CpCo(III) Precatalysts for [2+2+2] Cycloadditions

Catalysts applied in cobalt-catalyzed cyclotrimerizations reactions in general rely on the use of Co(I) precatalysts or the in situ generation of Co(I) catalysts from Co(II) sources by reduction in the presence of steering ligands, often by addition of less noble metals. In this paper, we report the synthesis and properties of novel stable CpCo(III) complexes as precatalysts and their exemplary evaluation for application in catalytic [2+2+2] cycloadditions. The role of phosphite neutral ligands, as well as iodide and cyanide as anionic ligands, on the reactivity of the complexes was evaluated. A modified one-pot approach to the synthesis of Cp ring-functionalized Cp’Co(III) complexes was developed. The investigations demonstrated that CpCo(III) complexes can be directly applied as catalysts in catalytic cyclotrimerizations of triynes without reducing agents as additives. © 2021 by the authors. Licensee MDPI, Basel, Switzerland

Management of proximal femur fractures in the elderly: current concepts and treatment options

As one of the leading causes of elderly patients' hospitalisation, proximal femur fractures (PFFs) will present an increasing socioeconomic problem in the near future. This is a result of the demographic change that is expressed by the increasing proportion of elderly people in society. Peri-operative management must be handled attentively to avoid complications and decrease mortality rates. To deal with the exceptional needs of the elderly, the development of orthogeriatric centres to support orthogeriatric co-management is mandatory. Adequate pain medication, balanced fluid management, delirium prevention and the operative treatment choice based on comorbidities, individual demands and biological rather than chronological age, all deserve particular attention to improve patients' outcomes. The operative management of intertrochanteric and subtrochanteric fractures favours intramedullary nailing. For femoral neck fractures, the Garden classification is used to differentiate between non-displaced and displaced fractures. Osteosynthesis is suitable for biologically young patients with non-dislocated fractures, whereas total hip arthroplasty and hemiarthroplasty are the main options for biologically old patients and displaced fractures. In bedridden patients, osteosynthesis might be an option to establish transferability from bed to chair and the restroom. Postoperatively, the patients benefit from early mobilisation and early geriatric care. During the COVID-19 pandemic, prolonged time until surgery and thus an increased rate of complications took a toll on frail patients with PFFs. This review aims to offer surgical guidelines for the treatment of PFFs in the elderly with a focus on pitfalls and challenges particularly relevant to frail patients

Cross-cultural evidence of value structures and priorities in childhood

We broaden the developmental focus of the theory of universals in basic human values (Schwartz, 1992) by presenting supportive evidence on children’s values from six countries: Germany, Italy, Poland, Bulgaria, the USA, and New Zealand. 3,088 7-11-year-old children completed the Picture-Based Value Survey for Children (PBVS-C, Döring et al., 2010). Grade 5 children also completed the Portrait Values Questionnaire (PVQ, Schwartz, 2003). Findings reveal that the broad value structures, sex-differences in value priorities, and pan-cultural value hierarchies typical of adults have already taken form at this early age. We discuss the conceptual implications of these findings for the new field of children’s basic values by embedding them in the recent developmental literature

The Mass of HD 38529 c from Hubble Space Telescope Astrometry and High-Precision Radial Velocities

(Abridged) Hubble Space Telescope (HST) Fine Guidance Sensor astrometric observations of the G4 IV star HD 38529 are combined with the results of the analysis of extensive ground-based radial velocity data to determine the mass of the outermost of two previously known companions. Our new radial velocities obtained with the Hobby-Eberly Telescope and velocities from the Carnegie-California group now span over eleven years. With these data we obtain improved RV orbital elements for both the inner companion, HD 38529 b and the outer companion, HD 38529 c. We identify a rotational period of HD 38529 (P_{rot}=31.65 +/- 0.17 d) with FGS photometry. We model the combined astrometric and RV measurements to obtain the parallax, proper motion, perturbation period, perturbation inclination, and perturbation size due to HD 38529 c. For HD 38529 c we find P = 2136.1 +/- 0.3 d, perturbation semi-major axis \alpha =1.05 +/-0.06$mas, and inclination$i$= 48.3 deg +/- 4 deg. Assuming a primary mass M_* = 1.48 M_{sun}, we obtain a companion mass M_c = 17.6 ^{+1.5}_{-1.2} M_{Jup}, 3-sigma above a 13 M_{Jup} deuterium burning, brown dwarf lower limit. Dynamical simulations incorporating this accurate mass for HD 38529 c indicate that a near-Saturn mass planet could exist between the two known companions. We find weak evidence of an additional low amplitude signal that can be modeled as a planetary-mass (~0.17 M$_{Jup}) companion at P~194 days. Additional observations (radial velocities and/or Gaia astrometry) are required to validate an interpretation of HD 38529 d as a planetary-mass companion. If confirmed, the resulting HD 38529 planetary system may be an example of a "Packed Planetary System".Comment: Accepted by The Astronomical Journa

The "Lake of Olympia": geoarchaeological evidence of a lake environment in the vicinity of ancient Olympia (western Peloponnese, Greece)

Our results yield evidence of a large lake environment that existed near the ancient site of Olympia which was so far unknown. The limnic sequence reveals considerable changes in the ecological conditions over time, based on Direct Push sensing, sedimentary and micropalaeontological analyses. Radiocarbon data show that the “Lake of Olympia“ existed from the 8th/7th millennium BC until, at least, the 1st century AD. The existence of the “Lake of Olympia” next to the cult site of Olympia has considerable historical, archaeological and geographical implications (e.g., as waterway or water supplier)