Light-Induced Activation of a Molybdenum Oxotransferase Model within a Ru(II)-Mo(VI) Dyad

Nature uses molybdenum-containing enzymes to catalyze oxygen atom transfer (OAT) from water to organic substrates. In these enzymes, the two electrons that are released during the reaction are rapidly removed, one at a time, by spatially separated electron transfer units. Inspired by this design, a Ru(II)-Mo(VI) dyad was synthesized and characterized, with the aim of accelerating the rate-determining step in the cis-dioxo molybdenum-catalyzed OAT cycle, the transfer of an oxo ligand to triphenyl phosphine, via a photo-oxidation process. The dyad consists of a photoactive bis(bipyridyl)-phenanthroline ruthenium moiety that is covalently linked to a bioinspired cis-dioxo molybdenum thiosemicarbazone complex. The quantum yield and luminescence lifetimes of the dyad [Ru(bpy)2(L(2))MoO2(solv)](2+) were determined. The major component of the luminescence decay in MeCN solution (τ = 1149 ± 2 ns, 67%) corresponds closely to the lifetime of excited [Ru(bpy)2(phen-NH2)](2+), while the minor component (τ = 320 ± 1 ns, 31%) matches that of [Ru(bpy)2(H2-L(2))](2+). In addition, the (spectro)electrochemical properties of the system were investigated. Catalytic tests showed that the dyad-catalyzed OAT from dimethyl sulfoxide to triphenyl phosphine proceeds significantly faster upon irradiation with visible light than in the dark. Methylviologen acts as a mediator in the photoredox cycle, but it is regenerated and hence only required in stoichiometric amounts with respect to the catalyst rather than sacrificial amounts. It is proposed that oxidative quenching of the photoexcited Ru unit, followed by intramolecular electron transfer, leads to the production of a reactive one-electron oxidized catalyst, which is not accessible by electrochemical methods. A significant, but less pronounced, rate enhancement was observed when an analogous bimolecular system was tested, indicating that intramolecular electron transfer between the photosensitizer and the catalytic center is more efficient than intermolecular electron transfer between the separate components

Ground-based follow-up observations of TRAPPIST-1 transits in the near-infrared

The TRAPPIST-1 planetary system is a favorable target for the atmospheric characterization of temperate earth-sized exoplanets by means of transmission spectroscopy with the forthcoming James Webb Space Telescope (JWST). A possible obstacle to this technique could come from the photospheric heterogeneity of the host star that could affect planetary signatures in the transit transmission spectra. To constrain further this possibility, we gathered an extensive photometric data set of 25 TRAPPIST-1 transits observed in the near-IR J band (1.2 $\mu$m) with the UKIRT and the AAT, and in the NB2090 band (2.1 $\mu$m) with the VLT during the period 2015-2018. In our analysis of these data, we used a special strategy aiming to ensure uniformity in our measurements and robustness in our conclusions. We reach a photometric precision of $\sim0.003$ (RMS of the residuals), and we detect no significant temporal variations of transit depths of TRAPPIST-1 b, c, e, and g over the period of three years. The few transit depths measured for planets d and f hint towards some level of variability, but more measurements will be required for confirmation. Our depth measurements for planets b and c disagree with the stellar contamination spectra originating from the possible existence of bright spots of temperature 4500 K. We report updated transmission spectra for the six inner planets of the system which are globally flat for planets b and g and some structures are seen for planets c, d, e, and f.Comment: accepted for publication in MNRA

Complex fractures of the distal humerus in the elderly: Is primary total elbow arthroplasty a valid treatment alternative? A series of 20 cases

SummaryIntroductionDistal humerus fractures are fairly rare. But as our population ages, these fractures become more complex and the choice of treatment more delicate. Poor bone quality results in many technical problems and the fixation hardware stability remains at risk. The goal of this study was to evaluate the functional recovery and morbidity of complex distal humerus fractures in elderly patients when treated with elbow prosthesis.HypothesisGood functional recovery can be achieved with a total joint replacement.Patients and methodsThis series consisted of 20 patients (18 women and two men) having an average age of 80years (range 65–93, median 80). Based on the AO classification, there were two Type A2 fractures, two Type B fractures, 15 Type C fractures and one fracture that could not be classified because of previous rheumatoid disease history at this elbow. Two fractures were open. In two cases, the olecranon was also fractured. Treatment consisted of the implantation of a Coonrad-Morrey, hinge-type total elbow prosthesis (Zimmer®, Warsaw, IN, USA). The Mayo Clinic surgical approach was used 17 times and the transolecranon approach was used three times. Primary arthroplasty was performed in 19 cases and the surgery was performed after six weeks of conservative treatment (diagnostic delay) in one case. Unrestricted motion was allowed after surgery, but a maximum of 0.5kg could be carried during the first 3months; this was subsequently increased to 2.5kg.ResultsFifteen of the 20 patients were available for reevaluation with an average follow-up of 3.6years (range 1.7–5.5, median 3.4). Four patients had died and one was lost to follow-up. The average range of motion was 97° (range 60–130°), comprising an average flexion of 130° (range 110–140°) and average loss of extension of 33° (range 0–80°). Pronation and supination were normal. The average Mayo Elbow Performance Score (MEPS) was 83 (range 60–100, median 80). X-rays revealed seven cases of radiolucent lines, with two being progressive. There was no visible wear of the polyethylene bushings at the hinge. Six patients had moderate periarticular heterotopic ossification. The two cases of olecranon osteotomy and one case of olecranon fracture had healed. There were no surgical site infections but two cases of ulnar compression, one of which required neurolysis. There was one case of humeral component loosening after 6years, but the implant was not changed.DiscussionThe clinical range of motion results were comparable to published data. The functional scores were slightly lower, mainly because of the pain factor. The initial results were encouraging and consistent with published data as long as the indications were well-chosen. Based on this retrospective study, total elbow arthroplasty can be a valid alternative in the surgeon's treatment armamentarium for complex distal humerus fractures in elderly patients who have moderate functional demands. Our results support our hypothesis, since we found good functional recovery without associated morbidity.Level of evidenceLevel IV retrospective study without comparator

MOLECULAR RECOMMENDATION ENGINE FOR MULTI-PROPERTIES OPTIMIZATION

28-2

Photolariats: synthesis, metal ion complexation and photochromism

International audiencePhotolariat development, as an extension to the family of synthetic photochromic crown ether receptors, or photocrowns, is reported. Incorporated additional chelating groups, namely two anisoles or thioanisoles, contribute in completing the metal ion coordination sphere with different affinities and selectivities for a range of ions. Single-crystal X-ray diffraction analysis suggests that the thermally stable trans-form of the receptor is unsuitable for ion binding, consistent with spectrophotometric and NMR titration results, which is largely improved in the cis-form as the basis for the photocontrolled ion coordination/ejection. In terms of the azobenzene-containing receptor photochemistry, a photostationary state highly enriched in the cis-form (94:6, cis-/trans-) is reached, with slow thermal return (1.1-1.4 × 10− 5 s− 1) in the dark, which can undergo multiple cycles without discernable photodegradation

Identification of target-specific bioisosteric fragments from ligand-protein crystallographic data

Bioisosteres are functional groups or atoms that are structurally different but that can form similar intermolecular interactions. Potential bioisosteres were identified here from analysing the X-ray crystallographic structures for sets of different ligands complexed with a fixed protein. The protein was used to align the ligands with each other, and then pairs of ligands compared to identify substructural features with high volume overlap that occurred in approximately the same region of geometric space. The resulting pairs of substructural features can suggest potential bioisosteric replacements for use in lead-optimisation studies. Experiments with 12 sets of ligand-protein complexes from the Protein Data Bank demonstrate the effectiveness of the procedure

Global analysis of the TRAPPIST Ultra-Cool Dwarf Transit Survey

ABSTRACT We conducted a global analysis of the TRAPPIST Ultra-Cool Dwarf Transit Survey – a prototype of the SPECULOOS transit search conducted with the TRAPPIST-South robotic telescope in Chile from 2011 to 2017 – to estimate the occurrence rate of close-in planets such as TRAPPIST-1b orbiting ultra-cool dwarfs. For this purpose, the photometric data of 40 nearby ultra-cool dwarfs were reanalysed in a self-consistent and fully automated manner starting from the raw images. The pipeline developed specifically for this task generates differential light curves, removes non-planetary photometric features and stellar variability, and searches for transits. It identifies the transits of TRAPPIST-1b and TRAPPIST-1c without any human intervention. To test the pipeline and the potential output of similar surveys, we injected planetary transits into the light curves on a star-by-star basis and tested whether the pipeline is able to detect them. The achieved photometric precision enables us to identify Earth-sized planets orbiting ultra-cool dwarfs as validated by the injection tests. Our planet-injection simulation further suggests a lower limit of 10 per cent on the occurrence rate of planets similar to TRAPPIST-1b with a radius between 1 and 1.3 R⊕ and the orbital period between 1.4 and 1.8 d.</jats:p

In search of lost hybridity: the French Daniel Deronda

Starting from a set of examples of borrowings from French in George Eliot’s Daniel Deronda, I explore the various ways in which the characters’ and narrator’s use of mixed English–French utterances generates inferences which make the transcending of their mono-cultural self possible. I go on to argue that in Jumeau’s recent French translation of the novel, the reader is not given access to those inferences, resulting in the erasing of an Anglo-European, cosmopolitan identity