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The electronic structures of the diruthenium compounds Ru(ap)Cl (1, ap = 2-anilinopyridinate) and Ru(ap)OTf (2) were investigated with UV-vis, resonance Raman, and magnetic circular dichroism (MCD) spectroscopies; SQUID magnetometry; and density functional theory (DFT) calculations. Both compounds have quartet spin ground states with large axial zero-field splitting of ∼60 cm that is characteristic of Ru compounds having a (π*, δ*) electron configuration and a Ru-Ru bond order of ∼2.5. Two major visible absorption features are observed at ∼770 and 430 nm in the electronic spectra, the assignments of which have previously been ambiguous. Both bands have significant charge-transfer character with some contributions from d → d transitions. MCD spectra were measured to enable the identification of d → d transitions that are not easily observable by UV-vis spectroscopy. In this way, we are able to identify bands due to δ → δ* and δ → π* transitions at ∼16 100 and 11 200-12 300 cm, respectively, the latter band being sensitive to the π-donating character of the axial ligand. The Ru-Ru stretches are coupled with pyridine rocking motions and give rise to observed resonance Raman peaks at ∼350 and 420 cm, respectively.
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http://dx.doi.org/10.1021/acs.inorgchem.7b02557 | DOI Listing |
Radiology
December 2024
From the Oxford Centre for Clinical Magnetic Resonance Research (OCMR), Division of Cardiovascular Medicine, Radcliffe Department of Medicine, University of Oxford, John Radcliffe Hospital, Headley Way, Oxford OX3 9DU, UK (L.E.M.F., M.P.C., M.J., A.S., Z.A., S.N., D.J.T., B.R., L.V.); Oncology and Haematology Centre, Churchill Hospital, Oxford, UK (A.S.); Axcella Therapeutics, Cambridge, Mass (K.A.); and Institute of Measurement Science, Slovak Academy of Sciences, Bratislava, Slovakia (L.V.).
Background Emerging evidence suggests mitochondrial dysfunction may play a role in the fatigue experienced by individuals with post-COVID-19 condition (PCC), commonly called long COVID, which can be assessed using MR spectroscopy. Purpose To compare mitochondrial function between participants with fatigue-predominant PCC and healthy control participants using MR spectroscopy, and to investigate the relationship between MR spectroscopic parameters and fatigue using the 11-item Chalder fatigue questionnaire. Materials and Methods This prospective, observational, single-center study (June 2021 to January 2024) included participants with PCC who reported moderate to severe fatigue, with normal blood test and echocardiographic results, alongside control participants without fatigue symptoms.
View Article and Find Full Text PDFSmall Methods
December 2024
Frumkin Institute of Physical Chemistry and Electrochemistry Russian Academy of Sciences, Leninsky pr., 31, building 4, Moscow, 119071, Russia.
A novel phthalocyanine-based hybrid nanofilm is for the first time successfully applied as an oxidative platform for surface enhanced Raman spectroscopy (SERS) sensing to fine-resolve Raman-inactive compounds. The hybrid is formed by self-assembly of zinc(II) 2,3,9,10,16,17,23,24-Octa[(3',5'-dicarboxy)-phenoxy]phthalocyaninate (ZnPc*) with the solid-supported monolayer of graphene oxide (GO) mediated by zinc acetate metal cluster. Atomic force microscopy, UV-vis and fluorescence spectroscopies confirm that this simple coordination motive in combination with molecular structure of ZnPc* prevents contact quenching of the light-excited triplet state through aromatic stacking with GO particles.
View Article and Find Full Text PDFJ Inorg Biochem
December 2024
Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489 Berlin, Germany. Electronic address:
This study deals with the unprecedented reactivity of a [(cyclam)Mn(OTf)] (3-cis; OTf = CFSO) with O, which, depending on the presence or absence of a hydrogen atom donor like 1-hydroxy-2,2,6,6-tetramethyl-piperidine (TEMPO-H), selectively generates di-μ-oxo Mn(III)Mn(IV) (1) or Mn (2) complexes, respectively. Both dimers have been characterized by different techniques including single-crystal X-ray diffraction, X-ray absorption spectroscopy, and electron paramagnetic resonance. Oxygenation reactions carried out with labeled O and Resonance Raman spectroscopy unambiguously show that the oxygen atoms present in the MnMn dimer originate from O.
View Article and Find Full Text PDFJ Synchrotron Radiat
January 2025
Institute Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Albert-Einstein-Straße 15, 12489 Berlin, Germany.
Resonant inelastic X-ray scattering (RIXS) is an ideal X-ray spectroscopy method to push the combination of energy and time resolutions to the Fourier transform ultimate limit, because it is unaffected by the core-hole lifetime energy broadening. Also, in pump-probe experiments the interaction time is made very short by the same core-hole lifetime. RIXS is very photon hungry so it takes great advantage from high-repetition-rate pulsed X-ray sources like the European XFEL.
View Article and Find Full Text PDFNanoscale
December 2024
Instituto de Física "Gleb Wataghin", Universidade Estadual de Campinas, Campinas, SP 13083-859, Brazil.
We use non-resonant Raman scattering to demonstrate a large enhancement of the effective refractive index experienced by Raman photons in a scattering medium comprising spatially-correlated photonic structures of core-shell TiO@Silica scatterers mixed with silica nanoparticles and suspended in ethanol. We show that the high refractive index extends outside the physical boundary of the medium, which is attributed to the evanescent contributions of electromagnetic modes that are strongly localized within the medium. Notably, the effective enhancement can be observed even at very low intensities of Raman emission.
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