Dynamic structure elucidation of chemical reactivity by laser pulses and X-ray probes

Visualising chemical reactions by X-ray methods is a tantalising prospect. New light sources provide the prospect for studying atomic, electronic and energy transfers accompanying chemical change by X-ray spectroscopy and inelastic scattering. Here we assess how this adventure can illuminate inorganic and catalytic chemistry. In particular X-ray inelastic scattering provides a means of exploiting X-ray free electron lasers, as a parallel to laser Raman spectroscopy

Letter. On the activation of [CrCl3{R-SN(H)S-R}] catalysts for selective trimerization of ethene: a freeze-quench Cr K-edge XAFS study

Homogeneous chromium catalysts for the selective conversion of ethene to hex-1-ene are formed from Cr(III) reagents, amino-thioether ligands of the type HN(CH2CH2SR)2, and aluminum reagents. In this study the early activation steps are investigated by EPR, UV-visible and Cr K-edge XAFS spectroscopy; rapid stopped-flow mixing and a freeze-quench allows good quality EXAFS analysis of a species formed in ~ 1 second of reaction. This is shown to involve reduction to Cr(II) and deprotonation of a NH group of the auxiliary ligand. This 4-coordinate metal-center may act as precursor for the coordination of ethene and subsequent selective oligomerization

USING WEARABLE TECHNOLOGY TO DETECT CHANGES TO TRUNK POSITION AND POWER IN CYCLING

This pilot study aimed to quantify the change of CoM acceleration when the trunk position and the power output was varied during indoor cycling. Triathletes (n=4) performed a varied indoor cycling power protocol in their natural training environment whilst wearing a trunk (sacrum) mounted wearable device containing a triaxial accelerometer. Mediolateral acceleration increased 26% as athletes moved from the drops position, to the aerodynamic position and back to the drops position. Although longitudinal acceleration increased 8%, minimal differences in anteroposterior CoM magnitude were observed. Power output was found to have an effect on both the mediolateral and longitudinal acceleration alongside increases in RPE. The results indicate that accelerometers may be effective in monitoring changes to trunk position and power output

LD4PE: A Competency-based Guide to Linked Data Principles and Practices

The IMLS-funded Linked Data for Professional Education (LD4PE) project has developed a competency-based prototype referatory of Learning Resources for teaching and learning practices in the design, implementation, and management of Linked Data. This report summarizes the work of the project in developing: 1) an RDF-modeled “Competency Index for Linked Data” (Index) based on the Achievements Standards Network Description Language (ASN-DL) for describing formally promulgated competencies and benchmarks; 2) an openly available, web-based tool set to support the management of the Index; the generation of RDF metadata about Learning Resources; the packaging and arrangement of selected Learning Resources by users in “Saved Sets”; and the creation of learning trajectory maps expressing curricular structures or personal learning journeys superimposed over the competency framework through the integration of these elements as WordPress custom posts and taxonomies on the LD4PE website; 3) a set of cataloged Learning Resources that have been mapped to the competencies and benchmarks of the Index to support competency-based resource discovery by teachers, trainers and learners; 4) the LD4PE project website (http://explore.dublincore.net), which will be managed by the Dublin Core Metadata Initiative (DCMI) as part of its educational agenda; and 5) a set of Best Practices describing the infrastructure and policies developed for the project that others can reuse in mapping future knowledge domains in a similar manner

Far Ultraviolet Absolute Flux of alpha Virginis

We present the far ultraviolet spectrum of alpha Virginis taken with EURD spectrograph on-board MINISAT-01. The spectral range covered is from ~900 to 1080 A with 5 A spectral resolution. We have fitted Kurucz models to IUE spectra of alpha Vir and compared the extension of the model to our wavelengths with EURD data. This comparison shows that EURD fluxes are consistent with the prediction of the model within 20-30%, depending on the reddening assumed. EURD fluxes are consistent with Voyager observations but are ~60% higher than most previous rocket observations of alpha Vir.Comment: 13 pages, 4 figures. Submitted to The Astrophysical Journa

Activation of [CrCl3{PPh2N(iPr)PPh2}] for the selective oligomerisation of ethene: a Cr K-edge XAFS study

The activation of the ethene tetramerisation catalyst system based upon [CrCl3(THF)3] and N(iPr)(PPh2)2 has been investigated in situ via the reaction of [CrCl3{PPh2N(R)PPh2}(THF)] 1a (R=iPr) with excess AlMe3 in toluene. The Cr K-edge XAFS spectrum of the solution freeze quenched after 1 min reaction time indicated monomethylation of the metal with the resultant product being [CrClMe(ClAlCl3){PPh2N(R)PPh2}(THF)] 4a (R=iPr). After 5 minutes reaction time the XAFS spectra indicate that ~50% of 4a had been converted to a Cr(II) species, with the central core being high spin [CrCl2{PPh2N(R)PPh2}] 7a (R=iPr); a similar species, [CrClMe{PPh2N(R)PPh2}] 9a (R=iPr) was observed as its adduct with AlMe3 (10a) (R=iPr) when spectra were recorded on samples maintained a room temperature. Detailed analysis (EXAFS and XANES) indicated that 7a and 9a are stabilised by adduct formation of a Cr-Cl bond to the Lewis acids B(C6F5)3 and AlMe3, respectiveley. Modelling with DFT methods indicated that five-coordination was achieved, respectively by Cr-F (11a) and Cr-C (10a) interactions. In the presence of [Ph3C][Al{OC(tBuF)3}4], the Cr XAFS of the room temperature solution was inconsistent with the maintenance of a phosphine complex, but could be modelled with a site like [Cr2Me8]4- {Cr-Cr 2.01(2), Cr-C 2.14(4)}, thus demonstrating considerable variation in the effects of differing Lewis acids

Community interventions for people with complex emotional needs that meet the criteria for personality disorder diagnoses: systematic review of economic evaluations and expert commentary

Background: Diagnoses of personality disorder are prevalent among people using community secondary mental health services. Identifying cost-effective community-based interventions is important when working with finite resources. / Aims: To assess the cost-effectiveness of primary or secondary care community-based interventions for people with complex emotional needs who meet criteria for a diagnosis of personality disorder to inform healthcare policy-making. / Method: Systematic review (PROSPERO: CRD42020134068) of databases. We included economic evaluations of interventions for adults with complex emotional needs associated with a diagnosis of personality disorder in community mental health settings published before 18 September 2019. Study quality was assessed using the CHEERS statement. / Results: Eighteen studies were included. The studies mainly evaluated psychotherapeutic interventions. Studies were also identified that evaluated altering the setting in which care was delivered and joint crisis plans. No strong economic evidence to support a single intervention or model of community-based care was identified. / Conclusions: Robust economic evidence to support a single intervention or model of community-based care for people with complex emotional needs is lacking. The strongest evidence was for dialectical behaviour therapy, with all three identified studies indicating that it is likely to be cost-effective in community settings compared with treatment as usual. More robust evidence is required on the cost-effectiveness of community-based interventions on which decision makers can confidently base guidelines or allocate resources. The evidence should be based on consistent measures of costs and outcomes with sufficient sample sizes to demonstrate impacts on these

Reflections on the cost of low-cost whole genome sequencing: Framing the health policy debate

The cost of whole genome sequencing is dropping rapidly. There has been a great deal of enthusiasm about the potential for this technological advance to transform clinical care. Given the interest and significant investment in genomics, this seems an ideal time to consider what the evidence tells us about potential benefits and harms, particularly in the context of health care policy. The scale and pace of adoption of this powerful new technology should be driven by clinical need, clinical evidence, and a commitment to put patients at the centre of health care policy