468 research outputs found

    Easy to synthesize, robust organo-osmium asymmetric transfer hydrogenation catalysts

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    Asymmetric transfer hydrogenation (ATH) is an important process in organic synthesis for which the Noyori-type RuII catalysts [(arene)Ru(Tsdiamine)] are now well established and widely used. We now demonstrate for the first time the catalytic activity of the osmium analogues. X-ray crystal structures of the 16-electron OsII catalysts are almost identical to those of RuII. Intriguingly the precursor complex was isolated as a dichlorido complex with a monodentate amine ligand. The OsII catalysts are readily synthesised (within 1 h) and exhibit excellent enantioselectivity in ATH reactions of ketones

    Atomic-scale control of magnetic anisotropy via novel spin-orbit coupling effect in La2/3Sr1/3MnO3/SrIrO3 superlattices

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    Magnetic anisotropy (MA) is one of the most important material properties for modern spintronic devices. Conventional manipulation of the intrinsic MA, i.e. magnetocrystalline anisotropy (MCA), typically depends upon crystal symmetry. Extrinsic control over the MA is usually achieved by introducing shape anisotropy or exchange bias from another magnetically ordered material. Here we demonstrate a pathway to manipulate MA of 3d transition metal oxides (TMOs) by digitally inserting non-magnetic 5d TMOs with pronounced spin-orbit coupling (SOC). High quality superlattices comprised of ferromagnetic La2/3Sr1/3MnO3 (LSMO) and paramagnetic SrIrO3 (SIO) are synthesized with the precise control of thickness at atomic scale. Magnetic easy axis reorientation is observed by controlling the dimensionality of SIO, mediated through the emergence of a novel spin-orbit state within the nominally paramagnetic SIO.Comment: Proceedings of the National Academy of Sciences, May 201

    Image-guidance in endoscopic pituitary surgery: an in-silico study of errors involved in tracker-based techniques

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    Background: Endoscopic endonasal surgery is an established minimally invasive technique for resecting pituitary adenomas. However, understanding orientation and identifying critical neurovascular structures in this anatomically dense region can be challenging. In clinical practice, commercial navigation systems use a tracked pointer for guidance. Augmented Reality (AR) is an emerging technology used for surgical guidance. It can be tracker based or vision based, but neither is widely used in pituitary surgery. Methods: This pre-clinical study aims to assess the accuracy of tracker-based navigation systems, including those that allow for AR. Two setups were used to conduct simulations: (1) the standard pointer setup, tracked by an infrared camera; and (2) the endoscope setup that allows for AR, using reflective markers on the end of the endoscope, tracked by infrared cameras. The error sources were estimated by calculating the Euclidean distance between a point’s true location and the point’s location after passing it through the noisy system. A phantom study was then conducted to verify the in-silico simulation results and show a working example of image-based navigation errors in current methodologies. Results: The errors of the tracked pointer and tracked endoscope simulations were 1.7 and 2.5 mm respectively. The phantom study showed errors of 2.14 and 3.21 mm for the tracked pointer and tracked endoscope setups respectively. Discussion: In pituitary surgery, precise neighboring structure identification is crucial for success. However, our simulations reveal that the errors of tracked approaches were too large to meet the fine error margins required for pituitary surgery. In order to achieve the required accuracy, we would need much more accurate tracking, better calibration and improved registration techniques

    Asymmetric transfer hydrogenation by synthetic catalysts in cancer cells

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    Catalytic anticancer metallodrugs active at low doses could minimise side-effects, introduce novel mechanisms of action which combat resistance, and widen the spectrum of anticancer drug activity. We have used new highly-stable chiral half-sandwich organometallic Os(II) arene sulfonyl diamine complexes, [Os(arene)(TsDPEN)] to achieve highly enantioselective reduction of pyruvate, a key intermediate in metabolic pathways, both in aqueous model systems and in human cancer cells, using non-toxic concentrations of sodium formate as a hydride source. Importantly the catalytic mechanism generates selectivity towards ovarian cancer cells versus non-cancerous fibroblasts (both ovarian and lung), which are commonly used as models of healthy proliferating cells. The formate precursor N-formylmethionine was explored as an alternative to formate in PC3 prostate cancer cells, which are known to over-express a deformylase enzyme. Transfer hydrogenation catalysts generating reductive stress in cancer cells offer a ground-breaking new approach to cancer therapy

    Transfer hydrogenation and antiproliferative activity of tethered half-sandwich organoruthenium catalysts

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    We report the synthesis and characterization of four neutral organometallic tethered complexes, [Ru(η6-Ph(CH2)3-ethylenediamine-N-R)Cl], where R = methanesulfonyl (Ms, 1), toluenesulfonyl (Ts, 2), 4-trifluoromethylbenzenesulfonyl (Tf, 3), and 4-nitrobenzenesulfonyl (Nb, 4), including their X-ray crystal structures. These complexes exhibit moderate antiproliferative activity toward human ovarian, lung, hepatocellular, and breast cancer cell lines. Complex 2 in particular exhibits a low cross-resistance with cisplatin. The complexes show potent catalytic activity in the transfer hydrogenation of NAD+ to NADH with formate as hydride donor in aqueous solution (310 K, pH 7). Substituents on the chelated ligand decreased the turnover frequency in the order Nb > Tf > Ts > Ms. An enhancement of antiproliferative activity (up to 22%) was observed on coadministration with nontoxic concentrations of sodium formate (0.5–2 mM). Complex 2 binds to nucleobase guanine (9-EtG), but DNA appears not to be the target, as little binding to calf thymus DNA or bacterial plasmid DNA was observed. In addition, complex 2 reacts rapidly with glutathione (GSH), which might hamper transfer hydrogenation reactions in cells. Complex 2 induced a dose-dependent G1 cell cycle arrest after 24 h exposure in A2780 human ovarian cancer cells while promoting an increase in reactive oxygen species (ROS), which is likely to contribute to its antiproliferative activity

    The thermal emission of the exoplanets WASP-1b and WASP-2b

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    We present a comparative study of the thermal emission of the transiting exoplanets WASP-1b and WASP-2b using the Spitzer Space Telescope. The two planets have very similar masses but suffer different levels of irradiation and are predicted to fall either side of a sharp transition between planets with and without hot stratospheres. WASP-1b is one of the most highly irradiated planets studied to date. We measure planet/star contrast ratios in all four of the IRAC bands for both planets (3.6-8.0um), and our results indicate the presence of a strong temperature inversion in the atmosphere of WASP-1b, particularly apparent at 8um, and no inversion in WASP-2b. In both cases the measured eclipse depths favor models in which incident energy is not redistributed efficiently from the day side to the night side of the planet. We fit the Spitzer light curves simultaneously with the best available radial velocity curves and transit photometry in order to provide updated measurements of system parameters. We do not find significant eccentricity in the orbit of either planet, suggesting that the inflated radius of WASP-1b is unlikely to be the result of tidal heating. Finally, by plotting ratios of secondary eclipse depths at 8um and 4.5um against irradiation for all available planets, we find evidence for a sharp transition in the emission spectra of hot Jupiters at an irradiation level of 2 x 10^9 erg/s/cm^2. We suggest this transition may be due to the presence of TiO in the upper atmospheres of the most strongly irradiated hot Jupiters.Comment: 10 pages, submitted to Ap
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