gómez

      Article first published online: 20 SEP 2015 | DOI: 10.1111/php.12500

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      Allocation and proportions of the soluble and insoluble phlorotannins could be related with UV tolerance of two Antarctic brown algae. In highly UV tolerant (measured as chlorophyll fluorescence) Ascoseira mirabilis, the insoluble phlorotannins were more abundant, while in the more UV sensitive Cystosphaera jacquinotii, the soluble fraction dominated. In C. jacquinotii, the receptacles showed higher UV tolerance than the vegetative blades. The reproductive tissues of both species contained more soluble phlorotannins than the vegetative tissues. High allocation of phenolic compounds in both reproductive and vegetative tissues of C. jacquinotii was confirmed by microscopical blue autofluorescence images of tissue cross-sections.

    12. Dunaliella tertiolecta (Chlorophyta) Avoids Cell Death Under Ultraviolet Radiation By Triggering Alternative Photoprotective Mechanisms (pages 1389–1402)

      María Segovia, Teresa Mata, Armando Palma, Candela García-Gómez, Rosario Lorenzo, Alicia Rivera and Félix L. Figueroa

      Article first published online: 25 SEP 2015 | DOI: 10.1111/php.12502

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      Two modes of photoprotection under P and UVB, respectively (light-gray areas). The white area represents the photoprotective mechanism observed only under simultaneous P+UVB, i.e. incomplete protection if one of them is absent. Dark-gray area represents UVB-caused damage.

    13. Model for Optimization of the UV-A/Riboflavin Strengthening (cross-linking) of the Cornea: Percolation Threshold (pages 1403–1411)

      Anton Semchishen, Michael Mrochen and Vladimir Semchishen

      Article first published online: 11 AUG 2015 | DOI: 10.1111/php.12498

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      To achieve the maximum level of collagen strengthening within the shortest treatment time possible, we have developed a mathematical model which is used to optimize the process of corneal cross-linking. This model is able to predict the temporal and spatial distribution of generated cross-links within the corneal stroma and hence the increase in the elasticity modulus. Theory predicts corneal strengthening at low radiation intensities and the absence of the strengthening effect at radiation intensities above the threshold level, which agrees with the experimental results. The model accounts for the initial riboflavin concentration and bleaching, light intensity and time of illumination.

    14. Effect of LED Blue Light on Penicillium digitatum and Penicillium italicum Strains (pages 1412–1421)

      María T. Lafuente and Fernando Alférez

      Article first published online: 7 OCT 2015 | DOI: 10.1111/php.12519

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      The effect of LED blue light on growth and morphology of Penicillium digitatum strains resistant and sensitive to fungicides and Penicillium italicum, the major postharvest pathogens of citrus fruits, has been investigated. The photographs show how blue light (L) affects morphology and delays fungal growth with respect to the control cultures held under darkness (D). Results also show that blue light has a nonreversible detrimental effect on fungal growth and that spore germination is avoided by exposing the cultures of all strains to high blue light quantum flux.

    15. Synergistic Photobactericidal Activity Based on Ultraviolet-A Irradiation and Ferulic Acid Derivatives (pages 1422–1428)

      Akihiro Shirai, Masato Kajiura and Takeshi Omasa

      Article first published online: 15 SEP 2015 | DOI: 10.1111/php.12507

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      This study describes the inactivation of Escherichia coli by combined treatment with trans-ferulic acid or its derivatives and UV-A LED light. In particular, a trans-ferulic acid derivative modified with l-tyrosine (FA-Tyr) as a cationic moiety significantly reduced E. coli viability during UV-A irradiation, compared with UV-A irradiation alone. The strong photobactericidal effect results from the generation of reactive oxygen species such as hydroxyl radicals within bacterial cells, suggesting that the cationic property of the trans-ferulic acid derivative is important in mediating interaction with the bacterial cell surface.

    16. Modulation of Melanogenesis and Antioxidant Status of Melanocytes in Response to Phototoxic Action of Doxycycline (pages 1429–1434)

      Jakub Rok, Ewa Buszman, Artur Beberok, Marcin Delijewski, Michał Otręba and Dorota Wrześniok

      Article first published online: 13 AUG 2015 | DOI: 10.1111/php.12497

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      Doxycycline enhances an UVA-mediated phototoxicity in normal human melanocytes.

    17. Baicalin Protects Keratinocytes from Toll-like Receptor-4 Mediated DNA Damage and Inflammation Following Ultraviolet Irradiation (pages 1435–1443)

      Wei Min, Israr Ahmad, Michelle E. Chang, Erin M. Burns, Qihong Qian and Nabiha Yusuf

      Article first published online: 11 SEP 2015 | DOI: 10.1111/php.12505

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      UVB radiation causes both direct and indirect damage to the skin including the generation of reactive oxygen species (ROS), inflammation and immunosuppression, which ultimately contribute to photocarcinogenesis. A plant-derived flavonoid, baicalin, has been shown to be effective as an antioxidant, anti-inflammatory and free radical scavenger. Baicalin treatment before and after UV radiation protected PAM212 keratinocytes from UVB-induced damage by inhibiting Toll-like receptor-4 (TLR4) and its downstream signaling molecules, MyD88, TRIF, TRAF6 and IRAK4. This inhibition resulted in NF-κB inactivation and downregulation of iNOS and COX-2. Intracellular ROS and markers of DNA damage, including cyclobutane pyrimidine dimers and 8-Oxo-2′-deoxyguanosine, were significantly reduced.

    18. Epigenetically Enhanced Photodynamic Therapy (ePDT) is Superior to Conventional Photodynamic Therapy for Inducing Apoptosis in Cutaneous T-Cell Lymphoma (pages 1444–1451)

      Katrin Agnes Salva and Gary S. Wood

      Article first published online: 12 OCT 2015 | DOI: 10.1111/php.12521

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      Aminolevulinate photodynamic therapy (ALA-PDT) induces apoptosis and effectively eradicates actinic keratoses, but has limited efficacy in cutaneous T-cell lymphoma (CTCL). Cutaneous T-cell lymphoma resists apoptosis due to low expression of death receptors like Fas cell surface death receptor (FAS). We showed previously that methotrexate (MTX) upregulates FAS epigenetically by promoter derepression and restores the susceptibility of CTCL to extrinsic apoptosis. Here, we demonstrate that MTX increases the response of CTCL to ALA-PDT—a concept we call epigenetically enhanced PDT (ePDT). ePDT caused upregulation of death receptors/ligands (DR/DRL) with increased activation of extrinsic apoptosis as compared to conventional PDT. These findings warrant clinical trials of ePDT for CTCL.

    19. Photodynamic Diagnosis Using 5-Aminolevulinic Acid in 41 Biopsies for Primary Central Nervous System Lymphoma (pages 1452–1457)

      Tetsuya Yamamoto, Eiichi Ishikawa, Shunichiro Miki, Noriaki Sakamoto, Alexander Zaboronok, Masahide Matsuda, Hiroyoshi Akutsu, Kei Nakai, Wataro Tsuruta and Akira Matsumura

      Article first published online: 15 SEP 2015 | DOI: 10.1111/php.12510

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      Positive fluorescence was observed in 34 of 41 biopsies (82.9%) obtained under 5-aminolevulinic acid-mediated photodynamic diagnosis (PDD) for primary central nervous system lymphoma (PCNSL) as final pathological diagnosis. In 21 of the 34 biopsies (61.8%), an intraoperative pathological diagnosis (IOD) of suspected PCNSL was made. In the remaining 13 biopsies, however, the IOD was either incorrect (atypical cell, 4; high-grade glioma, 1; gliosis, 1; unremarkable, 2) or not performed (5). PDD of biopsy samples in patients with suspected PCNSL is a feasible way to obtain accurate samples and may lead to improved diagnostic yield in the biopsy of PCNSL.

    20. Caffeic Acid Inhibits UVB-induced Inflammation and Photocarcinogenesis Through Activation of Peroxisome Proliferator-activated Receptor-γ in Mouse Skin (pages 1458–1468)

      Agilan Balupillai, Rajendra N. Prasad, Karthikeyan Ramasamy, Ganesan Muthusamy, Mohana Shanmugham, Kanimozhi Govindasamy and Srithar Gunaseelan

      Article first published online: 13 OCT 2015 | DOI: 10.1111/php.12522

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      Excessive UVB irradiation increased the skin tumor incidence, oxidative imbalance, angiogenic and inflammatory signaling and activation of NF-κB, a transcription factor involved in inflammation in mouse skin. Caffeic acid administration before each UVB irradiation decreased the angiogenic and inflammatory signaling with decreased expression of NF-kB. Caffeic acid might act as agonist of PPARγ, a transcription factor involved in the anti-inflammation reaction, and inhibit NF-κB-mediated inflammatory reactions thereby inhibiting photocarcinogenesis in mouse skin.

    21. Noninvasive Optical Imaging of UV-Induced Squamous Cell Carcinoma in Murine Skin: Studies of Early Tumor Development and Vitamin D Enhancement of Protoporphyrin IX Production (pages 1469–1478)

      Kishore R. Rollakanti, Sanjay Anand, Scott C. Davis, Brian W. Pogue and Edward V. Maytin

      Article first published online: 25 SEP 2015 | DOI: 10.1111/php.12503

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      Newly formed squamous cell skin cancers on the back of a hairless mouse (top panel), observed at 24 weeks after the start of a UV-exposure protocol, selectively express high levels of protoporphyrin IX following a 4-h application of aminolevulinate and noninvasive fluorescence detection (bottom panel).

    22. Protective Effect of Dermal Brimonidine Applications Against UV Radiation-induced Skin Tumors, Epidermal Hyperplasia and Cell Proliferation in the Skin of Hairless Mice (pages 1479–1487)

      Guy Bouvier, Douglas B. Learn, Christelle Nonne, Gérard Feraille, Emmanuel Vial and Bernard Ruty

      Article first published online: 14 OCT 2015 | DOI: 10.1111/php.12528

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      Brimonidine applied topically in hairless mice exposed to UVR in a photocarcinogenicity study significantly increased survival, reduced the tumor yield and tumor incidence and increased the unbiased median week to tumor and decreased incidences of erythema, flaking, wrinkling and skin thickening, compared to the vehicle group + UVR. All effects occurred dose-dependently. Brimonidine at 2% applied 1 h before or just after UVB irradiation on hairless mice decreased epidermal hyperplasia and epithelial cell proliferation induced by UVB similar to an EGFR inhibitor.

    23. In Vivo Spectrum of UVC-induced Mutation in Mouse Skin Epidermis May Reflect the Cytosine Deamination Propensity of Cyclobutane Pyrimidine Dimers (pages 1488–1496)

      Hironobu Ikehata, Toshio Mori and Masayuki Yamamoto

      Article first published online: 13 OCT 2015 | DOI: 10.1111/php.12525

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      The sequence context preference of UV signature mutation results from the wavelength-dependent preference of CPD formation for mCpG sites and the context-oriented cytosine deamination propensity of cyclobutane pyrimidine dimers.

    24. Early Diagnosis of Diabetes through the Eye (pages 1497–1504)

      Devi Kalyan Karumanchi, Elizabeth R. Gaillard and James Dillon

      Article first published online: 17 OCT 2015 | DOI: 10.1111/php.12524

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      Diabetes mellitus is a metabolic disorder characterized by high blood sugar levels which give rise to complications in the eye, kidney and brain. Current standard diagnostic methods are less than accurate for diagnosis at a very early stage due to fast hemoglobin turnover. The lens is avascular and has no protein turnover and therefore accumulates AGEs with aging and disease. By screening the fluorescence lifetimes from the eye lens and eye lens model protein systems, we can discriminate between nondiabetic and diabetic tissue which may lead to new, noninvasive diagnostic methods.

    25. Maximum Incident Erythemally Effective UV Exposure Received by Construction Workers, in Valencia, Spain (pages 1505–1509)

      Vicente Blanca Giménez, Gonzalo Gurrea Ysasi, Juan Carlos Moreno and María Antonia Serrano

      Article first published online: 17 OCT 2015 | DOI: 10.1111/php.12530

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      This article analyzes the influence of Ultraviolet Erythematic Radiation (UVER) dose received by construction workers in Valencia highlighting the upper limit of the dose received for a worker in different periods of a year. Viospor dosimeters placed on a mannequin have been used in this study. The measurements took place between 2012 December and 2013 July.