Multinuclear silver(I) XPhos complexes with cyclooctatetraene: photochemical C-C bond cleavage of acetonitrile and cyanide bridged Ag cluster formation

[EN] Cationic mono-, di-, tri-and tetra-nuclear silver complexes with Buchwald-type phosphane (XPhos) and cyclooctatetraene (COT) have been synthesized and characterized. Formation of [(XPhos-Ag) n(COT)][SbF6](n) (n = 1 and 2) complexes was confirmed by single-crystal X-ray crystallography and multinuclear NMR spectroscopy. Variable-temperature NMR spectroscopy in CD2Cl2 solution shows the fluxionality of the COT ring in the mono-Ag(I) XPhos complex. Fluxionality of COT was also confirmed in the case of the di-Ag(I) XPhos complex by solid-state and solution P-31 NMR spectroscopy. The C-C bond cleavage of coordinated acetonitrile [XPhos-Ag(I)-NCCH3] resulting in cyanide bridged Ag cluster formation [(XPhos-Ag)(2)(mu-CN)(n)(mu-Ag)(n-1)] (n = 1, 2, 3 and 4) upon light excitation of [(XPhos-Ag)(n)(COT)] was confirmed by HRESI-MS, UV-Absorption and HR-TEM.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ2015-69153-C2-1-R) and Generalidad Valenciana (Prometeo 2013-014) is gratefully acknowledged. We also thank Dr Vidal-Moya J. A. (ITQ) for assistance and discussions on NMR analysis.Grirrane ., A.; Alvarez-González, E.; Albero-Sancho, J.; García Gómez, H.; Corma Canós, A. (2016). Multinuclear silver(I) XPhos complexes with cyclooctatetraene: photochemical C-C bond cleavage of acetonitrile and cyanide bridged Ag cluster formation. Dalton Transactions. 45(13):5444-5450. https://doi.org/10.1039/c6dt00370bS54445450451

Unexpected solvent isotope effect on the triplet lifetime of methylene blue associated to cucurbit[7]uril

[EN] Methylene blue shows an isotope dependent triplet lifetime that is 50% longer in D2O compared with H2O as a result of electronic-to-vibrational relaxation. The effect is enhanced when the dye is bound to curcubit[7]uril due to a combination of restricted mobility and a unfavorable vibrational coupling.This work was supported by NSERC-Canada. M. G. B thanks the Spanish Ministry of Science and Innovation for a post-doctoral contract. E. A. Acknowledges Becas Chile and the University of Ottawa for postdoctoral fellowships. We also thank Michel Grenier for his help on the time resolved measurements.Alarcón, E.; González Béjar, M.; Montes Navajas, PM.; García Gómez, H.; Lissi, E.; Scaiano, JC. (2012). Unexpected solvent isotope effect on the triplet lifetime of methylene blue associated to cucurbit[7]uril. Photochemical & Photobiological Sciences. 11(2):269-273. doi:10.1039/c1pp05227fS269273112N. J. Turro , V.Ramamurthy and J. C.Scaiano, Modern molecular photochemistry of organic molecules, University Science Books, Sausalito, California, 2010Rekharsky, M. V., Ko, Y. H., Selvapalam, N., Kim, K., & Inoue, Y. (2007). Complexation Thermodynamics of Cucurbit[6]uril with Aliphatic Alcohols, Amines, and Diamines. Supramolecular Chemistry, 19(1-2), 39-46. doi:10.1080/10610270600915292Cohen, M. D., & Schmidt, G. M. J. (1964). 383. Topochemistry. Part I. A survey. Journal of the Chemical Society (Resumed), 1996. doi:10.1039/jr9640001996Cohen, M. D., Hirshberg, Y., & Schmidt, G. M. J. (1964). 389. Topochemistry. Part VII. The photoactivity of anils of salicylaldehydes in rigid solutions. Journal of the Chemical Society (Resumed), 2051. doi:10.1039/jr9640002051Cohen, M. D., Hirshberg, Y., & Schmidt, G. M. J. (1964). 390. Topochemistry. Part VIII. The effect of solvent, temperature, and light on the structure of anils of hydroxynaphthaldehydes. Journal of the Chemical Society (Resumed), 2060. doi:10.1039/jr9640002060Kim, J., Jung, I.-S., Kim, S.-Y., Lee, E., Kang, J.-K., Sakamoto, S., … Kim, K. (2000). New Cucurbituril Homologues:  Syntheses, Isolation, Characterization, and X-ray Crystal Structures of Cucurbit[n]uril (n= 5, 7, and 8). Journal of the American Chemical Society, 122(3), 540-541. doi:10.1021/ja993376pLee, J. W., Samal, S., Selvapalam, N., Kim, H.-J., & Kim, K. (2003). Cucurbituril Homologues and Derivatives:  New Opportunities in Supramolecular Chemistry. Accounts of Chemical Research, 36(8), 621-630. doi:10.1021/ar020254kHennig, A., Ghale, G., & Nau, W. M. (2007). Effects of cucurbit[7]uril on enzymatic activity. Chemical Communications, (16), 1614. doi:10.1039/b618703jKoner, A. L., & Nau, W. M. (2007). Cucurbituril Encapsulation of Fluorescent Dyes. Supramolecular Chemistry, 19(1-2), 55-66. doi:10.1080/10610270600910749Mohanty, J., Pal, H., Ray, A. K., Kumar, S., & Nau, W. M. (2007). Supramolecular Dye Laser with Cucurbit[7]uril in Water. ChemPhysChem, 8(1), 54-56. doi:10.1002/cphc.200600625Shaikh, M., Mohanty, J., Singh, P. K., Nau, W. M., & Pal, H. (2008). Complexation of acridine orange by cucurbit[7]uril and β-cyclodextrin: photophysical effects and pKashifts. Photochem. Photobiol. Sci., 7(4), 408-414. doi:10.1039/b715815gSueishi, Y., Asano, K., Yamaoka, M., & Yamamoto, S. (2008). Characterization of Water-Soluble Cucurbit[7]uril in Alcohol-Water Mixtures by High-Pressure Studies on the Inclusion Complexation with New Methylene Blue. Zeitschrift für Physikalische Chemie, 222(1), 153-161. doi:10.1524/zpch.2008.222.1.153Zhou, Y., Yu, H., Zhang, L., Sun, J., Wu, L., Lu, Q., & Wang, L. (2008). Host properties of cucurbit [7] uril: fluorescence enhancement of acridine orange. Journal of Inclusion Phenomena and Macrocyclic Chemistry, 61(3-4), 259-264. doi:10.1007/s10847-008-9414-8González-Béjar, M., Montes-Navajas, P., García, H., & Scaiano, J. C. (2009). Methylene Blue Encapsulation in Cucurbit[7]uril: Laser Flash Photolysis and Near-IR Luminescence Studies of the Interaction with Oxygen. Langmuir, 25(18), 10490-10494. doi:10.1021/la9011923Montes-Navajas, P., Corma, A., & Garcia, H. (2008). Complexation and Fluorescence of Tricyclic Basic Dyes Encapsulated in Cucurbiturils. ChemPhysChem, 9(5), 713-720. doi:10.1002/cphc.200700735Mohanty, J., & Nau, W. M. (2005). Ultrastable Rhodamine with Cucurbituril. Angewandte Chemie International Edition, 44(24), 3750-3754. doi:10.1002/anie.200500502Montes-Navajas, P., & Garcia, H. (2010). Cucurbituril Complexation Enhances Intersystem Crossing and Triplet Lifetime of 2,4,6-Triphenylpyrylium Ion. The Journal of Physical Chemistry C, 114(5), 2034-2038. doi:10.1021/jp9095166Van Houten, J., & Watts, R. J. (1975). Effect of ligand and solvent deuteration on the excited state properties of the tris(2,2’-bipyridyl)ruthenium(II) ion in aqueous solution. Evidence for electron transfer to solvent. Journal of the American Chemical Society, 97(13), 3843-3844. doi:10.1021/ja00846a062Schmidt, R., & Bodesheim, M. (1994). Time-Resolved Measurement of O2(1.SIGMA.+g) in Solution. Phosphorescence from an Upper Excited State. The Journal of Physical Chemistry, 98(11), 2874-2876. doi:10.1021/j100062a024Hurst, J. R., & Schuster, G. B. (1983). Nonradiative relaxation of singlet oxygen in solution. Journal of the American Chemical Society, 105(18), 5756-5760. doi:10.1021/ja00356a009Schmidt, R., & Brauer, H. D. (1987). Radiationless deactivation of singlet oxygen (1.DELTA.g) by solvent molecules. Journal of the American Chemical Society, 109(23), 6976-6981. doi:10.1021/ja00257a012Rodgers, M. A. J. (1983). TIME RESOLVED STUDIES OF 1.27 μm LUMINESCENCE FROM SINGLET OXYGEN GENERATED IN HOMOGENEOUS and MICROHETEROGENEOUS FLUIDS. Photochemistry and Photobiology, 37(1), 99-103. doi:10.1111/j.1751-1097.1983.tb04440.xRodgers, M. A. J., & Snowden, P. T. (1982). Lifetime of oxygen (O2(1.DELTA.g)) in liquid water as determined by time-resolved infrared luminescence measurements. Journal of the American Chemical Society, 104(20), 5541-5543. doi:10.1021/ja00384a070Ogilby, P. R., & Foote, C. S. (1983). Chemistry of singlet oxygen. 42. Effect of solvent, solvent isotopic substitution, and temperature on the lifetime of singlet molecular oxygen (1.DELTA.g). Journal of the American Chemical Society, 105(11), 3423-3430. doi:10.1021/ja00349a007Gardner, P. J., & Kasha, M. (1969). Electronic Consequences of Vibrational Deficiency in Polyatomic Molecules. The Journal of Chemical Physics, 50(4), 1543-1552. doi:10.1063/1.1671240Schweitzer, C., & Schmidt, R. (2003). Physical Mechanisms of Generation and Deactivation of Singlet Oxygen. Chemical Reviews, 103(5), 1685-1758. doi:10.1021/cr010371dS. L. Murov , I.Carmichael and G. L.Hug, Handbook of photochemistry, Mercel Decker Inc, New York, 1993Beeby, A., Parker, A. W., Simpson, M. S. C., & Phillips, D. (1992). The effect of solvent deuteration on the photophysics of sulphonated aluminium phthalocyanine. Journal of Photochemistry and Photobiology B: Biology, 16(1), 73-81. doi:10.1016/1011-1344(92)85154-mNau, W. M., & Mohanty, J. (2005). Taming fluorescent dyes with cucurbituril. International Journal of Photoenergy, 7(3), 133-141. doi:10.1155/s1110662x05000206Alarcón, E., Edwards, A. M., Aspee, A., Moran, F. E., Borsarelli, C. D., Lissi, E. A., … Scaiano, J. C. (2010). Photophysics and photochemistry of dyes bound to human serum albumin are determined by the dyelocalization. Photochem. Photobiol. Sci., 9(1), 93-102. doi:10.1039/b9pp00091gDavila, J., & Harriman, A. (1990). PHOTOREACTIONS OF MACROCYCLIC DYES BOUND TO HUMAN SERUM ALBUMIN. Photochemistry and Photobiology, 51(1), 9-19. doi:10.1111/j.1751-1097.1990.tb01678.xEngst, P., Kubát, P., & Jirsa, M. (1994). The influence of D2O on the photophysical properties of meso-tetra (4-sulphonatophenyl) porphine, Photosan III and tetrasulphonated aluminium and zinc phthalocyanines. Journal of Photochemistry and Photobiology A: Chemistry, 78(3), 215-219. doi:10.1016/1010-6030(93)03730-5Jensen, R. L., Arnbjerg, J., & Ogilby, P. R. (2010). Temperature Effects on the Solvent-Dependent Deactivation of Singlet Oxygen. Journal of the American Chemical Society, 132(23), 8098-8105. doi:10.1021/ja101753nLipert, R. J., & Colson, S. D. (1989). Deuterium isotope effects on S1 radiationless decay in phenol and on intermolecular vibrations in the phenol-water complex. The Journal of Physical Chemistry, 93(1), 135-139. doi:10.1021/j100338a030Tanielian, C., & Wolff, C. (1995). Determination of the Parameters Controlling Singlet Oxygen Production via Oxygen and Heavy-Atom Enhancement of Triplet Yields. The Journal of Physical Chemistry, 99(24), 9831-9837. doi:10.1021/j100024a02

Weather observations of remote polar areas using an AWS onboard a unique zero-emissions polar vehicle

The Antarctic Plateau is one of the land areas with the largest gaps in surface weather observations on Earth, gaps that are usually filled with simulations provided by climate models. However, these simulated values must be ground-validated, which is particularly difficult and costly in remote polar regions. We designed and developed a Mobile Automatic Weather Station (M-AWS) which, on board a zero-emissions polar vehicle, recorded a large set of ground measurements that could be used to evaluate numerical weather simulations in an inexpensive way during the Year of Polar Prediction Southern Hemisphere Special Observing Period (YOPP). The M-AWS registered several weather variables over a transect of 2538 km in the East Antarctic Plateau. These meteorological data were also used by other scientific projects that were part of the expedition and for improving weather forecasting during the mission. The innovative design of the M-AWS overcame the main challenges imposed by the harsh conditions of a voyage in one of the world’s most extreme regions.This is a contribution to the Year of Polar Prediction (YOPP), a flagship activity of the Polar Prediction Project (PPP), initiated by the World Weather Research Programme (WWRP) of the World Meteorological Organization (WMO). MICROAIRPOLAR is a project founded by AEI (Spain) and ERDF (EU), CTM2016-79741-R grant. AEMET Antarctic program is supported by the MSIU (Spain). Sergi Gonzalez’s research activities are partly supported by ANTALP Research Group funded by Generalitat de Catalunya (2017 SGR 1102)

Identification and Functional Analysis of a Novel CTNNB1 Mutation in Pediatric Medulloblastoma

Medulloblastoma is the primary malignant tumor of the Central Nervous System (CNS) most common in pediatrics. We present here, the histological, molecular, and functional analysis of a cohort of 88 pediatric medulloblastoma tumor samples. The WNT-activated subgroup comprised 10% of our cohort, and all WNT-activated patients had exon 3 CTNNB1 mutations and were immunostained for nuclear β-catenin. One novel heterozygous CTNNB1 mutation was found, which resulted in the deletion of β-catenin Ser37 residue (ΔS37). The ΔS37 β-catenin variant ectopically expressed in U2OS human osteosarcoma cells displayed higher protein expression levels than wild-type β-catenin, and functional analysis disclosed gain-of-function properties in terms of elevated TCF/LEF transcriptional activity in cells. Our results suggest that the stabilization and nuclear accumulation of ΔS37 β-catenin contributed to early medulloblastoma tumorigenesis.This work was funded by Asociación Pablo Ugarte APU (BC/A/14/015), Pequerropa (BC/A/15/010), and the childhood cancer support Platform from EITB Media, SAU (BIO13/CI/016/BC). R.P. was funded by Ministerio de Economía y Competitividad (Spain and Fondo Europeo de Desarrollo Regional, grant number SAF2016-79847-R). C.E.N.-X. was funded by Instituto de Salud Carlos III (Spain and the European Social Fund+, grant number: CP20/00008). P.A.-P. was supported by a Basque Government fellowship (PRE_2020_2_0116)

Hip fracture rates and bisphosphonate consumption in Spain. An ecologic study

Producción CientíficaIntroduction Bisphosphonates are used worldwide to treat osteoporosis and, thus, to prevent fractures. Though they have been proven in clinical trials to avoid some fractures, their effectiveness in reducing hip fractures is unclear. The aim of the present study was to explore the relationship between bisphosphonate use and hip fracture trends in Spain. Methods For this purpose, an ecologic study spanning 2002 to 2008 was conducted in Spain. Consumption data were obtained from the Spanish Ministry of Health and Social Policy. The number of hip fractures was obtained from hospital discharges; annual hip fracture rates were determined and standardized using the Spanish 2002 population census. A linear regression was performed between fracture rate and use of bisphosphonates; R2 and Pearson correlation coefficient were calculated. Results From 2002 to 2008, dispensed prescriptions of bisphosphonates in Spain increased from 3.28 to 17.66 DDD/1,000 inhabitants per day. In the same period, the crude hip fracture rate increased from 2.85 to 3.02 cases per 1,000 inhabitants older than 50 years; however, when age standardized rates were estimated, the rate declined from 2.85 to 2.79. Analyzed by sex, the standardized rate for men slightly increased from 1.45 to 1.48, while for women the rate significantly dropped from 4.00 to 3.91.Conclusion A small effect of bisphosphonates on hip fracture rates can not be ruled out; however, other factors might partially explain this decline. Assuming this medication was the only cause for hip fracture rate reduction, the elevated medication cost to avoid a single hip fracture makes it necessary to explore less expensive intervention

Effect of Linker Distribution in the Photocatalytic Activity of Multivariate Mesoporous Crystals

The use of Metal-Organic Frameworks as crystalline matrices for the synthesis of multiple component or multivariate solids by the combination of different linkers into a single material has emerged as a versatile route to tailor the properties of single-component phases or even access new functions. This approach is particularly relevant for Zr6-MOFs due to the synthetic flexibility of this inorganic node. However, the majority of materials are isolated as polycrystalline solids, which are not ideal to decipher the spatial arrangement of parent and exchanged linkers for the formation of homogeneous structures or heterogeneous domains across the solid. Here we use high-throughput methodologies to optimize the synthesis of single crystals of UiO-68 and UiO-68-TZDC, a photoactive analogue based on a tetrazine dicarboxylic derivative. The analysis of the single linker phases reveals the necessity of combining both linkers to produce multivariate frameworks that combine efficient light sensitization, chemical stability, and porosity, all relevant to photocatalysis. We use solvent-assisted linker exchange reactions to produce a family of UiO-68-TZDC% binary frameworks, which respect the integrity and morphology of the original crystals. Our results suggest that the concentration of TZDC in solution and the reaction time control the distribution of this linker in the sibling crystals for a uniform mixture or the formation of core-shell domains. We also demonstrate how the possibility of generating an asymmetric distribution of both linkers has a negligible effect on the electronic structure and optical band gap of the solids but controls their performance for drastic changes in the photocatalytic activity toward proton or methyl viologen reduction.This work was supported by the EU (ERC Stg Chem-fs-MOF 714122) and Spanish government (CTQ2017-83486-P, RTI2018-098568-A-I00, RYC-2016-1981, CEX2019-000919-M, PID2019-106383GB-C44/AEI/10.13039/501100011033 and RTI2018-098568-A-I00). B.L.-B. thanks the Spanish government for a FPU (FPU16/04162). S.T. thanks the Spanish government for a Ramón y Cajal Fellowship (RYC-2016-60719817). N.M.P. thanks the European Union for a Marie Skłodowska-Curie Global Fellowship (H2020-MSCA-IF-2016-GF-749359-EnanSET). J.G.P. thanks to the SIDIX at Servicios Generales de Apoyo a la Investigación (SEGAI) at La Laguna University. We also thank BSC-RES for computational resources (QS-2020-2-0024) and the University of Valencia for research facilities (Tirant and NANBIOSIS).Peer reviewe

Introducing high-throughput sequencing into mainstream genetic diagnosis practice in inherited platelet disorders

Inherited platelet disorders are a heterogeneous group of rare diseases, caused by inherited defects in platelet production and/or function. Their genetic diagnosis would benefit clinical care, prognosis and preventative treatments. Until recently, this diagnosis has usually been performed via Sanger sequencing of a limited number of candidate genes. High-throughput sequencing is revolutionizing the genetic diagnosis of diseases, including bleeding disorders. We have designed a novel high-throughput sequencing platform to investigate the unknown molecular pathology in a cohort of 82 patients with inherited platelet disorders. Thirty-four (41.5%) patients presented with a phenotype strongly indicative of a particular type of platelet disorder. The other patients had clinical bleeding indicative of platelet dysfunction, but with no identifiable features. The high-throughput sequencing test enabled a molecular diagnosis in 70% of these patients. This sensitivity increased to 90% among patients suspected of having a defined platelet disorder. We found 57 different candidate variants in 28 genes, of which 70% had not previously been described. Following consensus guidelines, we qualified 68.4% and 26.3% of the candidate variants as being pathogenic and likely pathogenic, respectively. In addition to establishing definitive diagnoses of well-known inherited platelet disorders, high-throughput sequencing also identified rarer disorders such as sitosterolemia, filamin and actinin deficiencies, and G protein-coupled receptor defects. This included disease-causing variants in DIAPH1 (n=2) and RASGRP2 (n=3). Our study reinforces the feasibility of introducing high-throughput sequencing technology into the mainstream laboratory for the genetic diagnostic practice in inherited platelet disorders.This study was supported by research grants from the Gerencia Regional de Salud (GRS 1370/A/16), ISCIII & Feder (PI14/01956), CIBERER CB15/00055, Fundación Séneca (19873/GERM/15) and Sociedad Española de Trombosis y Hemostasia (SETH). SPW holds a British Heart Foundation chair.Peer Reviewe

Handbook of Active Ageing and Quality of Life: From Concepts to Applications

La edición de este libro estuvo a cargo de Fermina Rojo-Pérez y Gloria Fernández-Mayoralas.El documento adjunto contiene la cubierta, portada e índice del libro.This handbook presents an overview of studies on the relationship of active ageing and quality of life. It addresses the new challenges of ageing from the paradigm of positive ageing (active, healthy and successful) for a better quality of life. It provides theoretical perspectives and empirical studies, including scientific knowledge as well as practical experiences about the good ageing and the quality of later life around the world, in order to respond to the challenges of an aged population. The handbook is structured in 4 sections covering theoretical and conceptual perspectives, social policy issues and research agenda, methods, measurement instrument-scales and evaluations, and lastly application studies including domains and geographical contexts.Peer reviewe

Photoresponsive Covalently-Functionalized Short Single Wall Carbon Nanotube

[EN] This chapter reviews some of the strategies that have been used to synthesize single walled carbon nanotubes having covalently bonded photoresponsive chromophores. In the first part, the synthetic route is discussed as well as the different characterization techniques and how the information gained by each of them has to be combined to have a more detailed information on the material. Emphasis is made on commenting the advantages of using short-soluble carbon nanotubes that can be more firmly characterized (particularly the occurrence of the covalent linkage) and how the covalent attachment reinforces considerably the interaction between the nanotube walls and the chromophore. The photophysics of the entities derived from the covalent functionalization of the carbon nanotubes by photoactive units is discussed in the second part. Examples are provided to show that single wall carbon nanotubes behave as semiconductors and behave accepting or donating electrons. Thus, in contrast to fullerenes that are always strong electron acceptors, the behavior of single wall carbon nanotubes in the photoinduced charge separation event depends on the nature of the partner attached covalently.Financial support by the Spanish ministry of Science (CTQ2009-11586 and CTQ2007-67805-AR07) is gratefully acknowledged. RM also thanks Spanish Ministry of Education for a postgraduate scholarship.Martín González, R.; Alvaro Rodríguez, MM.; García Gómez, H. (2011). Photoresponsive Covalently-Functionalized Short Single Wall Carbon Nanotube. Current Organic Chemistry. 15(8):1106-1120. https://doi.org/10.2174/138527211795203040S1106112015

Sunlight-assisted fenton reaction catalyzed by gold supported on diamond nanoparticles as pretreatment for biological degradation of aqueous phenol solutions

Gold nanoparticles supported on Fenton-treated diamond nanoparticles (Au/DNPs) have been reported as one of the most efficient solid catalysts effecting the Fenton reaction, achieving a turnover number (TON) as high as 321 000. However, at room temperature the main limitation for the catalytic activity of Au/DNPs is the pH of the solution, which should be less than 5. In this paper, we report that exposure of Au/DNPs to sunlight enhances the catalytic activity of Au/DNPs up to the point that it can promote the Fenton reaction at room temperature even at slightly basic pH values. Also, in addition to performing a deep Fenton treatment and considering that the excess of H 2O 2 used in the process should be minimized, we have achieved in our study, using a mild Fenton reaction promoted by Au/DNPs under sunlight irradiation, an optimum in the biodegradability, a minimum in the ecotoxicity, and no toxicity for the Vibrio fischeri test. The results have shown that, by using an H 2O 2-to-phenol molar ratio of 5.5 or higher, it is possible to achieve a high biodegradability as well as a complete lack of ecotoxicity and of Vibrio fischeri toxicity. The stability of Au/DNPs was confirmed by analyzing the gold leached to the solution and by performing four consecutive reuses of the catalyst with initial pH values ranging from 4 to 8. It was observed that, after finishing the reaction and exhaustive washings with basic aqueous solutions, the initial reaction rate of the used catalyst is recovered to the value exhibited by the fresh solid. Overall, our study shows that the synergism between catalysis and photocatalysis can overcome the limitations found for dark catalytic reactions and that the reaction parameters can be optimized to effect mild Fenton reactions aimed at increasing biodegradability in biorecalcitrant waste waters.Financial support by the Spanish DGI (CTQ-2009-11587) is gratefully acknowledged. SN thanks the Technical University of Valencia for a postgraduate research contract (Cantera Program).Navalón Oltra, S.; Martín González, R.; Álvaro Rodríguez, MM.; García Gómez, H. (2011). Sunlight-assisted fenton reaction catalyzed by gold supported on diamond nanoparticles as pretreatment for biological degradation of aqueous phenol solutions. ChemSusChem. 4(5):650-657. doi:10.1002/cssc.201000453S6506574