Ruthenium complexes of the 1,4-bis(diphenylphosphino)-1,3-butadiene-bridged diphosphine 1,2,3,4-Me-4-NUPHOS: Solvent-dependent interconversion of four- and six-electron donor coordination and transfer hydrogenation activity

In chloroform, [RuCl2(nbd)(py)(2)] (1) (nbd = norbornadiene; py = pyridine) reacts with 1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene (1,2,3,4-Me-4-NUPHOS) to give the dimer [Ru2Cl3(eta(4)-1,2,3,4-Me-4-NUPHOS)(2)]Cl (2a), whereas, in THF [RuCl2(1,2,3,4-Me-4-NUPHOS)(PY)(2)] (3) is isolated as the sole product of reaction. Compound 2 exists as a 4:1 mixture of two noninterconverting isomers, the major with C, symmetry and the minor with either C, or C-2 symmetry. A single-crystal X-ray analysis of [Ru2Cl3 (eta(4)-1,2,3,4-Me-4-NUPHOS)(2)] [SbF6] (2b), the hexafluoroantimonate salt of 2a, revealed that the diphosphine coordinates in an unusual manner, as a eta(4)-six-electron donor, bonded through both P atoms and one of the double bonds of the butadiene tether. Compounds 2a and 3 react with 1,2-ethylenediamine (en) in THF to afford [RuCl2(1,2,3,4-Me-4-NUPHOS)(en)] (4), which rapidly dissociates a chloride ligand in chloroform to give [RuCl(eta(4)-1,2,3,4-Me-4-NUPHOS)(en)] [Cl] (5a). Complexes 4 and 5a cleanly and quantitatively interconvert in a solvent-dependent equilibrium, and in THF 5a readily adds chloride to displace the eta(2)-interaction and re-form 4. A single-crystal X-ray structure determination of [RuCl(eta(4)-1,2,3,4-Me-4-NUPHOS)(en)][ClO4] (5b) confirmed that the diphosphine coordinates in an eta(4)-manner as a facial six-electron donor with the eta(2)-coordinated double bond occupying the site trans to chloride. The eta(4)-bonding mode can be readily identified by the unusually high-field chemical shift associated with the phosphorus atom adjacent to the eta(2)-coordinated double bond. Complexes 2a, 2b, 4, and 5a form catalysts that are active for transfer hydrogenation of a range of ketones. In all cases, catalysts formed from precursors 2a and 2b are markedly more active than those formed from 4 and 5a.

Solid-bound, proton-driven, fluorescent ‘off–on–off’ switches based on PET (photoinduced electron transfer)

Anthracene-based, H+-driven, ‘off–on–off’ fluorescent PET (photoinduced electron transfer) switches are immobilized on organic and inorganic polymeric solids in the form of Tentagel® and silica, respectively. The environment of the organic bead displaces apparent switching thresholds towards lower pH values whereas the Si–O- groups of silica electrostatically cause the opposite effect. These switches are ternary logic gate tags, one of which can be particularly useful in strengthening molecular computational identification (MCID) of small solid objects.

Solid and liquid charge-transfer complex formation between 1-methylnaphthalene and 1-alkyl-cyanopyridinium bis{(trifluoromethyl)sulfonyl}imide ionic liquids

Liquid charge-transfer (CT) complexes were observed to form on contacting electron-rich aromatics with electron withdrawing group appended 1-alkyl-4-cyanopyridinium ionic liquids (ILs). Cooling below the melting point of the ionic liquid resulted in crystallisation of ionic liquid from the complex for 2-cyano and 3-cyano pyridinium isomers and in the formation of a 1 : 1 IL : aromatic crystalline CT-complex with the 4-cyanopyridinium isomer. The liquid structure of a 1 : 1 mixture of 1-methyl-4-cyanopyridinium bis{(trifluoromethyl)sulfonyl} imide with 1-methylnaphthalene has been probed by neutron diffraction experiments and molecular dynamics simulations. A high degree of correlation between the experimental data and the simulations was found with a significant displacement of the anions from around the cation by the aromatic species and the resulting structure having pi-pi stacks between the cations and the aromatic.

Prokaryotes on the tentacles of deep-sea holothurians: A novel form of dietary supplementation

Bathyal and abyssal epibenthic holothurians have a layer of bacteria lying over the tentacular epidermis and below the cuticle. Thus the tentacles of deep-sea holothurians may provide ideal conditions for subcuticular bacteria. These bacteria appear to be regulated by phagocytosis, which, together with pinocytosis would facilitate transfer of bacterial metabolites to the holothurian. Their abundance suggests a previously unknown pathway for energy transformation and assimilation of particular significance in an environment where food is limiting.

Blue bottle light: lecture demonstrations of homogeneous and heterogeneous photo-induced electron transfer reactions

The classic, non-photochemical blue bottle experiment involves the reaction of methylene blue (MB) with deprotonated glucose, to form a bleached form of the dye, leuco-methylene blue (LMB), and subsequent colour recovery by shaking with air. This reaction is a popular demonstrator of key principles in kinetics and reaction mechanisms. Here it is modified so as to highlight features of homogenous and heterogeneous photoinduced electron transfer (PET) (Pure Appl. Chem., 2007, 79, 293-465) reactions, i.e. blue bottle light experiments. The homogeneous blue bottle light experiment uses methylene blue, MB, as the photo-sensitizer and triethanolamine as the sacrificial electron donor. Visible light irradiation of this system leads to its rapid bleaching, followed by the ready restoration of its original colour upon shaking away from the light source. The heterogeneous blue bottle light experiment uses titania as the photo-sensitizer, MB as a redox indicator and glucose as the sacrificial electron donor. UVA light irradiation of this system leads to the rapid bleaching of the MB and the gradual restoration of its original colour with shaking and standing. The latter 'dark' step can be made facile and more demonstrator-friendly by using platinised titania particles. These two photochemical versions of the blue bottle experiment are used to explore the factors which underpin homogeneous and heterogeneous PET reactions and provide useful demonstrations of homogeneous and heterogeneous photochemistry.

Genomic instability in Chinese hamster cells after exposure to X rays or alpha particles of different mean linear energy transfer

Evidence has accumulated that radiation induces a transmissible persistent destabilization of the genome, which mag. result in effects arising in the progeny of irradiated but surviving cells. An enhanced death rate among the progeny of cells surviving irradiation persists for many generations in the form of a reduced plating efficiency. Such delayed reproductive death is correlated with an increased occurrence of micronuclei. Since it has been suggested that radiation-induced chromosomal instability might depend on the radiation quality, we investigated the effects of alpha particles of different LET by looking at the frequency of delayed micronuclei in Chinese hamster V79 cells after cytochalasin-induced block of cell division, A dose-dependent increase in the frequency of micronuclei was found in cells assayed 1 week postirradiation or later. Also, there was a persistent increase in the frequency of dicentrics in surviving irradiated cells, Moreover, we found an increased micronucleus frequency in all of the 30 clones isolated from individual cells which had been irradiated with doses equivalent to either one, two or three alpha-particle traversals per cell nucleus, We conclude that the target for genomic instability in Chinese hamster cells must be larger than the cell nucleus. (C) 1997 by Radiation Research Society

Improving multi-site benefit functions via Bayesian model averaging: A new approach to benefit transfer

A benefit function transfer obtains estimates of willingness-to-pay (WTP) for the evaluation of a given policy at a site by combining existing information from different study sites. This has the advantage that more efficient estimates are obtained, but it relies on the assumption that the heterogeneity between sites is appropriately captured in the benefit transfer model. A more expensive alternative to estimate WTP is to analyze only data from the policy site in question while ignoring information from other sites. We make use of the fact that these two choices can be viewed as a model selection problem and extend the set of models to allow for the hypothesis that the benefit function is only applicable to a subset of sites. We show how Bayesian model averaging (BMA) techniques can be used to optimally combine information from all models. The Bayesian algorithm searches for the set of sites that can form the basis for estimating a benefit function and reveals whether such information can be transferred to new sites for which only a small data set is available. We illustrate the method with a sample of 42 forests from U.K. and Ireland. We find that BMA benefit function transfer produces reliable estimates and can increase about 8 times the information content of a small sample when the forest is 'poolable'. © 2008 Elsevier Inc. All rights reserved.

Line-driven Disk Winds in Activ Galactic Nuclei: The Critical Importance of Ionization and Radiative Transfer

Accretion disk winds are thought to produce many of the characteristic features seen in the spectra of active galactic nuclei (AGNs) and quasi-stellar objects (QSOs). These outflows also represent a natural form of feedback between the central supermassive black hole and its host galaxy. The mechanism for driving this mass loss remains unknown, although radiation pressure mediated by spectral lines is a leading candidate. Here, we calculate the ionization state of, and emergent spectra for, the hydrodynamic simulation of a line-driven disk wind previously presented by Proga & Kallman. To achieve this, we carry out a comprehensive Monte Carlo simulation of the radiative transfer through, and energy exchange within, the predicted outflow. We find that the wind is much more ionized than originally estimated. This is in part because it is much more difficult to shield any wind regions effectively when the outflow itself is allowed to reprocess and redirect ionizing photons. As a result, the calculated spectrum that would be observed from this particular outflow solution would not contain the ultraviolet spectral lines that are observed in many AGN/QSOs. Furthermore, the wind is so highly ionized that line driving would not actually be efficient. This does not necessarily mean that line-driven winds are not viable. However, our work does illustrate that in order to arrive at a self-consistent model of line-driven disk winds in AGN/QSO, it will be critical to include a more detailed treatment of radiative transfer and ionization in the next generation of hydrodynamic simulations.

Secure D2D Communication in Large-Scale Cognitive Cellular Networks with Wireless Power Transfer

In this paper, we investigate secure device-to-device (D2D) communication in energy harvesting large-scale cognitive cellular networks. The energy constrained D2D transmitter harvests energy from multi-antenna equipped power beacons (PBs), and communicates with the corresponding receiver using the spectrum of the cellular base stations (BSs). We introduce a power transfer model and an information signal model to enable wireless energy harvesting and secure information transmission. In the power transfer model, we propose a new power transfer policy, namely, best power beacon (BPB) power transfer. To characterize the power transfer reliability of the proposed policy, we derive new closed-form expressions for the exact power outage probability and the asymptotic power outage probability with large antenna arrays at PBs. In the information signal model, we present a new comparative framework with two receiver selection schemes: 1) best receiver selection (BRS), and 2) nearest receiver selection (NRS). To assess the secrecy performance, we derive new expressions for the secrecy throughput considering the two receiver selection schemes using the BPB power transfer policies. We show that secrecy performance improves with increasing densities of PBs and D2D receivers because of a larger multiuser diversity gain. A pivotal conclusion is reached that BRS achieves better secrecy performance than NRS but demands more instantaneous feedback and overhead.

Testing quasar unification: radiative transfer in clumpy winds

Various unification schemes interpret the complex phenomenology of quasars and luminous active galactic nuclei (AGN) in terms of a simple picture involving a central black hole, an accretion disc and an associated outflow. Here, we continue our tests of this paradigm by comparing quasar spectra to synthetic spectra of biconical disc wind models, produced with our state-of-the-art Monte Carlo radiative transfer code. Previously, we have shown that we could produce synthetic spectra resembling those of observed broad absorption line (BAL) quasars, but only if the X-ray luminosity was limited to 1043 erg s-1. Here, we introduce a simple treatment of clumping, and find that a filling factor of ˜0.01 moderates the ionization state sufficiently for BAL features to form in the rest-frame UV at more realistic X-ray luminosities. Our fiducial model shows good agreement with AGN X-ray properties and the wind produces strong line emission in, e.g., Lyα and C IV 1550 Å at low inclinations. At high inclinations, the spectra possess prominent LoBAL features. Despite these successes, we cannot reproduce all emission lines seen in quasar spectra with the correct equivalent-width ratios, and we find an angular dependence of emission line equivalent width despite the similarities in the observed emission line properties of BAL and non-BAL quasars. Overall, our work suggests that biconical winds can reproduce much of the qualitative behaviour expected from a unified model, but we cannot yet provide quantitative matches with quasar properties at all viewing angles. Whether disc winds can successfully unify quasars is therefore still an open question.