Tuning the in vitro cell cytotoxicity of dinuclear arene ruthenium trithiolato complexes: Influence of the arene ligand

A new series of cationic dinuclear arene ruthenium complexes bridged by three thiophenolato ligands, [(η6-arene)2Ru2(μ2-SR)3]+ with arene = indane, R = met: 1 (met = 4-methylphenyl); R = mco: 4 (mco = 4-methylcoumarin-7-yl); arene = biphenyl, R = met: 2; R = mco: 5; arene = 1,2,3,4-tetrahydronaphthalene, R = met: 3; R = mco: 6, have been prepared from the reaction of the neutral precursor [(η6-arene)Ru(μ2-Cl)Cl]2 and the corresponding thiophenol RSH. All cationic complexes have been isolated as chloride salts and fully characterized by spectroscopic and analytical methods. The molecular structure of 1, solved by X-ray structure analysis of a single crystal of the chloride salt, shows the two ruthenium atoms adopting a pseudo-octahedral geometry without metal–metal bond in accordance with the noble gas rule. All complexes are stable in H2O at 37 °C, but only 1 remains soluble in a 100 mM aqueous NaCl solution, while significant percentages (30–60 %) of 2–6 precipitate as chloride salts under these conditions. The 4-methylphenylthiolato complexes (R = met) are highly cytotoxic towards human ovarian cancer cells, the IC50 values being in the sub-micromolar range, while the 4-methylcoumarin-7-yl thiolato complexes (R = mco) are only slightly cytotoxic. Complexes 1 and 3 show the highest in vitro anticancer activity with IC50 values inferior to 0.06 μM for the A2780 cell line. The results demonstrate that the arene ligand is an important parameter that should be more systematically evaluated when designing new half-sandwich organometallic complexes.

Dynamic computer simulation of electrophoretic enantiomer migration order and separation in presence of a neutral cyclodextrin

One-dimensional dynamic computer simulation was employed to investigate the separation and migration order change of ketoconazole enantiomers at low pH in presence of increasing amounts of (2-hydroxypropyl)-β-cyclodextrin (OHP-β-CD). The 1:1 interaction of ketoconazole with the neutral cyclodextrin was simulated under real experimental conditions and by varying input parameters for complex mobilities and complexation constants. Simulation results obtained with experimentally determined apparent ionic mobilities, complex mobilities, and complexation constants were found to compare well with the calculated separation selectivity and experimental data. Simulation data revealed that the migration order of the ketoconazole enantiomers at low (OHP-β-CD) concentrations (i.e. below migration order inversion) is essentially determined by the difference in complexation constants and at high (OHP-β-CD) concentrations (i.e. above migration order inversion) by the difference in complex mobilities. Furthermore, simulations with complex mobilities set to zero provided data that mimic migration order and separation with the chiral selector being immobilized. For the studied CEC configuration, no migration order inversion is predicted and separations are shown to be quicker and electrophoretic transport reduced in comparison to migration in free solution. The presented data illustrate that dynamic computer simulation is a valuable tool to study electrokinetic migration and separations of enantiomers in presence of a complexing agent.

Guaranteed resonance enclosures and exclosures for atoms and molecules

In this paper, we confirm, with absolute certainty, a conjecture on a certain oscillatory behaviour of higher auto-ionizing resonances of atoms and molecules beyond a threshold. These results not only definitely settle a more than 30 year old controversy in Rittby et al. (1981 Phys. Rev. A 24, 1636–1639 (doi:10.1103/PhysRevA.24.1636)) and Korsch et al. (1982 Phys. Rev. A 26, 1802–1803 (doi:10.1103/PhysRevA.26.1802)), but also provide new and reliable information on the threshold. Our interval-arithmetic-based method allows one, for the first time, to enclose and to exclude resonances with guaranteed certainty. The efficiency of our approach is demonstrated by the fact that we are able to show that the approximations in Rittby et al. (1981 Phys. Rev. A 24, 1636–1639 (doi:10.1103/PhysRevA.24.1636)) do lie near true resonances, whereas the approximations of higher resonances in Korsch et al. (1982 Phys. Rev. A 26, 1802–1803 (doi:10.1103/PhysRevA.26.1802)) do not, and further that there exist two new pairs of resonances as suggested in Abramov et al. (2001 J. Phys. A 34, 57–72 (doi:10.1088/0305-4470/34/1/304)).

First direct observation of sputtered lunar oxygen

We present the first direct measurement of neutral oxygen in the lunar exosphere, detected by the Chandrayaan-1 Energetic Neutral Analyzer (CENA). With the lunar surface consisting of about 60% of oxygen in number, the neutral oxygen detected in CENA's energy range (11 eV−3.3 keV) is attributed to have originated from the lunar surface, where it was released through solar wind ion sputtering. Fitting of CENA's mass spectra with calibration spectra from ground and in-flight data resulted in the detection of a robust oxygen signal, with a flux of 0.2 to 0.4 times the flux of backscattered hydrogen, depending on the solar wind helium content and particle velocity. For the two solar wind types observed, we derive subsolar surface oxygen atom densities of N0= (1.1 ± 0.3) · 107m−3 and (1.4 ± 0.4) · 107m−3, respectively, which agree well with earlier model predictions and measured upper limits. From these surface densities, we derive column densities of NC= (1.5 ± 0.5) · 1013 m−2and (1.6 ± 0.5) · 1013 m−2. In addition, we identified for the first time a helium component. This helium is attributed to backscattering of solar wind helium (alpha particles) from the lunar surface as neutral energetic helium atoms, which has also been observed for the first time. This identification is supported by the characteristic energy of the measured helium atoms, which is roughly 4 times the energy of reflected solar wind hydrogen, and the correlation with solar wind helium content.

Search for neutral Higgs bosons of the minimal supersymmetric standard model in pp collisions at sqrts = 8 TeV with the ATLAS detector

A search for the neutral Higgs bosons predicted by the Minimal Supersymmetric Standard Model (MSSM) is reported. The analysis is performed on data from proton-proton collisions at a centre-of-mass energy of 8 TeV collected with the ATLAS detector at the Large Hadron Collider. The samples used for this search were collected in 2012 and correspond to integrated luminosities in the range 19.5-20.3 fb−1. The MSSM Higgs bosons are searched for in the τ τ final state. No significant excess over the expected background is observed, and exclusion limits are derived for the production cross section times branching fraction of a scalar particle as a function of its mass. The results are also interpreted in the MSSM parameter space for various benchmark scenarios.

Search for long-lived neutral particles decaying into lepton jets in proton-proton collisions at √s=8 TeV with the ATLAS detector

Several models of physics beyond the Standard Model predict neutral particles that decay into final states consisting of collimated jets of light leptons and hadrons (socalled “lepton jets”). These particles can also be long-lived with decay length comparable to, or even larger than, the LHC detectors’ linear dimensions. This paper presents the results of a search for lepton jets in proton-proton collisions at the centre-of-mass energy of √s = 8TeV in a sample of 20.3 fb−1 collected during 2012 with the ATLAS detector at the LHC. Limits on models predicting Higgs boson decays to neutral long-lived lepton jets are derived as a function of the particle’s proper decay length.

Measurement of the neutrino-oxygen neutral-current interaction cross section by observing nuclear deexcitation γ rays

We report the first measurement of the neutrino-oxygen neutral-current quasielastic (NCQE) cross section. It is obtained by observing nuclear deexcitation γ rays which follow neutrino-oxygen interactions at the Super-Kamiokande water Cherenkov detector. We use T2K data corresponding to 3.01 × 1020 protons on target. By selecting only events during the T2K beam window and with well-reconstructed vertices in the fiducial volume, the large background rate from natural radioactivity is dramatically reduced. We observe 43 events in the 4–30 MeV reconstructed energy window, compared with an expectation of 51.0, which includes an estimated 16.2 background events. The background is primarily nonquasielastic neutral-current interactions and has only 1.2 events from natural radioactivity. The flux-averaged NCQE cross section we measure is 1.55 × 10−38 cm2 with a 68% confidence interval of ð1.22; 2.20Þ × 10−38 cm2 at a median neutrino energy of 630 MeV, compared with the theoretical prediction of 2.01 × 10−38 cm2.

Kinetic simulation of neutral∕ionized gas and electrically charged dust in the coma of comet 67P∕Churyumov-Gerasimenko

The cometary coma is a unique phenomenon in the solar system being a planetary atmosphere influenced by little or no gravity. As a comet approaches the sun, the water vapor with some fraction of other gases sublimate, generating a cloud of gas, ice and other refractory materials (rocky and organic dust) ejected from the surface of the nucleus. Sublimating gas molecules undergo frequent collisions and photochemical processes in the near‐nucleus region. Owing to its negligible gravity, comets produce a large and highly variable extensive dusty coma with a size much larger than the characteristic size of the cometary nucleus. The Rosetta spacecraft is en route to comet 67P/Churyumov‐Gerasimenko for a rendezvous, landing, and extensive orbital phase beginning in 2014. Both, interpretation of measurements and safety consideration of the spacecraft require modeling of the comet’s dusty gas environment. In this work we present results of a numerical study of multispecies gaseous and electrically charged dust environment of comet Chyuryumov‐Gerasimenko. Both, gas and dust phases of the coma are simulated kinetically. Photolytic reactions are taken into account. Parameters of the ambient plasma as well as the distribution of electric/magnetic fields are obtained from an MHD simulation [1] of the coma connected to the solar wind. Trajectories of ions and electrically charged dust grains are simulated by accounting for the Lorentz force and the nucleus gravity.

Comparison of 3D kinetic and hydrodynamic models to ROSINA-COPS measurements of the neutral coma of 67P/Churyumov-Gerasimenko

67P/Churyumov-Gerasimenko (67P) is a Jupiter-family comet and the object of investigation of the European Space Agency mission Rosetta. This report presents the first full 3D simulation results of 67P’s neutral gas coma. In this study we include results from a direct simulation Monte Carlo method, a hydrodynamic code, and a purely geometric calculation which computes the total illuminated surface area on the nucleus. All models include the triangulated 3D shape model of 67P as well as realistic illumination and shadowing conditions. The basic concept is the assumption that these illumination conditions on the nucleus are the main driver for the gas activity of the comet. As a consequence, the total production rate of 67P varies as a function of solar insolation. The best agreement between the model and the data is achieved when gas fluxes on the night side are in the range of 7% to 10% of the maximum flux, accounting for contributions from the most volatile components. To validate the output of our numerical simulations we compare the results of all three models to in situ gas number density measurements from the ROSINA COPS instrument. We are able to reproduce the overall features of these local neutral number density measurements of ROSINA COPS for the time period between early August 2014 and January 1 2015 with all three models. Some details in the measurements are not reproduced and warrant further investigation and refinement of the models. However, the overall assumption that illumination conditions on the nucleus are at least an important driver of the gas activity is validated by the models. According to our simulation results we find the total production rate of 67P to be constant between August and November 2014 with a value of about 1 × 10²⁶ molecules s⁻¹.

ROSINA/DFMS and IES observations of 67P: Ion-neutral chemistry in the coma of a weakly outgassing comet

Context. The Rosetta encounter with comet 67P/Churyumov-Gerasimenko provides a unique opportunity for an in situ, up-close investigation of ion-neutral chemistry in the coma of a weakly outgassing comet far from the Sun. Aims. Observations of primary and secondary ions and modeling are used to investigate the role of ion-neutral chemistry within the thin coma. Methods. Observations from late October through mid-December 2014 show the continuous presence of the solar wind 30 km from the comet nucleus. These and other observations indicate that there is no contact surface and the solar wind has direct access to the nucleus. On several occasions during this time period, the Rosetta/ROSINA/Double Focusing Mass Spectrometer measured the low-energy ion composition in the coma. Organic volatiles and water group ions and their breakup products (masses 14 through 19), CO2+ (masses 28 and 44) and other mass peaks (at masses 26, 27, and possibly 30) were observed. Secondary ions include H3O+ and HCO+ (masses 19 and 29). These secondary ions indicate ion-neutral chemistry in the thin coma of the comet. A relatively simple model is constructed to account for the low H3O+/H2O+ and HCO+/CO+ ratios observed in a water dominated coma. Results from this simple model are compared with results from models that include a more detailed chemical reaction network. Results. At low outgassing rates, predictions from the simple model agree with observations and with results from more complex models that include much more chemistry. At higher outgassing rates, the ion-neutral chemistry is still limited and high HCO+/CO+ ratios are predicted and observed. However, at higher outgassing rates, the model predicts high H3O+/H2O+ ratios and the observed ratios are often low. These low ratios may be the result of the highly heterogeneous nature of the coma, where CO and CO2 number densities can exceed that of water.

The capabilities of ROSINA/DFMS to measure argon isotopes at comet 67P/Churyumov–Gerasimenko

Little is known about the noble gas abundances in comets. These highly volatile atoms are possible tracers of the history of cometary matter including the thermal evolution. They can help quantify the contribution of cometary impacts to terrestrial oceans and help elucidate on the formation history of comets and their role in the formation and evolution of planetary atmospheres. This paper focuses on argon and the capabilities to measure this noble gas with in situ mass spectrometry at comet 67P/Churyumov–Gerasimenko, the target of the European Space Agency׳s spacecraft Rosetta. Argon may have been detected by remote sensing in a single Oort cloud comet but to date nothing is known about the isotopic abundances of argon in comets. Furthermore, no detection of argon in a Jupiter-family comet has been reported. Comet 67P/Churyumov–Gerasimenko belongs to the group of Jupiter-family comets and originates most likely in the Kuiper belt. Onboard Rosetta is ROSINA/DFMS (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis/Double Focusing Mass Spectrometer). DFMS has unprecedented mass resolution and high sensitivity and is designed to measure isotopic ratios including argon (Balsiger et al., 2007). Argon measurements using the DFMS lab model (identical to the flight model) demonstrate this capability. At very least, this mass spectrometer has the resolution and sensitivity to reduce the upper limit on the argon outgassing rate relative to water by more than three orders of magnitude (for 38Ar). Most likely, ROSINA/DFMS will provide the first detection of argon in a Jupiter-family comet together with the first determination of the ³⁶Ar/³⁸Ar ratio at a comet.