Versatile Coordination of Cyclopentadienyl-Arene Ligands and Its Role in Titanium-Catalyzed Ethylene Trimerization

Cationic titanium(IV) complexes with ansa-(η5-cyclopentadienyl,η6-arene) ligands were synthesized and characterized by X-ray crystallography. The strength of the metal-arene interaction in these systems was studied by variable-temperature NMR spectroscopy. Complexes with a C1 bridge between the cyclopentadienyl and arene moieties feature hemilabile coordination behavior of the ligand and consequently are active ethylene trimerization catalysts. Reaction of the titanium(IV) dimethyl cations with CO results in conversion to the analogous cationic titanium(II) dicarbonyl species. Metal-to-ligand backdonation in these formally low-valent complexes gives rise to a strongly bonded, partially reduced arene moiety. In contrast to the η6-arene coordination mode observed for titanium, the more electron-rich vanadium(V) cations [cyclopentadienyl-arene]V(NiPr2)(NC6H4-4-Me)+ feature η1-arene binding, as determined by a crystallographic study. The three different metal-arene coordination modes that we experimentally observed model intermediates in the cycle for titanium-catalyzed ethylene trimerization. The nature of the metal-arene interaction in these systems was studied by DFT calculations.

The legal and ethical framework governing Body Donation in Europe-1st update on current practice

Previously, we have reported on the legal and ethical aspects and current practice of body donation in several European countries, reflecting cultural and religious variations as well as different legal and constitutional frameworks. We have also established good practice in body donation. Here we shall further extend the legal and ethical frameworks in place and also focus on novelties in the law and different directives. Of particular interest are points that address the commercialization of human bodies and body parts and weaknesses in the legal directives. Therefore, it is important to define what is ethical and what needs to be considered unethical in body donation and the subsequent utilisation of human bodies for teaching and research.peer-reviewe

Rh-POP Pincer Xantphos Complexes for C-S and C-H Activation. Implications for Carbothiolation Catalysis

The neutral Rh­(I)–Xantphos complex [Rh­(κ³-_P,O,P-Xantphos)­Cl]_<i>n</i>, <b>4</b>, and cationic Rh­(III) [Rh­(κ³-_P,O,P-Xantphos)­(H)₂]­[BAr^F₄], <b>2a</b>, and [Rh­(κ³-_P,O,P-Xantphos-3,5-C₆H₃(CF₃)₂)­(H)₂]­[BAr^F₄], <b>2b</b>, are described [Ar^F = 3,5-(CF₃)₂C₆H₃; Xantphos = 4,5-bis­(diphenylphosphino)-9,9-dimethylxanthene; Xantphos-3,5-C₆H₃(CF₃)₂ = 9,9-dimethylxanthene-4,5-bis­(bis­(3,5-bis­(trifluoromethyl)­phenyl)­phosphine]. A solid-state structure of <b>2b</b> isolated from C₆H₅Cl solution shows a κ¹-chlorobenzene adduct, [Rh­(κ³-_P,O,P-Xantphos-3,5-C₆H₃(CF₃)₂)­(H)₂(κ¹-ClC₆H₅)]­[BAr^F₄], <b>3</b>. Addition of H₂ to <b>4</b> affords, crystallographically characterized, [Rh­(κ³-_P,O,P-Xantphos)­(H)₂Cl], <b>5</b>. Addition of diphenyl acetylene to <b>2a</b> results in the formation of the C–H activated metallacyclopentadiene [Rh­(κ³-_P,O,P-Xantphos)­(ClCH₂Cl)­(σ,σ-(C₆H₄)­C­(H)CPh)]­[BAr^F₄], <b>7</b>, a rare example of a crystallographically characterized Rh–dichloromethane complex, alongside the Rh­(I) complex <i>mer</i>-[Rh­(κ³-_P,O,P-Xantphos)­(η²-PhCCPh)]­[BAr^F₄], <b>6</b>. Halide abstraction from [Rh­(κ³-_P,O,P-Xantphos)­Cl]_<i>n</i> in the presence of diphenylacetylene affords <b>6</b> as the only product, which in the solid state shows that the alkyne binds perpendicular to the κ³-POP Xantphos ligand plane. This complex acts as a latent source of the [Rh­(κ³-_P,O,P-Xantphos)]⁺ fragment and facilitates <i>ortho</i>-directed C–S activation in a number of 2-arylsulfides to give <i>mer</i>-[Rh­(κ³-_P,O,P-Xantphos)­(σ,κ¹-Ar)­(SMe)]­[BAr^F₄] (Ar = C₆H₄COMe, <b>8</b>; C₆H₄(CO)­OMe, <b>9</b>; C₆H₄NO₂, <b>10</b>; C₆H₄CNCH₂CH₂O, <b>11</b>; C₆H₄C₅H₄N, <b>12</b>). Similar C–S bond cleavage is observed with allyl sulfide, to give <i>fac</i>-[Rh­(κ³-_P,O,P-Xantphos)­(η³-C₃H₅)­(SPh)]­[BAr^F₄], <b>13</b>. These products of C–S activation have been crystallographically characterized. For <b>8</b> in situ monitoring of the reaction by NMR spectroscopy reveals the initial formation of <i>fac</i>-κ³-<b>8</b>, which then proceeds to isomerize to the <i>mer</i>-isomer. With the <i>para</i>-ketone aryl sulfide, 4-SMeC ₆H₄COMe, C–H activation <i>ortho</i> to the ketone occurs to give <i>mer</i>-[Rh­(κ³-_P,O,P-Xantphos)­(σ,κ¹-4-(COMe)­C₆H₃SMe)­(H)]­[BAr^F₄], <b>14</b>. The temporal evolution of carbothiolation catalysis using <i>mer</i>-κ³-<b>8</b>, and phenyl acetylene and 2-(methylthio)­acetophenone substrates shows initial fast catalysis and then a considerably slower evolution of the product. We suggest that the initially formed <i>fac</i>-isomer of the C–S activation product is considerably more active than the <i>mer</i>-isomer (i.e., <i>mer</i>-<b>8</b>), the latter of which is formed rapidly by isomerization, and this accounts for the observed difference in rates. A likely mechanism is proposed based upon these data

A multi-disciplinary perspective on emergent and future innovations in peer review [version 2; referees: 2 approved]

Peer review of research articles is a core part of our scholarly communication system. In spite of its importance, the status and purpose of peer review is often contested. What is its role in our modern digital research and communications infrastructure? Does it perform to the high standards with which it is generally regarded? Studies of peer review have shown that it is prone to bias and abuse in numerous dimensions, frequently unreliable, and can fail to detect even fraudulent research. With the advent of web technologies, we are now witnessing a phase of innovation and experimentation in our approaches to peer review. These developments prompted us to examine emerging models of peer review from a range of disciplines and venues, and to ask how they might address some of the issues with our current systems of peer review. We examine the functionality of a range of social Web platforms, and compare these with the traits underlying a viable peer review system: quality control, quantified performance metrics as engagement incentives, and certification and reputation. Ideally, any new systems will demonstrate that they out-perform and reduce the biases of existing models as much as possible. We conclude that there is considerable scope for new peer review initiatives to be developed, each with their own potential issues and advantages. We also propose a novel hybrid platform model that could, at least partially, resolve many of the socio-technical issues associated with peer review, and potentially disrupt the entire scholarly communication system. Success for any such development relies on reaching a critical threshold of research community engagement with both the process and the platform, and therefore cannot be achieved without a significant change of incentives in research environments

Movement and predation: a catch-and-release study on the acoustic tracking of bonefish in the Indian Ocean

Tourism generated through bonefish (Albula spp.) fishing contributes to the economies of many isolated tropical islands and atolls. However, little research has been conducted on bonefish in the Indian Ocean. This study aimed to contribute to the understanding of bonefish ecology in the Indian Ocean by quantifying the spatial and temporal movements of Albula glossodonta at a near-pristine and predator-rich atoll in the Seychelles; however, to achieve this, an analysis to identify the occurrence of possible post-release predation bias was first necessary. An acoustic telemetry study was initiated at the remote St. Joseph Atoll, within an array of 88 automated data-logging acoustic receivers. Thirty bonefish were surgically implanted with Vemco V13 acoustic transmitters and tracked for one year. Only 10% of the tagged bonefish were detected for longer than two weeks. A comparison of the final 100 h of movement data from fish detected for less than two weeks to the movement data of the fish detected for longer periods revealed distinct differences in area use and significant differences in the average daily distance moved, speed of movement and frequency of detections. This suggested that mortality in the form of post-release predation was at least 43% of tagged fish. The three surviving bonefish were tracked for 210 to 367 days. These individuals remained in the atoll and showed high use of the marginal habitats between the shallow sand flats and the lagoon. A generalised linear mixed model identified that water temperature, diel cycle and tide were significant predictors of bonefish presence in the lagoon. The high post-release mortality highlights that catch-and-release is likely not as benign as previously believed and management and policy should be adjusted accordingly

Infrared imagery and radiometry Summary report

Thermal properties of infrared transmissio

A922 Sequential measurement of 1 hour creatinine clearance (1-CRCL) in critically ill patients at risk of acute kidney injury (AKI)

Meeting abstrac

Anatomy Teaching, a “Model” Answer? Evaluating “Geoff”, a Painted Anatomical Horse, as a Tool for Enhancing Topographical Anatomy Learning

Development of new methods for anatomy teaching is increasingly important as we look to modernize and supplement traditional teaching methods. In this study, a life‐sized equine model, “Geoff” was painted with surface and deep anatomical structures with the aim of improving students’ ability to convert theoretical knowledge into improved topographical anatomy knowledge on the live horse. Third and fourth year veterinary medicine students (n = 45) were randomly allocated into experimental (used “Geoff”) and control (used textbook) groups. The efficacy of the model was evaluated through a structured oral exam using a live horse. Questionnaires gathered information on student confidence and enjoyment of the task. There was no significant difference in the performance of experimental and control groups either immediately (44±20% vs. 40±21%; P = 0.504) or 9 weeks after the learning intervention (55±17% vs. 55±20%; P = 0.980). There were however specific questions on which the experimental group performed better than controls, and for which gender effects were apparent. The students using “Geoff” showed a transient gain in confidence following the session (Likert scale 2.7 to 3.6) however the initial increase was no longer present at the second test. There was a significant influence of gender on confidence with greater confidence gains in females in the Experimental group. The students found the model to be extremely useful and both groups found the sessions enjoyable. The model will be of benefit as a complementary learning tool for students

Acceptance and commitment therapy processes and their association with distress in cancer: a systematic review and meta-analysis

Around 42% of individuals with cancer experience distress. Acceptance and Commitment Therapy (ACT) can reduce distress, but effects are small, and mechanisms unclear. This review aimed to identify associations between ACT processes and distress in cancer. Search terms included cancer, ACT processes, self-compassion, and distress. Six online databases and grey literature were searched to March 2022. Of 6555 papers screened, 108 studies were included with a total of 17195 participants. Five meta-analyses of seventy-seven studies were conducted. Random effects meta-analyses of correlations revealed higher scores on flexible processes (acceptance, present moment awareness, self-compassion) were associated with lower distress (rpooled = -0.24, -0.39, -0.48, respectively); whilst higher scores on inflexible processes (experiential avoidance, cognitive fusion) were associated with higher distress (rpooled = 0.58, 0.57, respectively). Meta-analyses displayed moderate-to-high heterogeneity with most studies assessed as low risk of bias. Meta-regressions revealed no significant moderators (stage, time since diagnosis, gender and age). This review provides a theoretically aligned evidence base for associations between ACT processes and distress in cancer, supporting elements of ACT theory and providing targeted directions for intervention development. Due to limited evidence, future research should focus on the under-investigated processes (self-as-context, values, committed action) and conducting mediation analysis of ACT processes on distress in cancer in controlled trials

Parasternal intercostal muscle activity during methacholine-induced bronchoconstriction

New Findings: What is the central question of this study? The parasternal intercostal electromyogram (EMGpara) is known to provide an accurate, non-invasive index of respiratory load-capacity balance. Although relationships between EMGpara and both airflow obstruction and hyperinflation have been shown, the independent contribution of each factor has not been examined. What is the main finding and its importance? Reductions in airway calibre and inspiratory capacity along with increases in EMGpara were induced via methacholine challenge. A strong inverse relationship was observed between EMGpara and airway obstruction, with no influence of inspiratory capacity. These data suggest that EMGpara is more strongly influenced by airway calibre than by changes in end-expiratory lung volume during airway challenge testing. Neural respiratory drive, measured via the parasternal intercostal electromyogram (EMGpara), provides a non-invasive index of the load-capacity balance of the respiratory muscle pump. Previous studies in patients with obstructive lung disease have shown strong relationships between EMGpara and the extent of both airflow obstruction and hyperinflation. The relative influence of the two factors has not, however, been described. Airflow obstruction was induced via methacholine challenge testing in 25 adult humans. Forced expiratory volume in 1 s (FEV1) and surface EMGpara during tidal breathing were measured after each dose, with 20 of the participants also undergoing measurements of inspiratory capacity (IC) at each stage. Linear mixed model analysis was used to assess dose-wise changes in FEV1 and EMGpara, and thereafter to determine the influence of changes in FEV1 and IC on change in EMGpara. Median (interquartile range) FEV1 decreased significantly [from 96.00 (80.00-122.30) to 67.80 (37.98-92.27)% predicted, P &lt;0.0001] and EMGpara increased significantly [from 5.37 (2.25-8.92) to 6.27 (3.37-19.60) μV, P &lt;0.0001] from baseline to end of test. Linear mixed model analysis showed a significant interaction between methacholine dose and induced change in EMGpara, with an increase in EMGpara of 0.24 (95% confidence interval 0.11-0.37) μV per methacholine dose2. Change in FEV1 further influenced this relationship [increase in slope of 0.002 (0.004-0.001) μV dose-2 per % predicted fall in FEV1, P = 0.011], but not with change in IC. These data suggest that bronchoconstriction exerts a more potent influence on levels of EMGpara than changes in end-expiratory lung volume during methacholine challenge.</p