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| http://dx.doi.org/10.1021/acscentsci.3c01225 | DOI Listing |
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Synthesis, Structure, and Redox Reactivity of Ni Complexes Bearing a Redox and Acid-Base Non-innocent Ligand with Ni, Ni, and Ni Formal Oxidation States.
J Am Chem Soc
January 2025
Department of Chemistry and Nano Science, Ewha Womans University, Seoul 03760, Korea.
A series of Ni complexes bearing a redox and acid-base noninnocent tetraamido macrocyclic ligand, H-(TAML-4) {H-(TAML-4) = 15,15-dimethyl-5,8,13,17-tetrahydro-5,8,13,17-tetraaza-dibenzo[]cyclotridecene-6,7,14,16-tetraone}, with formal oxidation states of Ni, Ni, and Ni were synthesized and characterized structurally and spectroscopically. The X-ray crystallographic analysis of the Ni complexes revealed a square planar geometry, and the [Ni(TAML-4)] complex with the formal oxidation state of Ni was characterized to be [Ni(TAML-4)] with the oxidation state of the Ni ion and the one-electron oxidized TAML-4 ligand, TAML-4. The Ni oxidation state and the TAML-4 radical cation ligand, TAML-4, were supported by X-ray absorption spectroscopy and density functional theory calculations.
View Article and Find Full Text PDFRectification of planar orientation angle switches behavior and replenishes contractile junctions.
J Cell Biol
April 2025
Department of Physics and Astronomy, University of Denver, Denver, CO, USA.
In the early Drosophila embryo, germband elongation is driven by oriented cell intercalation through t1 transitions, where vertical (dorsal-ventral aligned) interfaces contract and then resolve into new horizontal (anterior-posterior aligned) interfaces. Here, we show that contractile events produce a continuous "rectification" of cell interfaces, in which interfaces systematically rotate toward more vertical orientations. As interfaces rotate, their behavior transitions from elongating to contractile regimes, indicating that the planar polarized identities of cell-cell interfaces are continuously re-interpreted in time depending on their orientation angle.
View Article and Find Full Text PDFWhole Brain MRI Assessment of Age and Sex-Related R2* Changes in the Human Fetal Brain.
Hum Brain Mapp
February 2025
Department of Child and Adolescent Psychiatry, New York University School of Medicine, New York, New York, USA.
Iron in the brain is essential to neurodevelopmental processes, as it supports neural functions, including processes of oxygen delivery, electron transport, and enzymatic activity. However, the development of brain iron before birth is scarcely understood. By estimating R2* (1/T2*) relaxometry from a sizable sample of fetal multiecho echo-planar imaging (EPI) scans, which is the standard sequence for functional magnetic resonance imaging (fMRI), across gestation, this study investigates age and sex-related changes in iron, across regions and tissue segments.
View Article and Find Full Text PDFSynthesis and characterization of heterotrimetallic Mg-Ni-Mg complexes with amidinato ligands.
Dalton Trans
January 2025
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China.
Treatment of amidinato-based magnesium ethyl compounds LMgEt [L = PrPNC(Bu)NAr; Ar = 2,6-PrCH (La) or 2,6-(PhCH)-4-Pr-(CH) (Lb)] with Ni(COD) (COD: 1,5-cyclooctadiene) afforded heterotrimetallic Mg-Ni-Mg complexes [(LMg)Ni(CH)] through β-H elimination. These complexes exhibit approximately linear Mg-Ni-Mg linkage with the central nickel arranged in a planar configuration; the Ni(CH) unit can be considered as nickela-bis-cyclopropane. Reaction of [(LMg)Ni(CH)] with tetrahydrofuran (THF) gave a coordination product [(LMg·THF)Ni(CH)], in which the central structure remained intact and THF coordinated to two magnesium atoms respectively.
View Article and Find Full Text PDFRecent advances in synthesis and application of Magnéli phase titanium oxides for energy storage and environmental remediation.
Chem Sci
January 2025
Applied Chemistry and Environmental Science, School of Science, STEM College, RMIT University Melbourne Victoria 3000 Australia
High-temperature reduction of TiO causes the gradual formation of structural defects, leading to oxygen vacancy planar defects and giving rise to Magnéli phases, which are substoichiometric titanium oxides that follow the formula Ti O, with 4 ≤ ≤ 9. A high concentration of defects provides several possible configurations for Ti and Ti within the crystal, with the variation in charge ordered states changing the electronic structure of the material. The changes in crystal and electronic structures of Magnéli phases introduce unique properties absent in TiO, facilitating their diverse applications.
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