El discurso de política pública presidencial: Los casos de salud y educación durante los gobiernos de la Concertación (1990-2009)

This article uses Baumgartner and Jones’ policy agenda theoretical and methodological framework to study the Concertación presidents’ May 21 (state of the union) speeches, with an aim towards determining the importance, as well as changes and continuities, that health and education are given in the public policy agenda.Este artículo usa el marco teórico, y la metodología, del policy agenda de Baumgartner y Jones, para estudiar los discursos del 21 de mayo de los presidentes de la Concertación con el objeto de determinar la importancia, los cambios y la continuidad que las áreas de salud y educación poseen en la agenda pública

Accuracy on parameter recovery, with ordinals data, of structure covariance analysis and partial least squares path modeling

ReconocimientoSe compara la precisión en la recuperación de parámetros del Análisis de Estructura de Covarianza (ACOV) y el Modelo de Rutas mediante Mínimos Cuadrados Parciales (PLS-PM), en un modelo simple con variables manifiestas simuladas con escala ordinal de cinco puntos. Se utiliza un diseño experimental, manipulando el método de estimación, tamaño muestral, nivel de asimetría y tipo de especificación del modelo. Se valora la media de las diferencias absolutas para el modelo estructural. ACOV presenta estimaciones más precisas que PLS-PM, en distintas condiciones experimentales. Cuando se utiliza un tamaño muestral pequeño, ambas técnicas son igualmente precisas. Se sugiere utilizar ACOV frente a PLS-PM. Se desaconseja fundamentar la elección de PLS-PM frente a ACOV en la utilización de una muestra pequeñaThe accuracy on parameter recovery is compared between Structure Covariance Analysis (ACOV) and Partial Least Squares Path Modeling (PLS-PM), with simulated ordinals data with 5 points, in a simple model. An experimental design is used, controlling the estimation method, sample size, skewness level and model specification. Mean absolute differences are used to assess accuracy for the structural model. ACOV provided more accurate estimates of the structural parameters than PLS-PM in different experimental conditions. With a small sample size, both techniques are equally accurate. Using ACOV against PLS-PM is suggested. PLS choosing ACOV instead based on the use of a small sample size is not recommendedArtículo de investigación. FONDECYT de Iniciación 2013, N° 11130722. Beca Presidente de la República de Chile (2008), de la Comisión Nacional de Investigación Científica y Tecnológica de Chile (CONICYT

Triplet Excited States as a Source of Relevant (Bio)Chemical Information

[EN] The properties of triplet excited states are markedly medium-dependent, which turns this species into valuable tools for investigating the microenvironments existing in protein binding pockets. Monitoring of the triplet excited state behavior of drugs within transport proteins (serum albumins and alpha(1)-acid glycoproteins) by laser flash photolysis constitutes a valuable source of information on the strength of interaction, conformational freedom and protection from oxygen or other external quenchers. With proteins, formation of spatially confined triplet excited states is favored over competitive processes affording ionic species. Remarkably, under aerobic atmosphere, the triplet decay of drug@protein complexes is dramatically longer than in bulk solution. This offers a convenient dynamic range for assignment of different triplet populations or for stereochemical discrimination. In this review, selected examples of the application of the laser flash photolysis technique are described, including drug distribution between the bulk solution and the protein cavities, or between two types of proteins, detection of drug-drug interactions inside proteins, and enzyme-like activity processes mediated by proteins. Finally, protein encapsulation can also modify the photoreactivity of the guest. This is illustrated by presenting an example of retarded photooxidation.Financial support by Spanish Government (CTQ2013-47872-C2-1-P) and Generalitat Valenciana (Prometeo II/2013/005) is gratefully acknowledged.Jiménez Molero, MC.; Miranda Alonso, MÁ. (2014). Triplet Excited States as a Source of Relevant (Bio)Chemical Information. Current Topics in Medicinal Chemistry. 14(23):2734-2742. https://doi.org/10.2174/1568026614666141216100907S27342742142

Regioselectivity in the adiabatic photocleavage of DNA-based oxetanes

[EN] Direct absorption of UVB light by DNA may induce formation of cyclobutane pyrimidine dimers and pyrimidine-pyrimidone (6-4) photoproducts. The latter arise from the rearrangement of unstable oxetane intermediates, which have also been proposed to be the electron acceptor species in the photoenzymatic repair of this type of DNA damage. In the present work, direct photolysis of oxetanes composed of substituted uracil (Ura) or thymine (Thy) derivatives and benzophenone (BP) have been investigated by means of transient absorption spectroscopy from the femtosecond to the microsecond time-scales. The results showed that photoinduced oxetane cleavage takes place through an adiabatic process leading to the triplet excited BP and the ground state nucleobase. This process was markedly affected by the oxetane regiochemistry (head-to-head, HH, vs. head-to-tail, HT) and by the nucleobase substitution; it was nearly quantitative for all investigated HH-oxetanes while it became strongly influenced by the substitution at positions 1 and 5 for the HT-isomers. The obtained results clearly confirm the generality of the adiabatic photoinduced cleavage of BP/Ura or Thy oxetanes, as well as its dependence on the regiochemistry, supporting the involvement of triplet exciplexes. As a matter of fact, when formation of this species was favored by keeping together the Thy and BP units after splitting by means of a linear linker, a transient absorption at similar to 400 nm, ascribed to the exciplex, was detected.Financial support from the Spanish Government (RYC-2015-17737 and CTQ2017-89416-R) and from the Conselleria d'Educacio Cultura i Esport (PROMETEO/2017/075 and GRISOLIAP/2017/005) is gratefully acknowledged.Blasco-Brusola, A.; Vayá Pérez, I.; Miranda Alonso, MÁ. (2020). Regioselectivity in the adiabatic photocleavage of DNA-based oxetanes. Organic & Biomolecular Chemistry. 18(44):9117-9123. https://doi.org/10.1039/D0OB01974GS91179123184

Influence of the linking bridge on the photoreactivity of benzophenone-thymine conjugates

[EN] Benzophenone (BP) is present in a variety of bioactive molecules. This chromophore is able to photosensitize DNA damage, where one of the most relevant BP/ DNA interactions occurs with thymine (Thy). In view of the complex photoreactivity previously observed for dyads containing BP covalently linked to thymidine, the aim of this work is to investigate whether appropriate changes in the nature of the spacer could modulate the intramolecular BP/Thy photoreactivity, resulting in an enhanced selectivity. Accordingly, the photobehavior of a series of dyads derived from BP and Thy, separated by linear linkers of different length, has been investigated by steady-state photolysis, as well as femtosecond and nanosecond transient absorption spectroscopy. Irradiation of the dyads led to photoproducts arising from formal hydrogen abstraction or Paterno-Buchi (PB) photoreaction, with a chemoselectivity that was clearly dependent on the nature of the linking bridge; moreover, the PB process occurred with complete regio- and stereoselectivity. The overall photoreactivity increased with the length of the spacer and correlated well with the rate constants estimated from the BP triplet lifetimes. A reaction mechanism explaining these results is proposed, where the key features are the strain associated with the reactive conformations and the participation of triplet exciplexes.Financial support from the Spanish Government (RYC-2015-17737 and CTQ2017-89416-R) and from the Conselleria d'Educació Cultura i Esport (PROMETEO/2017/075 and GRISOLIAP/2017/005) is gratefully acknowledged. The authors would like to thank the use of RIAIDT-USC analytical facilities for the X-ray crystallography analysis.Blasco-Brusola, A.; Vayá Pérez, I.; Miranda Alonso, MÁ. (2020). Influence of the linking bridge on the photoreactivity of benzophenone-thymine conjugates. The Journal of Organic Chemistry. 85(21):14068-14076. https://doi.org/10.1021/acs.joc.0c02088S14068140768521Kraemer, K. H. (1997). Sunlight and skin cancer: Another link revealed. Proceedings of the National Academy of Sciences, 94(1), 11-14. doi:10.1073/pnas.94.1.11Cadet, J., Mouret, S., Ravanat, J.-L., & Douki, T. (2012). Photoinduced Damage to Cellular DNA: Direct and Photosensitized Reactions†. Photochemistry and Photobiology, 88(5), 1048-1065. doi:10.1111/j.1751-1097.2012.01200.xRastogi, R. P., Richa, Kumar, A., Tyagi, M. B., & Sinha, R. P. (2010). Molecular Mechanisms of Ultraviolet Radiation-Induced DNA Damage and Repair. Journal of Nucleic Acids, 2010, 1-32. doi:10.4061/2010/592980Sinha, R. P., & Häder, D.-P. (2002). UV-induced DNA damage and repair: a review. Photochemical & Photobiological Sciences, 1(4), 225-236. doi:10.1039/b201230hChatterjee, N., & Walker, G. C. (2017). Mechanisms of DNA damage, repair, and mutagenesis. Environmental and Molecular Mutagenesis, 58(5), 235-263. doi:10.1002/em.22087Brash, D. E., & Haseltine, W. A. (1982). UV-induced mutation hotspots occur at DNA damage hotspots. Nature, 298(5870), 189-192. doi:10.1038/298189a0Taylor, J. S., & Cohrs, M. P. (1987). DNA, light, and Dewar pyrimidinones: the structure and biological significance to TpT3. Journal of the American Chemical Society, 109(9), 2834-2835. doi:10.1021/ja00243a052Taylor, J. S., Garrett, D. S., & Cohrs, M. P. (1988). Solution-state structure of the Dewar pyrimidinone photoproduct of thymidylyl-(3’ .fwdarw. 5’)-thymidine. Biochemistry, 27(19), 7206-7215. doi:10.1021/bi00419a007Kim, S. T., Malhotra, K., Smith, C. A., Taylor, J. S., & Sancar, A. (1994). Characterization of (6-4) photoproduct DNA photolyase. Journal of Biological Chemistry, 269(11), 8535-8540. doi:10.1016/s0021-9258(17)37228-9Li, J., Liu, Z., Tan, C., Guo, X., Wang, L., Sancar, A., & Zhong, D. (2010). Dynamics and mechanism of repair of ultraviolet-induced (6–4) photoproduct by photolyase. Nature, 466(7308), 887-890. doi:10.1038/nature09192Todo, T., Ryo, H., Yamamoto, K., Toh, H., Inui, T., Ayaki, H., … Ikenaga, M. (1996). Similarity Among the Drosophila (6-4)Photolyase, a Human Photolyase Homolog, and the DNA Photolyase-Blue-Light Photoreceptor Family. Science, 272(5258), 109-112. doi:10.1126/science.272.5258.109Todo, T., Takemori, H., Ryo, H., lhara, M., Matsunaga, T., Nikaido, O., … Nomura, T. (1993). A new photoreactivating enzyme that specifically repairs ultraviolet light-induced (6-4)photoproducts. Nature, 361(6410), 371-374. doi:10.1038/361371a0Todo, T., Tsuji, H., Otoshi, E., Hitomi, K., Sang-Tae Kim, & Ikenaga, M. (1997). Characterization of a human homolog of (6-4)photolyase. Mutation Research/DNA Repair, 384(3), 195-204. doi:10.1016/s0921-8777(97)00032-3Epe, B., Pflaum, M., & Boiteux, S. (1993). DNA damage induced by photosensitizers in cellular and cell-free systems. Mutation Research/Genetic Toxicology, 299(3-4), 135-145. doi:10.1016/0165-1218(93)90091-qMichaud, S., Hajj, V., Latapie, L., Noirot, A., Sartor, V., Fabre, P.-L., & Chouini-Lalanne, N. (2012). Correlations between electrochemical behaviors and DNA photooxidative properties of non-steroïdal anti-inflammatory drugs and their photoproducts. Journal of Photochemistry and Photobiology B: Biology, 110, 34-42. doi:10.1016/j.jphotobiol.2012.02.007Marguery, M. C., Chouini-Lalanne, N., Ader, J. C., & Paillous, N. (1998). Comparison of the DNA Damage Photoinduced by Fenofibrate and Ketoprofen, Two Phototoxic Drugs of Parent Structure. Photochemistry and Photobiology, 68(5), 679-684. doi:10.1111/j.1751-1097.1998.tb02529.xVinette, A. L., McNamee, J. P., Bellier, P. V., McLean, J. R. N., & Scaiano, J. C. (2003). Prompt and Delayed Nonsteroidal Anti-inflammatory Drug–photoinduced DNA Damage in Peripheral Blood Mononuclear Cells Measured with the Comet Assay¶. Photochemistry and Photobiology, 77(4), 390. doi:10.1562/0031-8655(2003)0772.0.co;2Lhiaubet, V., Gutierrez, F., Penaud–Berruyer, F., Amouyal, E., Daudey, J.-P., Poteau, R., … Paillous, N. (2000). Spectroscopic and theoretical studies of the excited states of fenofibric acid and ketoprofen in relation with their photosensitizing properties. New Journal of Chemistry, 24(6), 403-410. doi:10.1039/a909539jLhiaubet, V., Paillous, N., & Chouini-Lalanne, N. (2001). Comparison of DNA Damage Photoinduced by Ketoprofen, Fenofibric Acid and Benzophenone via Electron and Energy Transfer¶. Photochemistry and Photobiology, 74(5), 670. doi:10.1562/0031-8655(2001)0742.0.co;2Cuquerella, M. C., Lhiaubet-Vallet, V., Cadet, J., & Miranda, M. A. (2012). Benzophenone Photosensitized DNA Damage. Accounts of Chemical Research, 45(9), 1558-1570. doi:10.1021/ar300054eBignon, E., Marazzi, M., Besancenot, V., Gattuso, H., Drouot, G., Morell, C., … Monari, A. (2017). Ibuprofen and ketoprofen potentiate UVA-induced cell death by a photosensitization process. Scientific Reports, 7(1). doi:10.1038/s41598-017-09406-8Boscá, F., & Miranda, M. A. (1998). New Trends in Photobiology (Invited Review) Photosensitizing drugs containing the benzophenone chromophore. Journal of Photochemistry and Photobiology B: Biology, 43(1), 1-26. doi:10.1016/s1011-1344(98)00062-1Rogers, J. E., & Kelly, L. A. (1999). Nucleic Acid Oxidation Mediated by Naphthalene and Benzophenone Imide and Diimide Derivatives:  Consequences for DNA Redox Chemistry. Journal of the American Chemical Society, 121(16), 3854-3861. doi:10.1021/ja9841299Surana, K., Chaudhary, B., Diwaker, M., & Sharma, S. (2018). Benzophenone: a ubiquitous scaffold in medicinal chemistry. MedChemComm, 9(11), 1803-1817. doi:10.1039/c8md00300aCuquerella, M. C., Lhiaubet-Vallet, V., Bosca, F., & Miranda, M. A. (2011). Photosensitised pyrimidine dimerisation in DNA. Chemical Science, 2(7), 1219. doi:10.1039/c1sc00088hBlasco-Brusola, A., Navarrete-Miguel, M., Giussani, A., Roca-Sanjuán, D., Vayá, I., & Miranda, M. A. (2020). Regiochemical memory in the adiabatic photolysis of thymine-derived oxetanes. A combined ultrafast spectroscopic and CASSCF/CASPT2 computational study. Physical Chemistry Chemical Physics, 22(35), 20037-20042. doi:10.1039/d0cp03084hBurrows, C. J., & Muller, J. G. (1998). Oxidative Nucleobase Modifications Leading to Strand Scission. Chemical Reviews, 98(3), 1109-1152. doi:10.1021/cr960421sBelmadoui, N., Climent, M. J., & Miranda, M. A. (2006). Photochemistry of a naphthalene–thymine dyad in the presence of acetone. Tetrahedron, 62(7), 1372-1377. doi:10.1016/j.tet.2005.11.035Bonancía, P., Vayá, I., Climent, M. J., Gustavsson, T., Markovitsi, D., Jiménez, M. C., & Miranda, M. A. (2012). Excited-State Interactions in Diastereomeric Flurbiprofen–Thymine Dyads. The Journal of Physical Chemistry A, 116(35), 8807-8814. doi:10.1021/jp3063838Encinas, S., Climent, M. J., Gil, S., Abrahamsson, U. O., Davidsson, J., & Miranda, M. A. (2004). Singlet Excited-State Interactions in Naphthalene-Thymine Dyads. ChemPhysChem, 5(11), 1704-1709. doi:10.1002/cphc.200400262Belmadoui, N., Encinas, S., Climent, M. J., Gil, S., & Miranda, M. A. (2006). Intramolecular Interactions in the Triplet Excited States of Benzophenone–Thymine Dyads. Chemistry - A European Journal, 12(2), 553-561. doi:10.1002/chem.200500345Dumont, E., Wibowo, M., Roca-Sanjuán, D., Garavelli, M., Assfeld, X., & Monari, A. (2015). Resolving the Benzophenone DNA-Photosensitization Mechanism at QM/MM Level. The Journal of Physical Chemistry Letters, 6(4), 576-580. doi:10.1021/jz502562dDelatour, T., Douki, T., D’Ham, C., & Cadet, J. (1998). Photosensitization of thymine nucleobase by benzophenone through energy transfer, hydrogen abstraction and one-electron oxidation. Journal of Photochemistry and Photobiology B: Biology, 44(3), 191-198. doi:10.1016/s1011-1344(98)00142-0Tamai, N., Asahi, T., & Masuhara, H. (1992). Intersystem crossing of benzophenone by femtosecond transient grating spectroscopy. Chemical Physics Letters, 198(3-4), 413-418. doi:10.1016/0009-2614(92)85074-kGut, I. G., Wood, P. D., & Redmond, R. W. (1996). Interaction of Triplet Photosensitizers with Nucleotides and DNA in Aqueous Solution at Room Temperature. Journal of the American Chemical Society, 118(10), 2366-2373. doi:10.1021/ja9519344Miro, P., Gomez‐Mendoza, M., Sastre, G., Cuquerella, M. C., Miranda, M. A., & Marin, M. L. (2019). Generation of the Thymine Triplet State by Through‐Bond Energy Transfer. Chemistry – A European Journal, 25(28), 7004-7011. doi:10.1002/chem.201900830Joseph, A., Prakash, G., & Falvey, D. E. (2000). Model Studies of the (6−4) Photoproduct Photolyase Enzyme:  Laser Flash Photolysis Experiments Confirm Radical Ion Intermediates in the Sensitized Repair of Thymine Oxetane Adducts. Journal of the American Chemical Society, 122(45), 11219-11225. doi:10.1021/ja002541uMartínez, L. J., & Scaiano, J. C. (1997). Transient Intermediates in the Laser Flash Photolysis of Ketoprofen in Aqueous Solutions:  Unusual Photochemistry for the Benzophenone Chromophore. Journal of the American Chemical Society, 119(45), 11066-11070. doi:10.1021/ja970818tPerez-Ruiz, R., Groeneveld, M., van Stokkum, I. H. M., Tormos, R., Williams, R. M., & Miranda, M. A. (2006). Fast transient absorption spectroscopy of the early events in photoexcited chiral benzophenone–naphthalene dyads. Chemical Physics Letters, 429(1-3), 276-281. doi:10.1016/j.cplett.2006.07.077Martens, J.; Maison, W.; Schlemminger, I.; Westerhoff, O.; Groger, H. Preparation of Precursors for PNA monomers. WO20000028642000

A Sunscreen-Based Photocage for Carbonyl Groups

This is the peer reviewed version of the following article: M. Lineros-Rosa, M. A. Miranda, V. Lhiaubet-Vallet, Chem. Eur. J. 2020, 26, 7205, which has been published in final form at https://doi.org/10.1002/chem.202000123. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.[EN] Photolabile protecting groups (PPGs) have been exploited in a wide range of chemical and biological applications, due to their ability to provide spatial and temporal control over light-triggered activation. In this work, we explore the concept of a new photocage compound based on the commercial UVA/UVB filter oxybenzone (OB; 2-hydroxy-4-methoxybenzophenone) for photoprotection and controlled release of carbonyl groups. The point here is that oxybenzone not only acts as a mere PPG, but also provides, once released, UV photoprotection to the carbonyl derivative. This design points to a possible therapeutic approach to reduce the severe photoadverse effects of drugs containing a carbonyl chromophore.This work was supported by the Spanish Government (project PGC2018-096684-B-I00) and the Universitat Politecnica de Valencia (FPI grant to M.L.-R.). Carmen Clemente Martínez is acknowledged for her technical help during the UPLC-HRMS experiments.Lineros-Rosa, M.; Miranda Alonso, MÁ.; Lhiaubet, VL. (2020). A Sunscreen-Based Photocage for Carbonyl Groups. Chemistry - A European Journal. 26(32):7205-7211. https://doi.org/10.1002/chem.202000123S720572112632Silva, J. M., Silva, E., & Reis, R. L. (2019). Light-triggered release of photocaged therapeutics - Where are we now? Journal of Controlled Release, 298, 154-176. doi:10.1016/j.jconrel.2019.02.006Klausen, M., Dubois, V., Verlhac, J., & Blanchard‐Desce, M. (2019). Tandem Systems for Two‐Photon Uncaging of Bioactive Molecules. ChemPlusChem, 84(6), 589-598. doi:10.1002/cplu.201900139Brieke, C., Rohrbach, F., Gottschalk, A., Mayer, G., & Heckel, A. (2012). Light‐Controlled Tools. Angewandte Chemie International Edition, 51(34), 8446-8476. doi:10.1002/anie.201202134Brieke, C., Rohrbach, F., Gottschalk, A., Mayer, G., & Heckel, A. (2012). Lichtgesteuerte Werkzeuge. Angewandte Chemie, 124(34), 8572-8604. doi:10.1002/ange.201202134Šolomek, T., Wirz, J., & Klán, P. (2015). Searching for Improved Photoreleasing Abilities of Organic Molecules. Accounts of Chemical Research, 48(12), 3064-3072. doi:10.1021/acs.accounts.5b00400Klán, P., Šolomek, T., Bochet, C. G., Blanc, A., Givens, R., Rubina, M., … Wirz, J. (2012). Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy. Chemical Reviews, 113(1), 119-191. doi:10.1021/cr300177kHerrmann, A. (2007). Kontrollierte Freisetzung flüchtiger Verbindungen unter milden Reaktionsbedingungen: von der Natur zu Alltagsprodukten. Angewandte Chemie, 119(31), 5938-5967. doi:10.1002/ange.200700264Wang, P. (2017). Developing photolabile protecting groups based on the excited state meta effect. Journal of Photochemistry and Photobiology A: Chemistry, 335, 300-310. doi:10.1016/j.jphotochem.2016.11.031Griesbeck, A., Kropf, C., Porschen, B., Landes, A., Hinze, O., Huchel, U., & Gerke, T. (2016). Photocaged Hydrocarbons, Aldehydes, Ketones, Enones, and Carboxylic Acids and Esters that Release by the Norrish II Cleavage Protocol and Beyond: Controlled Photoinduced Fragrance Release. Synthesis, 49(03), 539-553. doi:10.1055/s-0036-1588645Herrmann, A. (2012). Using photolabile protecting groups for the controlled release of bioactive volatiles. Photochem. Photobiol. Sci., 11(3), 446-459. doi:10.1039/c1pp05231dFalvey, D. E., & Sundararajan, C. (2004). Photoremovable protecting groups based on electron transfer chemistry. Photochemical & Photobiological Sciences, 3(9), 831. doi:10.1039/b406866aHébert, J., & Gravel, D. (1974). o-Nitrophenylethylene Glycol: a Photosensitive Protecting Group for Aldehydes and Ketones. Canadian Journal of Chemistry, 52(1), 187-189. doi:10.1139/v74-030Gravel, D., Hebert, J., & Thoraval, D. (1983). o-Nitrophenylethylene glycol as photoremovable protective group for aldehydes and ketones: syntheses, scope, and limitations. Canadian Journal of Chemistry, 61(2), 400-410. doi:10.1139/v83-072Wang, P., Hu, H., & Wang, Y. (2007). Application of the Excited State Meta Effect in Photolabile Protecting Group Design. Organic Letters, 9(15), 2831-2833. doi:10.1021/ol071085cWang, P., Hu, H., & Wang, Y. (2007). Novel Photolabile Protecting Group for Carbonyl Compounds. Organic Letters, 9(8), 1533-1535. doi:10.1021/ol070346fYang, H., Zhang, X., Zhou, L., & Wang, P. (2011). Development of a Photolabile Carbonyl-Protecting Group Toolbox. The Journal of Organic Chemistry, 76(7), 2040-2048. doi:10.1021/jo102429gKostikov, A. P., Malashikhina, N., & Popik, V. V. (2009). Caging of Carbonyl Compounds as Photolabile (2,5-Dihydroxyphenyl)ethylene Glycol Acetals. The Journal of Organic Chemistry, 74(4), 1802-1804. doi:10.1021/jo802612fBlanc, A., & Bochet, C. G. (2002). Bis(o-nitrophenyl)ethanediol:  A Practical Photolabile Protecting Group for Ketones and Aldehydes. The Journal of Organic Chemistry, 68(3), 1138-1141. doi:10.1021/jo026347xYu, J., Tang, W.-J., Wang, H.-B., & Song, Q.-H. (2007). Anthraquinon-2-ylethyl-1′,2′-diol (Aqe-diol) as a new photolabile protecting group for aldehydes and ketones. Journal of Photochemistry and Photobiology A: Chemistry, 185(1), 101-105. doi:10.1016/j.jphotochem.2006.05.010Lu, M., Fedoryak, O. D., Moister, B. R., & Dore, T. M. (2003). Bhc-diol as a Photolabile Protecting Group for Aldehydes and Ketones. Organic Letters, 5(12), 2119-2122. doi:10.1021/ol034536bLevrand, B., & Herrmann, A. (2006). Light-induced controlled release of fragrance aldehydes from 1-alkoxy-9,10-anthraquinones for applications in functional perfumery. Flavour and Fragrance Journal, 21(3), 400-409. doi:10.1002/ffj.1728Levrand, B., & Herrmann, A. (2007). Controlled Light-Induced Release of Volatile Aldehydes and Ketones by Photofragmentation of 2-Oxo-(2-phenyl)acetates. CHIMIA International Journal for Chemistry, 61(10), 661-664. doi:10.2533/chimia.2007.661Griesbeck, A. G., Hinze, O., Görner, H., Huchel, U., Kropf, C., Sundermeier, U., & Gerke, T. (2012). Aromatic aldols and 1,5-diketones as optimized fragrance photocages. Photochemical & Photobiological Sciences, 11(3), 587. doi:10.1039/c2pp05286eBrinson, R. G., & Jones, P. B. (2004). Caged trans-4-Hydroxy-2-nonenal. Organic Letters, 6(21), 3767-3770. doi:10.1021/ol048478lBrinson, R. G., Hubbard, S. C., Zuidema, D. R., & Jones, P. B. (2005). Two new anthraquinone photoreactions. Journal of Photochemistry and Photobiology A: Chemistry, 175(2-3), 118-128. doi:10.1016/j.jphotochem.2005.03.027Blankespoor, R. L., DeVries, T., Hansen, E., Kallemeyn, J. M., Klooster, A. M., Mulder, J. A., … Vander Griend, D. A. (2002). Photochemical Synthesis of Aldehydes in the Solid Phase. The Journal of Organic Chemistry, 67(8), 2677-2681. doi:10.1021/jo025508uMcHale, W. A., & Kutateladze, A. G. (1998). An Efficient Photo-SET-Induced Cleavage of Dithiane−Carbonyl Adducts and Its Relevance to the Development of Photoremovable Protecting Groups for Ketones and Aldehydes. The Journal of Organic Chemistry, 63(26), 9924-9931. doi:10.1021/jo981697yLi, Z., Wan, Y., & Kutateladze, A. G. (2003). Dithiane-Based Photolabile Amphiphiles:  Toward Photolabile Liposomes1,2. Langmuir, 19(16), 6381-6391. doi:10.1021/la034188mMajjigapu, J. R. R., Kurchan, A. N., Kottani, R., Gustafson, T. P., & Kutateladze, A. G. (2005). Release and Report:  A New Photolabile Caging System with a Two-Photon Fluorescence Reporting Function. Journal of the American Chemical Society, 127(36), 12458-12459. doi:10.1021/ja053654mKottani, R., Valiulin, R. A., & Kutateladze, A. G. (2006). Direct screening of solution phase combinatorial libraries encoded with externally sensitized photolabile tags. Proceedings of the National Academy of Sciences, 103(38), 13917-13921. doi:10.1073/pnas.0606380103Majjigapu, K., Majjigapu, J. R. R., & Kutateladze, A. G. (2007). Photoamplification and Multiple Tag Release in a Linear Peptide-Based Array of Dithiane Adducts. Angewandte Chemie International Edition, 46(32), 6137-6140. doi:10.1002/anie.200701512Majjigapu, K., Majjigapu, J. R. R., & Kutateladze, A. G. (2007). Photoamplification and Multiple Tag Release in a Linear Peptide-Based Array of Dithiane Adducts. Angewandte Chemie, 119(32), 6249-6252. doi:10.1002/ange.200701512Vath, P., Falvey, D. E., Barnhurst, L. A., & Kutateladze, A. G. (2001). Photoinduced C−C Bond Cleavage in Dithiane−Carbonyl Adducts:  A Laser Flash Photolysis Study. The Journal of Organic Chemistry, 66(8), 2887-2890. doi:10.1021/jo010102nŠtacko, P., Šebej, P., Veetil, A. T., & Klán, P. (2012). Carbon–Carbon Bond Cleavage in Fluorescent Pyronin Analogues Induced by Yellow Light. Organic Letters, 14(18), 4918-4921. doi:10.1021/ol302244fAparici-Espert, I., Cuquerella, M. C., Paris, C., Lhiaubet-Vallet, V., & Miranda, M. A. (2016). Photocages for protection and controlled release of bioactive compounds. Chemical Communications, 52(99), 14215-14218. doi:10.1039/c6cc08175dAparici-Espert, I., Miranda, M., & Lhiaubet-Vallet, V. (2018). Sunscreen-Based Photocages for Topical Drugs: A Photophysical and Photochemical Study of A Diclofenac-Avobenzone Dyad. Molecules, 23(3), 673. doi:10.3390/molecules23030673Marin, M., Lhiaubet-Vallet, V., & Miranda, M. A. (2012). Enhanced Photochemical [6π] Electrocyclization within the Lipophilic Protein Binding Site. Organic Letters, 14(7), 1788-1791. doi:10.1021/ol3003805Görner, H. (2008). Photoinduced Oxygen Uptake of Diphenylamines in Solution and Their Ring Closure Revisited. The Journal of Physical Chemistry A, 112(6), 1245-1250. doi:10.1021/jp076788

Revenue management software in the hotel sector

La disponibilidad de software se ha erigido como un requisito fundamental para la aplicación de Revenue Management desde sus inicios. El gran volumen y variedad de datos requeridos para la adopción de decisiones de Revenue Management ha impulsado el desarrollo de soluciones, tanto genéricas que hemos denominado software de Revenue Management, como específicas, nombradas como herramientas de Revenue Management; en el contexto nacional e internacional. En este trabajo se analiza la evolución y la utilización de ambos tipos en función de la pertenencia o no a cadena hotelera. A nivel internacional se aprecia la difusión, en etapas tempranas de la implantación de Revenue Management, de software genérico. Centrándonos en el caso de España, actualmente se usa un mayor número de herramientas. Se identifican cinco software de Revenue Management mayoritariamente utilizados por cadenas hoteleras (EasyRMS, Synergy, Price Match, Ideas y ARMS); y 25 herramientas de apoyo (shoppers, channel managers, entre otros)que aseguran estar utilizando actualmente un elevado porcentaje de los hoteles que pertenecen a cadenas (93%) y todos los independientes (100%).The availability of software has constituted a fundamental requirement for the application of Revenue Management from its beginnings. The great volume and the variety of data required to adopt Revenue Management decisions has boosted the development of solutions in the national and international contexts that are both generic – which we have called Revenue Management software - and specific –Revenue Management tools. In this work, we analyse the evolution and the use of both types according to belonging to a hotel chain or not. At the international level, the diffusion of generic software is noted in the early stages of implementing Revenue Management. Centring on the case of Spain, more tools are currently used. Five software of Revenue Management have been identified, mainly utilised by hotel chains (EasyRMS, Synergy, Price Match, Ideas and ARMS), and 25 support tools (shoppers, channel managers, among others). The last ones are to a greater or lesser extent employed by a high percentage of the hotels that belong to chains (93%) and all those which are independent (100%)

Sunscreen-Based Photocages for Topical Drugs: A Photophysical and Photochemical Study of A Diclofenac-Avobenzone Dyad

[EN] Photosensitization by drugs is a problem of increasing importance in modern life. This phenomenon occurs when a chemical substance in the skin is exposed to sunlight. Photosensitizing drugs are reported to cause severe skin dermatitis, and indeed, it is generally advised to avoid sunbathing and to apply sunscreen. In this context, the nonsteroidal anti-inflammatory drug (NSAID) diclofenac is a photosensitive drug, especially when administered in topical form. In this work, efforts have been made to design and study an innovative pro-drug/pro-filter system containing diclofenac and the UVA filter avobenzone in order to develop a safer use of this topical drug. The design is based on the presence of a well-established photoremovable phenacyl group in the avobenzone structure. Steady-state photolysis of the dyad in hydrogen-donor solvents, monitored by UV-Vis spectrophotometry and HPLC, confirms the simultaneous photorelease of diclofenac and avobenzone. Laser flash photolysis and phosphorescence emission experiments allow us to gain insight into the photoactive triplet excited-state properties of the dyad. Finally, it is shown that avobenzone provides partial photoprotection to diclofenac from photocyclization to carbazole derivatives.The present work was supported by the Spanish Government (CTQ2015-70164-P, BES-2013-066566), Generalitat Valenciana (Prometeo/2017/075).Aparici-Espert, MI.; Miranda Alonso, MÁ.; Lhiaubet, VL. (2018). Sunscreen-Based Photocages for Topical Drugs: A Photophysical and Photochemical Study of A Diclofenac-Avobenzone Dyad. Molecules. 23(3):1-11. https://doi.org/10.3390/molecules23030673S111233Siegel, R. L., Miller, K. D., & Jemal, A. (2018). Cancer statistics, 2018. CA: A Cancer Journal for Clinicians, 68(1), 7-30. doi:10.3322/caac.21442Curtius, K., Wright, N. A., & Graham, T. A. (2017). An evolutionary perspective on field cancerization. Nature Reviews Cancer, 18(1), 19-32. doi:10.1038/nrc.2017.102Brem, R., Guven, M., & Karran, P. (2017). Oxidatively-generated damage to DNA and proteins mediated by photosensitized UVA. Free Radical Biology and Medicine, 107, 101-109. doi:10.1016/j.freeradbiomed.2016.10.488Epe, B. (2012). DNA damage spectra induced by photosensitization. Photochem. Photobiol. Sci., 11(1), 98-106. doi:10.1039/c1pp05190cKarran, P., & Brem, R. (2016). Protein oxidation, UVA and human DNA repair. DNA Repair, 44, 178-185. doi:10.1016/j.dnarep.2016.05.024Montoro, J., Rodriguez, M., Diaz, M., & Bertomeu, F. (2003). Photoallergic contact dermatitis due to diclofenac. Contact Dermatitis, 48(2), 115-115. doi:10.1034/j.1600-0536.2003.480212_1.xFernández-Jorge, B., Goday-Buján, J. J., Murga, M., Molina, F. P., Pérez-Varela, L., & Fonseca, E. (2009). Photoallergic contact dermatitis due to diclofenac with cross-reaction to aceclofenac: two case reports. Contact Dermatitis, 61(4), 236-237. doi:10.1111/j.1600-0536.2009.01596.xMonteiro, A. F., Rato, M., & Martins, C. (2016). Drug-induced photosensitivity: Photoallergic and phototoxic reactions. Clinics in Dermatology, 34(5), 571-581. doi:10.1016/j.clindermatol.2016.05.006Akat, P. (2013). Severe photosensitivity reaction induced by topical diclofenac. Indian Journal of Pharmacology, 45(4), 408. doi:10.4103/0253-7613.114999Kowalzick, L., & Ziegler, H. (2006). Photoallergic contact dermatitis from topical diclofenac in SolarazeR gel. Contact Dermatitis, 54(6), 348-349. doi:10.1111/j.0105-1873.2006.0645f.xEncinas, S., Boscá, F., & Miranda, M. A. (1998). Photochemistry of 2,6-Dichlorodiphenylamine and 1-Chlorocarbazole, the Photoactive Chromophores of Diclofenac, Meclofenamic Acid and Their Major Photoproducts. Photochemistry and Photobiology, 68(5), 640. doi:10.1562/0031-8655(1998)0682.3.co;2Encinas, S., Bosca, F., & Miranda, M. A. (1998). Phototoxicity Associated with Diclofenac:  A Photophysical, Photochemical, and Photobiological Study on the Drug and Its Photoproducts. Chemical Research in Toxicology, 11(8), 946-952. doi:10.1021/tx9800708Moore, D. E., Roberts-Thomson, S., Zhen, D., & Duke, C. C. (1990). PHOTOCHEMICAL STUDIES ON THE ANTIINFLAMMATORY DRUG DICLOFENAC. Photochemistry and Photobiology, 52(4), 685-690. doi:10.1111/j.1751-1097.1990.tb08667.xIoele, G., De Luca, M., Tavano, L., & Ragno, G. (2014). The difficulties for a photolabile drug in topical formulations: The case of diclofenac. International Journal of Pharmaceutics, 465(1-2), 284-290. doi:10.1016/j.ijpharm.2014.01.030Ioele, G., Tavano, L., De Luca, M., Ragno, G., Picci, N., & Muzzalupo, R. (2015). Photostability and ex-vivo permeation studies on diclofenac in topical niosomal formulations. International Journal of Pharmaceutics, 494(1), 490-497. doi:10.1016/j.ijpharm.2015.08.053Aparici-Espert, I., Cuquerella, M. C., Paris, C., Lhiaubet-Vallet, V., & Miranda, M. A. (2016). Photocages for protection and controlled release of bioactive compounds. Chemical Communications, 52(99), 14215-14218. doi:10.1039/c6cc08175dKlán, P., Šolomek, T., Bochet, C. G., Blanc, A., Givens, R., Rubina, M., … Wirz, J. (2012). Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy. Chemical Reviews, 113(1), 119-191. doi:10.1021/cr300177kŠolomek, T., Wirz, J., & Klán, P. (2015). Searching for Improved Photoreleasing Abilities of Organic Molecules. Accounts of Chemical Research, 48(12), 3064-3072. doi:10.1021/acs.accounts.5b00400Young, D. D., & Deiters, A. (2007). Photochemical control of biological processes. Org. Biomol. Chem., 5(7), 999-1005. doi:10.1039/b616410mYu, H., Li, J., Wu, D., Qiu, Z., & Zhang, Y. (2010). Chemistry and biological applications of photo-labile organic molecules. Chem. Soc. Rev., 39(2), 464-473. doi:10.1039/b901255aPravst, I., Zupan, M., & Stavber, S. (2006). Solvent-free bromination of 1,3-diketones and β-keto esters with NBS. Green Chem., 8(11), 1001-1005. doi:10.1039/b608446jParis, C., Lhiaubet-Vallet, V., Jiménez, O., Trullas, C., & Miranda, M. Á. (2009). A Blocked Diketo Form of Avobenzone: Photostability, Photosensitizing Properties and Triplet Quenching by a Triazine-derived UVB-filter. Photochemistry and Photobiology, 85(1), 178-184. doi:10.1111/j.1751-1097.2008.00414.

Type I vs Type II photodegradation of pollutants

[EN] Rose Bengal (RB) is a widely used photocatalyst due to its high quantum yield of singlet oxygen (O-1(2)) formation. Hence, when RB has been employed for wastewater remediation, the observed photodegradation has been attributed to reaction between the pollutants and the O-1(2) formed (Type II mechanism). However, RB could also react, in principle, via electron transfer (Type I mechanism). Herein, competition between Type I vs Type II oxidation has been investigated for RB in the photodegradation of emerging pollutants such as diclofenac (DCF) and acetaminophen (ACP). In parallel, the photocatalyst perinaphthenone (PN) has also been evaluated for comparison. The degree of removal achieved for both pollutants in aerated/deaerated aqueous solutions irrespective of the employed photocatalyst does not support the involvement of O-1(2) as the main species responsible for removal of the pollutants. Photophysical experiments showed that the triplet excited states of RB and PN are efficiently quenched by both DCF and ACP. Moreover, O-1(2) emission was also quenched by DCF and ACP. Thus the contribution of Type I versus Type II in the photodegradation has been evaluated from the experimentally determined rate constants. Nevertheless, at the upper limit for the typical concentration of emerging pollutants (10(-5) M) photodegradation proceeds mainly via Type I mechanism.Financial support from Spanish Government (Grants SEV-2016-0683 and CTQ2012-38754-C03-03) and Generalitat Valenciana (Prometeo Program) is gratefully acknowledged. We also thank support from VLC/Campus. R. Martinez-Haya thanks financial support from Spanish Government (Grant SEV-2012-0267).Martínez-Haya, R.; Miranda Alonso, MÁ.; Marín García, ML. (2018). Type I vs Type II photodegradation of pollutants. Catalysis Today. 313:161-166. https://doi.org/10.1016/j.cattod.2017.10.034S16116631