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Herein we report the direct observation of C–H bond activation at an isolated mononuclear Pd( iii ) center. The oxidation of the Pd( ii ) complex ( Me N4)Pd II (neophyl)Cl (neophyl = –CH 2 C(CH 3 ) 2 Ph; Me N4 = N , N ′-dimethyl-2,11-diaza[3.3](2,6)pyridinophane) using the mild oxidant ferrocenium hexafluorophosphate (FcPF 6 ) yields the stable Pd( iii ) complex [( Me N4)Pd III (neophyl)Cl]PF 6 . Upon the addition of an acetate source, [( Me N4)Pd III (neophyl)Cl]PF 6 undergoes Csp 2 –H bond activation to yield the cyclometalated product [( Me N4)Pd III (cycloneophyl)]PF 6 . This metalacycle can be independently prepared, allowing for a complete characterization of both the starting and final Pd( iii ) complexes. The C–H activation step can be monitored directly by EPR and UV-Vis spectroscopies, and kinetic isotope effect (KIE) studies suggest that either a pre-association step such as an agostic interaction may be rate limiting, or that the C–H activation is partially rate-limiting in conjunction with ligand rearrangement. Density functional theory calculations support that the reaction proceeds through a κ 3 ligand coordination and that the flexible ligand structure is important for this transformation. Overall, this study represents the first example of discrete C–H bond activation occurring at a Pd( iii ) center through a concerted metalation–deprotonation mechanism, akin to that observed for Pd( ii ) and Pd( iv ) centers. 

Scientists of the Steward Observatory and Wyant College of Optical Sciences at the University of Arizona created a highly energy efficient adaptable method of forming precision freeform metal panels utilizing the combined effects of induction heating, electromagnetic force, an adjustable mold assembly, and infrared and visible metrology. This transformative component-level manufacturing technology has a broad application in industries requiring custom shaped high accuracy metal sheets (radio communication, automotive, aerospace, renewable energy, architecture). 

Platelets are currently stored at room temperature before transfusion to maximize circulation time. This approach has numerous downsides, including limited storage duration, bacterial growth risk, and increased costs. Cold storage could alleviate these problems. However, the functional consequences of cold exposure for platelets are poorly understood. In the present study, we compared the function of cold-stored platelets (CSP) and room temperature-stored platelets (RSP) in vitro, in vivo, and post-transfusion. CSP formed larger aggregates under in vitro shear while generating similar contractile forces compared to RSP. We found significantly reduced GPVI levels after cold exposure of 5-7 days. After transfusion in humans, CSP were mostly equivalent to RSP yet aggregated significantly less to the GPVI agonist collagen. In a mouse model of platelet transfusion, we found a significantly lower response to the GPVI-dependent agonist convulxin and significantly lower GPVI levels on the surface of transfused platelets after cold storage. In summary, our data support an immediate but short-lived benefit of CSP and highlight the need for thorough investigations of this product. (NCT03787927) 

Abstract We present cosmological results from the measurement of baryon acoustic oscillations (BAO) in galaxy, quasar and Lyman-αforest tracers from the first year of observations from the Dark Energy Spectroscopic Instrument (DESI), to be released in the DESI Data Release 1. DESI BAO provide robust measurements of the transverse comoving distance and Hubble rate, or their combination, relative to the sound horizon, in seven redshift bins from over 6 million extragalactic objects in the redshift range 0.1 <z< 4.2. To mitigate confirmation bias, a blind analysis was implemented to measure the BAO scales. DESI BAO data alone are consistent with the standard flat ΛCDM cosmological model with a matter density Ω_m=0.295±0.015. Paired with a baryon density prior from Big Bang Nucleosynthesis and the robustly measured acoustic angular scale from the cosmic microwave background (CMB), DESI requiresH₀=(68.52±0.62) km s^-1Mpc^-1. In conjunction with CMB anisotropies fromPlanckand CMB lensing data fromPlanckand ACT, we find Ω_m=0.307± 0.005 andH₀=(67.97±0.38) km s^-1Mpc^-1. Extending the baseline model with a constant dark energy equation of state parameterw, DESI BAO alone requirew=-0.99^+0.15_-0.13. In models with a time-varying dark energy equation of state parametrised byw₀andw_a, combinations of DESI with CMB or with type Ia supernovae (SN Ia) individually preferw₀> -1 andw_a< 0. This preference is 2.6σfor the DESI+CMB combination, and persists or grows when SN Ia are added in, giving results discrepant with the ΛCDM model at the 2.5σ, 3.5σor 3.9σlevels for the addition of the Pantheon+, Union3, or DES-SN5YR supernova datasets respectively. For the flat ΛCDM model with the sum of neutrino mass ∑m_νfree, combining the DESI and CMB data yields an upper limit ∑m_ν< 0.072 (0.113) eV at 95% confidence for a ∑m_ν> 0 (∑m_ν> 0.059) eV prior. These neutrino-mass constraints are substantially relaxed if the background dynamics are allowed to deviate from flat ΛCDM.