The effect of halogenation of salicylaldehyde on the antiproliferative activities of {Δ/Λ-[Ru(bpy)2(X,Y-sal)]BF4} complexes

Ru(II) polypyridyl complexes are widely used in biological fields, due to their physico-chemical and photophysical properties. In this paper, a series of new chiral Ru(II) polypyridyl complexes (1-5) with the general formula {Δ/Λ-[Ru(bpy)2(X,Y-sal)]BF4} (bpy = 2,2'-bipyridyl; X,Y-sal = 5-bromosalicylaldehyde (1), 3,5-dibromosalicylaldehyde (2), 5-chlorosalicylaldehyde (3), 3,5-dichlorosalicylaldehyde (4) and 3-bromo-5-chlorosalicylaldehy (5)) were synthesized and characterized by elemental analysis, FT-IR, and 1H/13C NMR spectroscopy. Also, the structures of complexes 1 and 5 were determined by X-ray crystallography; these results showed that the central Ru atom adopts a distorted octahedral coordination sphere with two bpy and one halogen-substituted salicylaldehyde. DFT and TD-DFT calculations have been performed to explain the excited states of these complexes. The singlet states with higher oscillator strength are correlated with the absorption signals and are mainly described as 1MLCT from the ruthenium centre to the bpy ligands. The lowest triplet states (T1) are described as 3MLCT from the ruthenium center to the salicylaldehyde ligand. The theoretical results are in good agreement with the observed unstructured band at around 520 nm for complexes 2, 4 and 5. Biological studies on human cancer cells revealed that dihalogenated ligands endow the Ru(II) complexes with enhanced cytotoxicity compared to monohalogenated ligands. In addition, as far as the type of halogen is concerned, bromine is the halogen that provides the highest cytotoxicity to the synthesized complexes. All complexes induce cell cycle arrest in G0/G1 and apoptosis, but only complexes bearing Br are able to provoke an increase in intracellular ROS levels and mitochondrial dysfunction

Preliminary characterization of columnar aerosol properties (AOD-AE) at the saharan tamanrasset (Algeria) station

Postprint (published version

Scintillator identification and performance characteristics of LSO and GSO PSPMTdetector modules combined through common X and Y resistive dividers

Combining signal channels from detector arrays can reduce complexity and minimize cost but, potentially, at the expense of other performance parameters. We evaluated a method that reduces the number of signals by combining the anode outputs of three position-sensitive photomultiplier tubes (PSPMTs) through a common X resistive charge divider and three individual Y resistive charge dividers. Field flood images at 511 keV of two LSO modules combined with a single GSO module were compared to images obtained when the modules were illuminated separately. At moderate count rates only a small reduction in position detection accuracy was observed in the combined tubes. Event mis-positioning was minimal for total count rates < 300,000 cps. At higher rates, pulse pileup degraded accuracy. Delayed charge integration, a method for identifying scintillators by differences in their light decay times, allowed the LSO and GSO arrays to be distinguished from one another and also reduced the effect of pulse pileup. Thus, combining PSPMTs anodes through common X and common Y rcsistivc dividers may be useful in reducing signal number from PSPMT deteclor modules while maintaining good event localization and scintillator identification accuracy at reasonable event rates.Publicad

Density functional method for nonequilibrium electron transport

We describe an ab initio method for calculating the electronic structure, electronic transport, and forces acting on the atoms, for atomic scale systems connected to semi-infinite electrodes and with an applied voltage bias. Our method is based on the density functional theory (DFT) as implemented in the well tested Siesta approach (which uses non-local norm-conserving pseudopotentials to describe the effect of the core electrons, and linear combination of finite-range numerical atomic orbitals to describe the valence states). We fully deal with the atomistic structure of the whole system, treating both the contact and the electrodes on the same footing. The effect of the finite bias (including selfconsistency and the solution of the electrostatic problem) is taken into account using nonequilibrium Green's functions. We relate the nonequilibrium Green's function expressions to the more transparent scheme involving the scattering states. As an illustration, the method is applied to three systems where we are able to compare our results to earlier ab initio DFT calculations or experiments, and we point out differences between this method and existing schemes. The systems considered are: (1) single atom carbon wires connected to aluminum electrodes with extended or finite cross section, (2) single atom gold wires, and finally (3) large carbon nanotube systems with point defects.Comment: 18 pages, 23 figure

Evaluation of night-time aerosols measurements and lunar irradiance models in the frame of the first multi-instrument nocturnal intercomparison campaign

The first multi-instrument nocturnal aerosol optical depth (AOD) intercom-parison campaign was held at the high-mountain Iza ̃na Observatory (Tener-ife, Spain) in June 2017, involving 2-minutes synchronous measurements fromtwo different types of lunar photometers (Cimel CE318-T and Moon Preci-sion Filter Radiometer, LunarPFR) and one stellar photometer. The Robotic Lunar Observatory (ROLO) model developed by the U.S. Geological Survey(USGS) was compared with the open-access ROLO Implementation for Moonphotometry Observation (RIMO) model. Results showed rather small differ-ences at Iza ̃na over a 2-month time period covering June and July, 2017(±0.01 in terms of AOD calculated by means of a day/night/day coherencetest analysis and±2 % in terms of lunar irradiance). The RIMO model hasbeen used in this field campaign to retrieve AOD from lunar photometricmeasurements. No evidence of significant differences with the Moon’s phase angle wasfound when comparing raw signals of the six Cimel photometers involved inthis field campaign.The raw signal comparison of the participating lunar photometers (Cimeland LunarPFR) performed at coincident wavelengths showed consistent mea-surements and AOD differences within their combined uncertainties at 870 nmand 675 nm. Slightly larger AOD deviations were observed at 500 nm, point-ing to some unexpected instrumental variations during the measurement pe-riod.Lunar irradiances retrieved using RIMO for phase angles varying between0◦and 75◦(full Moon to near quarter Moon) were compared to the irradi-ance variations retrieved by Cimel and LunarPFR photometers. Our resultsshowed a relative agreement within±3.5 % between the RIMO model andthe photometer-based lunar irradiances.The AOD retrieved by performing a Langley-plot calibration each nightshowed a remarkable agreement (better than 0.01) between the lunar pho-tometers. However, when applying the Lunar-Langley calibration using RIMO,AOD differences of up to 0.015 (0.040 for 500 nm) were found, with differ-ences increasing with the Moon’s phase angle. These differences are thoughtto be partly due to the uncertainties in the irradiance models, as well asinstrumental deficiencies yet to be fully understood.High AOD variability in stellar measurements was detected during thecampaign. Nevertheless, the observed AOD differences in the Cimel/stellarcomparison were within the expected combined uncertainties of these twophotometric techniques. Our results indicate that lunar photometry is amore reliable technique, especially for low aerosol loading conditions.The uncertainty analysis performed in this paper shows that the com-bined standard AOD uncertainty in lunar photometry is dependent on thecalibration technique (up to 0.014 for Langley-plot with illumination-basedcorrection, 0.012-0.022 for Lunar-Langley calibration, and up to 0.1 for the 2 Sun-Moon Gain Factor method). This analysis also corroborates that theuncertainty of the lunar irradiance model used for AOD calculation is withinthe 5-10 % expected range.This campaign has allowed us to quantify the important technical diffi-culties that still exist when routinely monitoring aerosol optical propertiesat night-time. The small AOD differences observed between the three typesof photometers involved in the campaign are only detectable under pristinesky conditions such as those found in this field campaign. Longer campaignsare necessary to understand the observed discrepancies between instrumentsas well as to provide more conclusive results about the uncertainty involvedin the lunar irradiance model

A regulated deficit irrigation strategy for hedgerow olive orchards with high plant density

Background & Aims There is not a consensus on the best irrigation approach for super-high density (SHD) olive orchards. Our aim was to design and test a regulated deficit irrigation (RDI) strategy for a sustainable balance between water saving, tree vigour and oil production. Methods We tested our RDI strategy for 3 years in an ‘Arbequina’ orchard with 1,667 trees ha−1. Two levels of irrigation reduction were applied, 60RDI and 30RDI, scaled to replacing 60 % and 30 %, respectively, of the of irrigation needs (IN). We also had a full irrigation (FI) treatment as control, with IN totalling 4,701 m3 ha−1 Results The 30RDI treatment showed the best balance between water saving, tree vigour and oil production. With a yearly irrigation amount (IA) of 1,366 m3 ha−1, which meant 72 % water saving as compared to FI, the reduction in oil yield was 26 % only. Conclusions Our results, together with recent knowledge on the effect of water stress on fruit development, allowed us to suggest a potentially improved RDI strategy for which a total IA of ca. 2,100 m3 ha−1 was calculated. Both some management details and the benefits of this suggested RDI strategy are still to be tested

Structural Conformers of (1,3-Dithiol-2-ylidene)ethanethioamides: The Balance Between Thioamide Rotation and Preservation of Classical Sulfur-Sulfur Hypervalent Bonds

The reaction of N-(2-phthalimidoethyl)-N-alkylisopropylamines and S2Cl2 gave 4-N-(2-phthalimidoethyl)-N-alkylamino-5-chloro-1,2-dithiol-3-thiones that quantitatively cycloadded to dimethyl or diethyl acetylenedicarboxylate to give stable thioacid chlorides, which in turn reacted with one equivalent of aniline or a thiole to give thioanilides or a dithioester. Several compounds of this series showed atropisomers that were studied by a combination of dynamic NMR, simulation of the signals, conformational analysis by DFT methods, and single crystal X-ray diffraction, showing a good correlation between the theoretical calculations, the experimental values of energies, and the preferred conformations in the solid state. The steric hindering of the crowded substitution at the central amine group was found to be the reason for the presence of permanent atropisomers in this series of compounds and the cause of a unique disposition of the thioxo group at close-to-right angles with respect to the plane defined by the 1,3-dithiole ring in the dithiafulvene derivatives, thus breaking the sulfur–sulfur hypervalent bond that is always found in this kind of compounds.Ministerio de Economıá y Competitividad, Spain (Project CTQ2012- 31611), Junta de Castilla y León, Consejería de Educación y Cultura y Fondo Social Europeo (Project BU246A12-1), and the European Commission, Seventh Framework Programme (Project SNIFFER FP7-SEC-2012-312411

Effect of Host Species on the Distribution of Mutational Fitness Effects for an RNA Virus

Knowledge about the distribution of mutational fitness effects (DMFE) is essential for many evolutionary models. In recent years, the properties of the DMFE have been carefully described for some microorganisms. In most cases, however, this information has been obtained only for a single environment, and very few studies have explored the effect that environmental variation may have on the DMFE. Environmental effects are particularly relevant for the evolution of multi-host parasites and thus for the emergence of new pathogens. Here we characterize the DMFE for a collection of twenty single-nucleotide substitution mutants of Tobacco etch potyvirus (TEV) across a set of eight host environments. Five of these host species were naturally infected by TEV, all belonging to family Solanaceae, whereas the other three were partially susceptible hosts belonging to three other plant families. First, we found a significant virus genotype-by-host species interaction, which was sustained by differences in genetic variance for fitness and the pleiotropic effect of mutations among hosts. Second, we found that the DMFEs were markedly different between Solanaceae and non-Solanaceae hosts. Exposure of TEV genotypes to non-Solanaceae hosts led to a large reduction of mean viral fitness, while the variance remained constant and skewness increased towards the right tail. Within the Solanaceae hosts, the distribution contained an excess of deleterious mutations, whereas for the non-Solanaceae the fraction of beneficial mutations was significantly larger. All together, this result suggests that TEV may easily broaden its host range and improve fitness in new hosts, and that knowledge about the DMFE in the natural host does not allow for making predictions about its properties in an alternative host