[structure: see text] The free energy of activation, deltaG*, for nitrogen inversion was calculated from the coalescence temperature for the methyl signals obtained via variable temperature NMR for a series of imino derivatives of the title compounds. There was a direct correlation between the long-range nonbonding circumannular orbital interactions between the heteroatoms in the 1,3-positions and the deltaG* for inversion of groups on nitrogen. Values of deltaG* range from 26 kcal/mol on systems with maximum interaction in the transition state (I and II) to 17 kcal/mole on those systems with minimal interaction (III and IV).
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Inorg Chem
January 2025
University of Göttingen, Institute of Inorganic Chemistry, Tammannstrasse 4, D-37077 Göttingen, Germany.
Alkyl nickel intermediates relevant to catalytic processes often feature agostic stabilization, but relatively little is known about the situation in oligonickel systems. The dinickel(I) complex K[LNi], which is based on a compartmental pyrazolato-bridged ligand L with two β-diketiminato chelate arms, or its masked version, the dihydride complex [KL(Ni-H)] that readily releases H, oxidatively add methyl tosylate to give diamagnetic [LNi(CH)] () with (Ni···Ni) ≈ 3.7 Å.
View Article and Find Full Text PDFLangmuir
January 2025
Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India.
Plasma membrane (PM) simulations at longer length and time scales at nearly atomistic resolution can provide invaluable insights into cell signaling, apoptosis, lipid trafficking, and lipid raft formation. We propose a coarse-grained (CG) model of a mammalian PM considering major lipid head groups distributed asymmetrically across the membrane bilayer and validate the model against bilayer structural properties from atomistic simulation. Using the proposed CG model, we identify a recurring pattern in the passive collective cholesterol transbilayer motion and study the individual cholesterol flip-flop events and associated pathways along with lateral ordering in the bilayer during a flip-flop event.
View Article and Find Full Text PDFJ Phys Condens Matter
January 2025
AIMR, Tohoku University, 2-1-1, Katahira, Aoba-ku, Sendai, 980-8578, JAPAN.
Monolayer atomic thin films of group-V elements have a high potential for application in spintronics and valleytronics because of their unique crystal structure and strong spin-orbit coupling. We fabricated Sb and Bi monolayers on a SiC(0001) substrate by the molecular-beam-epitaxy method and studied the electronic structure by angle-resolved photoemission spectroscopy (ARPES) and first-principles calculations. The fabricated Sb film shows the (√3×√3)R30º superstructure associated with the formation of ⍺-Sb, and exhibits a semiconducting nature with a band gap of more than 1.
View Article and Find Full Text PDFPhysiother Res Int
January 2025
College of Rehabilitation Sciences, Shanghai University of Medicine and Health Sciences, Shanghai, China.
Background: Proprioceptive deficits are common among stroke survivors and can negatively impact their balance and postural control. However, there has been little evaluation of the change in proprioceptive deficits in the lower limbs over time after stroke. This study aimed to examine proprioceptive deficits over time after stroke in both the affected and "unaffected" lower limbs.
View Article and Find Full Text PDFNeuromuscul Disord
December 2024
Service de Neuromyologie, Centre de référence des maladies neuromusculaires Nord/Est/Ile de France Institut de Myologie, Sorbonne Université, APHP, Paris, France. Electronic address:
Dysferlinopathies, caused by mutations in the dysferlin gene (DYSF) encoding the dysferlin protein, are a clinically heterogeneous group of autosomal recessive muscular dystrophies whose phenotypic spectrum is still evolving. Here we described a patient reporting diffuse muscular pain non related to physical exercise, mimicking fibromyalgic syndrome. Electroneuromyography was normal.
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