Comparison of the experimental, semi-experimental and ab initio equilibrium structures of acetylene: Influence of relativisitic effects and of the diagonal Born-Oppenheimer corrections

The equilibrium structure of acetylene (also named ethyne) has been reinvestigated to resolve the small discrepancies noted between different determinations. The size of the system as well as the large amount of available experimental data provides the quite unique opportunity to check the magnitude and relevance of various contributions to equilibrium structure as well as to verify the accuracy of experimental results. With respect to pure theoretical investigation, quantum-chemical calculations at the coupled-cluster level have been employed together with extrapolation to the basis set limit, consideration of higher excitations in the cluster operator, inclusion of core correlation effects as well as relativistic and diagonal Born-Oppenheimer corrections. In particular, it is found that the extrapolation to the complete basis set limit, the inclusion of higher excitations in the electronic-correlation treatment and the relativistic corrections are of the same order of magnitude. It also appears that a basis set as large as a core-valence quintuple-zeta set is required for accurately accounting for the inner-shell correlation contribution. From a pure experimental point of view, the equilibrium structure has been determined using very accurate rotational constants recently obtained by a global analysis (that is to say that all non-negligible interactions are explicitely included in the Hamiltonian matrix) of rovibrational spectra. Finally, a semi-experimental equilibrium structure (where the equilibrium rotational constants are obtained from the experimental ground state rotational constants and computed rovibrational corrections) has been obtained from the available experimental ground-state rotational constants for ten isotopic species corrected for computed vibrational corrections. Such a determination led to the revision of the ground-state rotational constants of two isotopologues, thus showing that structural determination is a good method to identify errors in experimental rotational constants. The three structures are found in a very good agreement, and our recommended values are rCC 120.2958(7) pm and rCH 106.164(1) pm. © 2011 American Institute of Physics.

Differential cytotoxic and prooxidnant activity of knipholone and knipholone anthrone

Knipholone (KP) and knipholone anthrone (KA) are natural 4-phenylanthraquinone structural analogues with established differential biological effects including in vitro antioxidant [1] and antimicrobial properties [2]. The present study was designed to investigate the comparative in vitro cytotoxic activity and the possible mechanism of action of these two compounds. We demonstrated that KA is by order of magnitude more cytotoxic to mammalian cells than KP. In parallel with the demonstrated cytotoxic effect, KA but not KP induces prooxidative DNA damage in the presence of copper ions. In order to establish the possible involvement of reactive oxygen species in the KA-mediated prooxidative effect, we investigated the protective effect of several metal chelators and reactive oxygen species scavengers. Our data suggest that reactive oxygen species such as hydrogen peroxide are involved and a good correlation between prooxidative action, antioxidant effect and cytotoxicity is established for these two structural analogues. The chemistry, pharmacology and potential medicinal/toxicological potential of these compounds are discussed.

Comparative antioxidant, prooxidant and cytotoxic activity of sigmoidin A and eriodictyol

Sigmoidin A (SGN) is a prenylated flavanone derivative of eriodictyol (ERD) with reported moderate antioxidant, antimicrobial and anti-inflammatory activity. Since ERD and other structurally similar antioxidant phenolic compounds have been shown to induce prooxidative macromolecular damage and cytotoxicity in cancer cells, the comparative in vitro effects of these structural analogues on cancer cell viability and Cu(II)-dependent DNA damage were studied. In the presence of Cu(II) ions, both SGN and ERD (7.4-236 µM) caused comparable concentration-dependent pBR322 plasmid DNA strand scission. The DNA damage induced by SGN and ERD could be abolished by ROS scavengers, glutathione (GSH) and catalase as well as EDTA and a specific Cu(I) chelator neocuproine. Both ERD and SGN readily reduce Cu(II) to Cu(I) suggesting a prooxidative mechanism of DNA damage. In a cell free system, ERD and SGN did also show comparable radical scavenging activity. SGN was, however, by an order of magnitude more cytotoxic to cancer cells than ERD and this effect was significantly attenuated by GSH suggesting a prooxidative mechanism of cell death. A depletion of intracellular GSH level by SGN in cancer cells is also demonstrated.

Synthesis of cycloruthenated compounds as potential anticancer agents

A library of 19 cycloruthenated derivatives is constructed by making use of the well-known cyclometalation reaction. Their geometries are modified in a straightforward manner by addition of either mono- or bidentate ligands, such as bipyridine, phenanthroline, 1,2-bis(diphenylphosphanyl)ethane, dimethylphenylphosphane, triphenylphosphane, and 1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane (PTA) ligands, to cationic cycloruthenated centers. The antitumor properties of the compounds thus obtained are investigated in order to compare them with recently reported ruthenium complexes and cisplatin. IC50 values against mammalian cells (A-172, HCT-116, and RDM-4) are determined for the library compounds and some of them, such as those derived from orthoruthenated phenylpyridine and a bidentate N,N ligand, display activity of the same order of magnitude as cisplatin.

The use of biological indicators of heavy metal contamination in estuaries. Occasional Publication of the Marine Biological Association 1

The use of the deposit-feeding molluscs Scrobicularia plana and Macoma balthica and the burrowing polychaete Nereis diversicolor as indicators of the biological availability of heavy metals in sediments has been evaluated. Concentrations of Ag, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sn and Zn have been measured in organisms and sediments from more than 30 estuaries in south west England and South Wales and indicate that the biological availability of most metals varies by order of magnitude between uncontaminated and contaminated sites. The results have been compared with those obtained with the use of other species of indicator organisms in estuaries.

Quantitative Cytochemical Effects Of 3 Metal-Ions On A Lysosomal Hydrolase Of A Hydroid

The quantitative effects of Cu8+, Cd2+ and Hg2+ on the cytochemical staining reaction for lysosomal N-acetyl-/?-D-glucosaminidase have been determined and related to the inhibitory effects of the metals on colonial growth rate in the experimentally cultured hydroid Campanularia flexuosa. Cytochemical threshold concentrations are comparable to known environmental levels and are about one order of magnitude lower than those obtained by measuring colony growth rates. Pretreatment of colonies with Cuz+ gave no indication of tolerance adaptation, although there is evidence of the cumulative toxicity of Cu2+ and the possible sequestration of this metal in endodermal cell lysosomes. There is also an indication that the Cu2+ may exert its toxic effect by decreasing the stability of the lysosomal membranes, thus increasing the level of free glucosaminidase activity.

Colloidal stability of nanoparticles derived from simulated cloud-processed mineral dusts

Laboratory simulation of cloud processing of three model dust types with distinct Fe-content (Moroccan dust, Libyan dust and Etna ash) and reference goethite and ferrihydrite were conducted in order to gain a better understanding of natural nanomaterial inputs and their environmental fate and bioavailability. The resulting nanoparticles (NPs) were characterised for Fe dissolution kinetics, aggregation/size distribution, micromorphology and colloidal stability of particle suspensions using a multi-method approach. We demonstrated that the: (i) acid-leachable Fe concentration was highest in volcanic ash (1 m Mg(-1) dust) and was followed by Libyan and Moroccan dust with an order of magnitude lower levels; (ii) acid leached Fe concentration in the<20 nm fraction was similar in samples processed in the dark with those under artificial sunlight, but average hydrodynamic diameter of NPs after cloud-processing (pH~6) was larger in the former; iii) NPs formed at pH~6 were smaller and less poly-disperse than those at low pH, whilst unaltered zeta potentials indicated colloidal instability; iv) relative Fe percentage in the finer particles derived from cloud processing does not reflect Fe content of unprocessed dusts (e.g. volcanic ash>Libyan dust). The common occurrence of Fe-rich "natural nanoparticles" in atmospheric dust derived materials may indicate their more ubiquitous presence in the marine environment than previously thought.

Volcanic ash supply to the surface ocean – remote sensing of biological responses and their wider biogeochemical significance

Transient micronutrient enrichment of the surface ocean can enhance phytoplankton growth rates and alter microbial community structure with an ensuing spectrum of biogeochemical feedbacks. Strong phytoplankton responses to micronutrients supplied by volcanic ash have been reported recently. Here we: (i) synthesize findings from these recent studies; (ii) report the results of a new remote sensing study of ash fertilization; and (iii) calculate theoretical bounds of ash-fertilized carbon export. Our synthesis highlights that phytoplankton responses to ash do not always simply mimic that of iron amendment; the exact mechanisms for this are likely biogeochemically important but are not yet well understood. Inherent optical properties of ash-loaded seawater suggest rhyolitic ash biases routine satellite chlorophyll-a estimation upwards by more than an order of magnitude for waters with <0.1 mg chlorophyll-a m-3, and less than a factor of 2 for systems with >0.5 mg chlorophyll-a m-3. For this reason post-ash-deposition chlorophyll-a changes in oligotrophic waters detected via standard Case 1 (open ocean) algorithms should be interpreted with caution. Remote sensing analysis of historic events with a bias less than a factor of 2 provided limited stand-alone evidence for ash-fertilization. Confounding factors were poor coverage, incoherent ash dispersal, and ambiguity ascribing biomass changes to ash supply over other potential drivers. Using current estimates of iron release and carbon export efficiencies, uncertainty bounds of ash-fertilized carbon export for 3 events are presented. Patagonian iron supply to the Southern Ocean from volcanic eruptions is less than that of windblown dust on thousand year timescales but can dominate supply at shorter timescales. Reducing uncertainties in remote sensing of phytoplankton response and nutrient release from ash are avenues for enabling assessment of the oceanic response to large-scale transient nutrient enrichment.

B-type supergiants in the SMC: Chemical compositions and comparison of static and unified models

High-resolution UCLES/AAT spectra are presented for nine B-type supergiants in the SMC, chosen on the basis that they may show varying amounts of nuclear-synthetically processed material mixed to their surface. These spectra have been analysed using a new grid of approximately 12 000 non-LTE line blanketed tlusty model atmospheres to estimate atmospheric parameters and chemical composition. The abundance estimates for O, Mg and Si are in excellent agreement with those deduced from other studies, whilst the low estimate for C may reflect the use of the C II doublet at 4267 Å. The N estimates are approximately an order of magnitude greater than those found in unevolved B-type stars or H II regions but are consistent with the other estimates in AB-type supergiants. These results have been combined with results from a unified model atmosphere analysis of UVES/VLT spectra of B-type supergiants (Trundle et al. 2004, A&A, 417, 217) to discuss the evolutionary status of these objects. For two stars that are in common with those discussed by Trundle et al., we have undertaken a careful comparison in order to try to understand the relative importance of the different uncertainties present in such analyses, including observational errors and the use of static or unified models. We find that even for these relatively luminous supergiants, tlusty models yield atmospheric parameters and chemical compositions similar to those deduced from the unified code fastwind.

Excitation rate coefficients for transitions from the ground level of Gd XXXVII

Excitation rate coefficients, for transitions from the ground level to excited levels of Gd XXXVII, have been calculated over the temperature range 5002500 eV using the R-matrix method. It is observed that the contribution of resonances enhances the rates by up to an order of magnitude over the available (non- resonant) results of Hagelstein.

Electron impact excitation of Gd XXXVII and radiative rates for Ni-like ions with 60

Energy levels and radiative rates for transitions among the 107 finestructure levels belonging to the (1s(2)2s(2)2p(6)) 3s(2)3p(6)3d(10), 3s(2)3p(6)3d(9)4l, 3s(2)3p(5)3d(10)4l, and 3s3p(6)3d(10)4l configurations of Ni-like ions with 60 less than or equal to Z less than or equal to 90 have been calculated using the GRASP code. The collision strengths (Omega) have also been computed for transitions in Gd XXXVII at energies below 800 Ryd, using the DARC code. Resonances have been resolved in a fine energy mesh in the threshold region, and excitation rate coefficients have been calculated for transitions from the ground level to excited levels at temperatures below 2500 eV. These have been compared with those available in the literature, and enhancement in the values of rates, due to resonances, has been observed up to an order of magnitude for some of the transitions.

Cold collisions of electrons with molecules

Results are presented of high-resolution scattering experiments involving electron collisions with CO2 and CS2, between a few meV and 200 meV impact energy. Virtual state scattering is shown to dominate the low-energy behaviour for both species. The most striking features of the scattering spectrum for CS2 are, however, giant resonances with cross sections greater by more than an order of magnitude than those generally encountered in low-energy scattering. A strong feature centred at 15 meV is attributed to the involvement of CS2- and is interpreted to be a consequence of the virtual state effect.

Effect of Target Polarization in Electron-Ion Recombination

We present results of a study of the effect of target polarization on electron-ion recombination, and show that coherent radiation by the target electrons gives a large contribution to the recombination rate. It significantly modifies the nonresonant photorecombination background. A procedure has been devised whereby this contribution can be evaluated together with the conventional radiative recombination, independently of the dielectronic recombination component. Numerical results are presented for Zn2+, Cd2+, Sn4+, and Xe8+, showing up to an order-of-magnitude enhancement.