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Asymmetry-enhanced Co NMR thermometry in Co(iii) complexes.
Inorg Chem Front
November 2023
Department of Chemistry, Colorado State University Fort Collins Colorado 80523 USA
Design strategies for molecular thermometers by magnetic resonance are essential for enabling new noninvasive means of temperature mapping for disease diagnoses and treatments. Herein we demonstrate a new design strategy for thermometry based on chemical control of the vibrational partition function. To do so, we performed variable-temperature Co NMR investigations of four air-stable Co(iii) complexes: Co(accp) (1), Co(bzac) (2), Co(Bu-acac) (3), and Co(acac) (4) (accp = 2-acetylcyclopentanonate; bzac = benzoylacetonate; Bu-acac = 2,2,6,6-tetramethyl-3,5-heptanedionate and acac = acetylacetonate).
View Article and Find Full Text PDFExposing the Oxygen-Centered Radical Character of the Tetraoxido Ruthenium(VIII) Cation [RuO ].
Chemphyschem
November 2023
Physikalisches Institut, Albert-Ludwigs-Universität Freiburg, Hermann-Herder-Straße 3, 79104, Freiburg, Germany.
The tetraoxido ruthenium(VIII) radical cation, [RuO ] , should be a strong oxidizing agent, but has been difficult to produce and investigate so far. In our X-ray absorption spectroscopy study, in combination with quantum-chemical calculations, we show that [RuO ] , produced via oxidation of ruthenium cations by ozone in the gas phase, forms the oxygen-centered radical ground state. The oxygen-centered radical character of [RuO ] is identified by the chemical shift at the ruthenium M edge, indicative of ruthenium(VIII), and by the presence of a characteristic low-energy transition at the oxygen K edge, involving an oxygen-centered singly-occupied molecular orbital, which is suppressed when the oxygen-centered radical is quenched by hydrogenation of [RuO ] to the closed-shell [RuO H] ion.
View Article and Find Full Text PDFAlkaline pH in intracranial tuberculomas: A Phosphorus magnetic resonance spectroscopy study.
J Neurosci Rural Pract
December 2022
Department of Radio-Diagnosis, Jawaharlal Institute of Postgraduate Medical Education and Research, Puducherry, India.
Objectives: Intracranial tuberculomas are one of the common causes of space-occupying lesions of the brain in developing countries. Proton (H) magnetic resonance spectroscopy (MRS) has shown lipid peak in intracranial tuberculomas as a characteristic feature. Phosphorus (P) MRS has been used to evaluate intracranial lesions and to calculate tissue pH non-invasively.
View Article and Find Full Text PDFPredicting dinitrogen activation by borenium and borinium cations.
Phys Chem Chem Phys
June 2022
State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China.
The activation of thermodynamically stable and kinetically inert dinitrogen (N) has been a great challenge due to the significant strength of the triple bond. Recently, in an experimental study on N activation by boron species, a highly reactive two-coordinated borylene broke through the limitations of traditional strategies of N activation by metal species. Still, studies on metal-free N activation remain underdeveloped.
View Article and Find Full Text PDFMR-based proton density fat fraction (PDFF) of the vertebral bone marrow differentiates between patients with and without osteoporotic vertebral fractures.
Osteoporos Int
February 2022
Department of Radiology, Klinikum Rechts Der Isar, School of Medicine, Technical University of Munich, Ismaningerstr. 22, 81675, Munich, Germany.
Unlabelled: The bone marrow proton density fat fraction (PDFF) assessed with MRI enables the differentiation between osteoporotic/osteopenic patients with and without vertebral fractures. Therefore, PDFF may be a potentially useful biomarker for bone fragility assessment.
Introduction: To evaluate whether magnetic resonance imaging (MRI)-based proton density fat fraction (PDFF) of vertebral bone marrow can differentiate between osteoporotic/osteopenic patients with and without vertebral fractures.
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