C ion-implanted TiO2 thin film for photocatalytic applications

Third-generation TiO2 photocatalysts were prepared by implantation of C+ ions into 110 nm thick TiO2 films. An accurate structural investigation was performed by Rutherford backscattering spectrometry, secondary ion mass spectrometry, X-ray diffraction, Raman-luminescence spectroscopy, and UV/VIS optical characterization. The C doping locally modified the TiO2 pure films, lowering the band-gap energy from 3.3 eV to a value of 1.8 eV, making the material sensitive to visible light. The synthesized materials are photocatalytically active in the degradation of organic compounds in water under both UV and visible light irradiation, without the help of any additional thermal treatment. These results increase the understanding of the C-doped titanium dioxide, helpful for future environmental applications. (C) 2015 AIP Publishing LLC

Current status of laboratory and imaging diagnosis of neonatal necrotizing enterocolitis

Necrotizing enterocolitis continues to be a devastating disease process for very low birth weight infants in Neonatal Intensive Care Units. The aetiology and pathogenesis of necrotizing enterocolitis are not definitively understood. It is known that necrotizing enterocolitis is secondary to a complex interaction of multiple factors that results in mucosal damage, which leads to intestinal ischemia and necrosis. Advances in neonatal care, including resuscitation and ventilation support technology, have seen increased survival rates among premature neonates and a concomitant detection in the incidence of this intestinal disease.Diagnosis can be difficult, and identifying infants at the onset of disease remains a challenge. Early diagnosis, which relies on imaging findings, and initiation of prompt therapy are essential to limit morbidity and mortality. Moreover, early management is critical and life-saving.This review summarizes what is known on the laboratory and instrumental diagnostic strategies needed to improve neonatal outcomes and, possibily, to prevent the onset of an overt necrotizing enterocolitis

On carbon and oxygen isotope ratios in starburst galaxies: New data from NGC253 and Mrk231 and their implications

Using the IRAM 30-m telescope, CN and CO isotopologues have been measured toward the central regions of the nearby starburst galaxy NGC253 and the prototypical ultraluminous infrared galaxy Mrk231. In NGC253, the 12C/13C ratio is 40+-10. Assuming that the ratio also holds for the CO emitting gas, this yields 16O/18O = 145+-36 and 16O/17O = 1290+-365 and a 32S/34S ratio close to that measured for the local interstellar medium (20-25). No indication for vibrationally excited CN is found. Peak line intensity ratios between NGC253 and Mrk231 are ~100 for 12C16O and 12C18O J=1-0, while the ratio for 13C16O J=1-0 is ~250. This and similar 13CO and C18O line intensities in the J=1-0 and 2-1 transitions of Mrk231 suggest 12C/13C ~ 100 and 16O/18O ~ 100, in agreement with values obtained for the less evolved ultraluminous merger Arp220. Also accounting for other extragalactic data, 12C/13C ratios appear to vary over a full order of magnitude, from >100 in ultraluminous high redshift galaxies to ~100 in more local such galaxies to ~40 in weaker starbursts not undergoing a large scale merger to 25 in the Central Molecular Zone of the Milky Way. With 12C being predominantly synthesized in massive stars, while 13C is mostly ejected by longer lived lower mass stars at later times, this is qualitatively consistent with our results of decreasing carbon isotope ratios with time and rising metallicity. It is emphasized, however, that both infall of poorly processed material, initiating a nuclear starburst, as well as the ejecta from newly formed massive stars (in particular in case of a top-heavy stellar initial mass function) can raise the carbon isotope ratio for a limited amount of time.Comment: Accepted by Astronomy & Astrophysics, 6 figures, 4 table

Copper nanoparticle heterogeneous catalytic 'click' cycloaddition confirmed by single-molecule spectroscopy

Colloidal or heterogeneous nanocatalysts can improve the range and diversity of Cu(I)catalysed click reactions and facilitate catalyst separation and reuse. Catalysis by metal nanoparticles raises the question as to whether heterogeneous catalysts may cause homogeneous catalysis through metal ion leaching, since the catalytic process could be mediated by the particle, or by metal ions released from it. The question is critical as unwanted homogeneous processes could offset the benefits of heterogeneous catalysis. Here, we combine standard bench scale techniques with single-molecule spectroscopy to monitor single catalytic events in real time and demonstrate that click catalysis occurs directly at the surface of copper nanoparticles; this general approach could be implemented in other systems. We use 'from the mole to the molecule' to describe this emerging idea in which mole scale reactions can be optimized through an intimate understanding of the catalytic process at the single-molecule-single catalytic nanoparticle level.The Natural Sciences and Engineering Research Council of Canada supported this work through its Discovery and CREATE programs, while the Canadian Foundation for Innovation enabled the purchase of the instrumentation used in this work. M. L. M. thanks the Spanish Ministerio de Educacion, Cultura y Deporte (Programa Salvador de Madariaga) for its financial support.Decan, MR.; Impellizzeri, S.; Marín García, ML.; Scaiano, J. (2014). Copper nanoparticle heterogeneous catalytic 'click' cycloaddition confirmed by single-molecule spectroscopy. Nature Communications. 5:4612-4615. doi:10.1038/ncomms5612S461246155Rostovtsev, V. V., Green, L. G., Fokin, V. V. & Sharpless, K. B. A stepwise Huisgen cycloaddition process: copper(I)-catalyzed regioselective ‘ligation’ of azides and terminal alkynes. Angew. Chem. Int. Ed. 41, 2596–2599 (2002).Tornøe, C. W., Christensen, C. & Meldal, M. Peptidotriazoles on solid phase: [1,2,3]-triazoles by regiospecific copper(I)-catalyzed 1,3-dipolar cycloadditions of terminal alkynes to azides. J. Org. Chem. 67, 3057–3064 (2002).Hein, J. & Fokin, V. Copper-catalyzed azide–alkyne cycloaddition (CuAAC) and beyond: new reactivity of copper(I) acetylides. Chem. Soc. Rev. 39, 1302–1315 (2010).Kolb, H. C., Finn, M. G. & Sharpless, K. B. Click chemistry: diverse chemical function from a few good reactions. Angew. Chem. Int. Ed. 40, 2004 (2001).Meldal, M. & Tornoe, C. W. Cu-catalyzed azide-alkyne cycloaddition. Chem. Rev. 108, 2952–3015 (2008).Moses, J. E. & Moorhouse, A. D. The growing applications of click chemistry. Chem. Soc. Rev. 36, 1249–1262 (2007).Thirumurugan, P., Matosiuk, D. & Jozwiak, K. Click chemistry for drug development and diverse chemical—biology applications. Chem. Rev. 113, 4905–4979 (2013).Cintas, P., Barge, A., Tagliapietra, S., Boffa, L. & Cravotto, G. Alkyne–azide click reaction catalyzed by metallic copper under ultrasound. Nat. Protoc. 5, 607–616 (2010).Hong, V., Presolski, S., Ma, C. & Finn, M. Analysis and optimization of copper-catalyzed azide-alkyne cycloaddition for bioconjugation. Angew. Chem. Int. Ed. 48, 9879–9883 (2009).Kappe, C. & Van Der Eycken, E. Click chemistry under non-classical reaction conditions. Chem. Soc. Rev. 39, 1280–1290 (2010).Pachón, L., Van Maarseveen, J. & Rothenberg, G. Click chemistry: copper clusters catalyse the cycloaddition of azides with terminal alkynes. Adv. Synth. Catal. 347, 811–815 (2005).Adzima, B. et al. Spatial and temporal control of the alkyne–azide cycloaddition by photoinitiated Cu(II) reduction. Nat. Chem. 3, 258–261 (2011).Jin, T., Yan, M. & Yamamoto, Y. Click chemistry of alkyne-azide cycloaddition using nanostructured copper catalysts. ChemCatChem 4, 1217–1229 (2012).Woo, H. et al. Azide-alkyne Huisgen [3+2] cycloaddition using CuO nanoparticles. Molecules 17, 13235–13252 (2012).Rance, G., Solomonsz, W. & Khlobystov, A. Click chemistry in carbon nanoreactors. Chem. Commun. 49, 1067–1069 (2013).Alonso, F., Moglie, Y., Radivoy, G. & Yus, M. Unsupported copper nanoparticles in the 1,3-dipolar cycloaddition of terminal alkynes and azides. Eur. J. Org. Chem. 10, 1875–1884 (2010).Alonso, F., Moglie, Y., Radivoy, G. & Yus, M. Multicomponent synthesis of 1,2,3-triazoles in water catalyzed by copper nanoparticles on activated carbon. Adv. Synth. Catal. 352, 3208–3214 (2010).Raut, D. et al. Copper nanoparticles in ionic liquids: Recyclable and efficient catalytic system for 1,3-dipolar cycloaddition reaction. Catal. Commun. 10, 1240–1243 (2009).Kumar, B. S. P. A., Reddy, K. H. V., Madhav, B., Ramesh, K. & Nageswar, Y. V. D. Magnetically separable CuFe2O4 nano particles catalyzed multicomponent synthesis of 1,4-disubstituted 1,2,3-triazoles in tap water using ‘click chemistry’. Tetrahedron Lett. 53, 4595–4599 (2012).Hudson, R., Li, C. & Moores, A. Magnetic copper–iron nanoparticles as simple heterogeneous catalysts for the azide–alkyne click reaction in water. Green Chem. 14, 622–624 (2012).Sarkar, A., Mukherjee, T. & Kapoor, S. PVP-stabilized copper nanoparticles: a reusable catalyst for ‘click’ reaction between terminal alkynes and azides in nonaqueous solvents. J. Phys. Chem. C 112, 3334–3340 (2008).Pacioni, N. L., Filippenko, V., Presseau, N. & Scaiano, J. C. Oxidation of copper nanoparticles in water: mechanistic insights revealed by oxygen uptake and spectroscopic methods. Dalton Trans. 42, 5832–5838 (2013).Davies, I. W., Matty, L., Hughes, D. L. & Reider, P. J. Are heterogeneous catalysts precursors to homogeneous catalysts? J. Am.Chem. Soc. 123, 10139–10140 (2001).Witham, C. A. et al. Converting homogeneous to heterogeneous in electrophilic catalysis using monodisperse metal nanoparticles. Nat. Chem. 2, 36–41 (2010).Schmidt, A. F. & Kurokhtina, A. A. Distinguishing between the homogeneous and heterogeneous mechanisms of catalysis in the Mizoroki-Heck and Suzuki-Miyaura reactions: problems and prospects. Kinet. Catal. 53, 714–730 (2012).Nishina, Y., Miyata, J., Kawai, R. & Gotoh, K. Recyclable Pd-graphene catalyst: mechanistic insights into heterogeneous and homogeneous catalysis. RSC Advances 2, 9380–9382 (2012).Esfandiari, N. M. & Blum, S. A. Homogeneous vs heterogeneous polymerization catalysis revealed by single-particle fluorescence microscopy. J. Am.Chem. Soc. 133, 18145–18147 (2011).Hensle, E. M. & Blum, S. A. Phase separation polymerization of dicyclopentadiene characterized by in operando fluorescence microscopy. J. Am.Chem. Soc. 135, 12324–12328 (2013).De Cremer, G. et al. High-resolution single-turnover mapping reveals intraparticle diffusion limitation in Ti-MCM-41-catalyzed epoxidation. Angew. Chem. Int. Ed. 49, 908–911 (2010).Roeffaers, M. B. J. et al. Super-resolution reactivity mapping of nanostructured catalyst particles. Angew. Chem. Int. Ed. 48, 9285–9289 (2009).Roeffaers, M. B. J. et al. Spatially resolved observation of crystal-face-dependent catalysis by single turnover counting. Nature 439, 572–575 (2006).Xu, W., Kong, J. S., Yeh, Y.-T.E. & Chen, P. Single-molecule nanocatalysis reveals heterogeneous reaction pathways and catalytic dynamics. Nat. Mater. 7, 992–996 (2008).Zhou, X., Xu, W., Liu, G., Panda, D. & Chen, P. Size-dependent catalytic activity and dynamics of gold nanoparticles at the single-molecule level. J. Am.Chem. Soc. 132, 138–146 (2010).Zhou, X. et al. Quantitative super-resolution imaging uncovers reactivity patterns on single nanocatalysts. Nat. Nanotechnol. 7, 237–241 (2012).Chen, P. et al. Single-molecule fluorescence imaging of nanocatalytic processes. Chem. Soc. Rev. 39, 4560–4570 (2010).Chen, P. et al. Spatiotemporal catalytic dynamics within single nanocatalysts revealed by single-molecule microscopy. Chem. Soc. Rev. 43, 1107–1117 (2014).Buurmans, I. L. C. & Weckhuysen, B. M. Heterogeneities of individual catalyst particles in space and time as monitored by spectroscopy. Nat. Chem. 4, 873–886 (2012).Cordes, T. & Blum, S. A. Opportunities and challenges in single-molecule and single-particle fluorescence microscopy for mechanistic studies of chemical reactions. Nat. Chem. 5, 993–999 (2013).Zhou, X., Choudhary, E., Andoy, N. M., Zou, N. & Chen, P. Scalable parallel screening of catalyst activity at the single-particle level and subdiffraction resolution. ACS Catal. 3, 1448–1453 (2013).Esfandiari, N. M. et al. Single-molecule imaging of platinum ligand exchange reaction reveals reactivity distribution. J. Am. Chem. Soc. 132, 15167–15169 (2010).Wee, T., Schmidt, L. C. & Scaiano, J. C. Photooxidation of 9-anthraldehyde catalyzed by gold nanoparticles: solution and single nanoparticle studies using fluorescence lifetime imaging. J. Phys. Chem. C 116, 24373–24379 (2012).Fiolka, R., Belyaev, Y., Ewers, H. & Stemmer, A. Even illumination in total internal reflection fluorescence microscopy using laser light. Microsc. Res. Tech. 71, 45–50 (2007).Canham, S. M. et al. Toward the single-molecule investigation of organometallic reaction mechanisms: single-molecule imaging of fluorophore-tagged palladium(II) complexes. Organometallics 27, 2172–2175 (2008).Jares-Erijman, E. & Jovin, T. FRET imaging. Nat. Biotechnol. 21, 1387–1395 (2003).Roy, R., Hohng, S. & Ha, T. A practical guide to single-molecule FRET. Nat. Methods 5, 507–516 (2008).Kasper, L. et al. Probing the free-energy surface for protein folding with single-molecule spectroscopy. Nature 419, 743–747 (2002).Chung, H., Louis, J. & Eaton, W. Distinguishing between protein dynamics and dye photophysics in single-molecule FRET experiments. Biophys. J. 98, 696–706 (2010).Hohlbein, J., Craggs, T. & Cordes, T. Alternating-laser excitation: single-molecule FRET and beyond. Chem. Soc. Rev. 43, 1156–1171 (2014).Greenleaf, W. J., Woodside, M. T. & Block, S. M. High-resolution, single-molecule measurements of biomolecular motion. Annu. Rev. Biophys. Biomol. Struct. 36, 171–190 (2007).Di Fiori, N. & Meller, A. The effect of dye-dye interactions on the spatial resolution of single-molecule FRET measurements in nucleic acids. Biophys. J. 98, 2265–2272.Ahlquist, M. r. & Fokin, V. Enhanced reactivity of dinuclear copper(I) acetylides in dipolar cycloadditions. Organometallics 26, 4389–4391 (2007).Straub, B. μ-Acetylide and μ-alkenylidene ligands in ‘click’ triazole syntheses. Chem. Commun. 37, 3868–3870 (2007)

Use of CR100 scale for session-RPE in soccer and interchangeability with CR10

©2016 Human Kinetics,Inc. Purpose: To examine the construct validity of the session rating perceived exertion (s-RPE) assessed with the Borg CR100® scale to measure training loads in elite soccer and to examine if the CR100® is interchangeable and can provide more accurate ratings compared to the CR10® scale. Methods: Two studies were conducted. The validity of the CR100® was determined in 19-elite soccer players (age 28 ± 6 y, height 180 ± 7 cm, body mass 77 ± 6 kg) during training sessions through correlations with Edwards heart rate method (study one). The interchangeability with CR10® was assessed in 78 soccer players (age 19.3 ± 4.1 y, height 178 ± 5.9 cm, body mass 71.4 ± 6.1 kg) through Bland?Altman method and correlations between change scores in different sessions. To examine whether the CR100® is more fine graded than the CR10®, the proportion of responses corresponding to the verbal expressions were calculated (study two). Results: Individual correlations between Edwards' and s-RPE were large to very large (0.52 to 0.85). The mean difference between the two scales was -0.3 ± 0.33 AU (90% CI -0.41 to -0.29 AU) with 95% limits of agreements 0.31 to -0.96 AU. Correlations between scales and between changes scores were nearly perfect (0.95 and 0.91 to 0.98). Ratings corresponding to the verbal anchors were 49% in CR10® and 26% in CR100®. Conclusions: The CR100® is valid for assessing the training load in elite soccer players. It can be used interchangeably with the CR10® and may provide more precise measures of exercise intensity

ALLSMOG: an APEX Low-redshift Legacy Survey for MOlecular Gas. I - molecular gas scaling relations, and the effect of the CO/H2 conversion factor

We present ALLSMOG, the APEX Low-redshift Legacy Survey for MOlecular Gas. ALLSMOG is a survey designed to observe the CO(2-1) emission line with the APEX telescope, in a sample of local galaxies (0.01 < z < 0.03), with stellar masses in the range 8.5 < log(M*/Msun) < 10. This paper is a data release and initial analysis of the first two semesters of observations, consisting of 42 galaxies observed in CO(2-1). By combining these new CO(2-1) emission line data with archival HI data and SDSS optical spectroscopy, we compile a sample of low-mass galaxies with well defined molecular gas masses, atomic gas masses, and gas-phase metallicities. We explore scaling relations of gas fraction and gas consumption timescale, and test the extent to which our findings are dependent on a varying CO/H2 conversion factor. We find an increase in the H2/HI mass ratio with stellar mass which closely matches semi-analytic predictions. We find a mean molecular gas fraction for ALLSMOG galaxies of MH2/M* = (0.09 - 0.13), which decreases with stellar mass. We measure a mean molecular gas consumption timescale for ALLSMOG galaxies of 0.4 - 0.7 Gyr. We also confirm the non-universality of the molecular gas consumption timescale, which varies (with stellar mass) from ~100 Myr to ~2 Gyr. Importantly, we find that the trends in the H2/HI mass ratio, gas fraction, and the non-universal molecular gas consumption timescale are all robust to a range of recent metallicity-dependent CO/H2 conversion factors.Comment: 25 pages, 15 figures. Accepted for publication in MNRA

Protective Effect of Hydroxytyrosol Against Oxidative Stress Induced by the Ochratoxin in Kidney Cells: in vitro and in vivo Study

Ochratoxin-A (OTA) is a mycotoxin that is a common contaminant of food products for both humans and animals. This mycotoxin has several toxic effects. In particular, ochratoxin has significant nephrotoxic potential. In fact, OTA has been described as being responsible for naturally occurring animal and human kidney disorders. The toxicity of this mycotoxin involves the induction of the oxidative stress pathways. Therefore, in the present study, we wanted to evaluate the potential protective effects of hydroxytyrosol (HT), a phenolic constituent with potent antioxidant activity, of extra virgin olive oil in three different renal cell lines, the Madin-Darby canine kidney cell line (MDCK), a pig kidney cell line (LLC-PK1), and a rabbit kidney cell line (RK 13), and in rats. Our results clearly showed that renal cells respond to OTA exposure by reducing cell proliferation and the induction of oxidative stress. Pre-incubation of the cells with HT prevented the cellular cytotoxicity and increased reactive oxygen species (ROS) levels induced by OTA. In addition, the antioxidative activity of HT was studied by measuring malondialdehyde (MDA) and lactate dehydrogenase (LDH) levels and nitrosative stress. Finally, we investigated the capability of HT (20 mg/kg, intraperitoneally) to act in vivo. In rats, HT reduced oxidative stress and collagen accumulation in the kidney and counteracted the augmentations in AST, ALT, and creatinine levels following OTA induction (250 μg/kg for 90 days orally). In conclusion, our findings demonstrate that HT is able to protect three renal cell lines from the damage induced by OTA and protect the kidneys of rats. Therefore, the use of this compound could be an important strategy for the treatment and prevention of this type of kidney dysfunction

Adelmidrol, in combination with hyaluronic acid, displays increased anti-inflammatory and analgesic effects against monosodium iodoacetate-induced osteoarthritis in rats

Background Osteoarthritis (OA) is a degenerative joint disease produced by a cascade of events that can ultimately lead to joint damage. The aim of this study was to evaluate the effect of adelmidrol, a synthetic palmitoylethanolamide analogue, combined with hyaluronic acid on pain severity and modulation of the inflammatory response in a rat model of monosodium iodoacetate (MIA)-induced osteoarthritis. Methods OA was induced by intra-articular injection of MIA in the knee joint. On day 21 post-MIA administration, the knee joint was analyzed. Rats subjected to OA were treated by intra-articular injection of adelmidrol in combination with sodium hyaluronate at different doses and time points after MIA induction. Limb nociception was assessed by the paw withdrawal latency and threshold measurement. Samples were examined macroscopically, histologically, and by immunohistochemistry. Results At day 21 post-MIA injection, the MIA\u2009+\u2009solvent and MIA\u2009+\u20091.0% sodium hyaluronate groups showed irregularities and fibrillation in the surface layer, a decrease in blood cells and multilayering in transition and radial zones, no pannus formation, and modified Mankin scores significantly higher than sham knees. The combination of hyaluronic acid and adelmidrol dose-dependently (adelmidrol 0.6%\u2009+\u20091.0% sodium hyaluronate and adelmidrol 2%\u2009+\u20091.0% sodium hyaluronate) reduced the histological alterations induced by MIA. Moreover, degeneration of articular cartilage, mast cell infiltration, and pro-inflammatory cytokine and chemokine plasma levels were significantly downregulated by treatment with a combination of hyaluronic acid and adelmidrol at the above doses. Conclusions Our results clearly demonstrate that the combination of hyaluronic acid and adelmidrol improves the signs of OA induced by MIA

HIGH-VELOCITY BIPOLAR MOLECULAR EMISSION from AN AGN TORUS

We have detected in ALMA observations CO J = 6 - 5 emission from the nucleus of the Seyfert galaxy NGC 1068. The low-velocity (up to +/- 70 km/s relative to systemic) CO emission resolves into a 12x7 pc structure, roughly aligned with the nuclear radio source. Higher-velocity emission (up to +/- 400 km/s) is consistent with a bipolar outflow in a direction nearly perpendicular (roughly 80 degrees) to the nuclear disk. The position-velocity diagram shows that in addition to the outflow, the velocity field may also contain rotation about the disk axis. These observations provide compelling evidence in support of the disk-wind scenario for the AGN obscuring torus.FONDECYT (Grant ID: 3140436), Science and Technology Facilities CouncilThis is the author accepted manuscript. The final version is available from Institute of Physics Publishing via http://dx.doi.org/10.3847/2041-8205/829/1/L