Lanthanides are widely assumed not to form covalent bonds due to the localized nature of their 4f valence electrons. This work demonstrates that the ionic bond of Sm(II) with cyclononatetraenyl (η-CH) in [Sm(η-CH)] can be modulated and becomes more covalent by photon-induced transfer of Sm 4f electrons to Sm 5d orbitals. This photon-induced change in bonding properties facilitates a subsequent reconfiguration of [Sm(η-CH)]. As a result, Sm-C bond length contraction is detected and the local Sm coordination environment exhibits more extensive disorder. Both Sm 4f and 5d electrons have increased participation in covalent Sm-ligand interactions. The Sm L-edge valence band resonant inelastic X-ray scattering (VB-RIXS), high-resolution X-ray absorption near-edge structure (HR-XANES), and quantum chemical computations showcase a spectroscopic methodology for in-depth studies of bond covalency of lanthanide atoms.

Download full-text PDF

Source
http://dx.doi.org/10.1021/jacs.3c13934DOI Listing

Publication Analysis

Top Keywords

bond covalency
8
photon-modulated bond
4
covalency [smiiη-ch]
4
[smiiη-ch] lanthanides
4
lanthanides assumed
4
assumed form
4
form covalent
4
covalent bonds
4
bonds localized
4
localized nature
4

Similar Publications

This study explores the synergistic effects of linoleic acid (LA) oxidation on the aggregation behavior and structural properties of wheat gluten (WG). Using lipoxygenase to induce LA oxidation, it was observed that this process significantly influenced WG's viscoelasticity and structural characteristics. Specifically, LA oxidation enhanced WG's viscoelastic properties while reducing its instantaneous elastic and recovery deformations.

View Article and Find Full Text PDF

variants in children with neurodevelopmental impairment are difficult to assess due to their heterogeneity and unclear pathogenic mechanisms. We describe a child with neonatal-onset epilepsy, developmental impairment of intermediate severity, and G256W heterozygosity. Analyzing prior KCNQ2 channel cryoelectron microscopy models revealed G256 as a node of an arch-shaped non-covalent bond network linking S5, the pore turret, and the ion path.

View Article and Find Full Text PDF

Covalent Inhibitor Screening for Targeting LOXL2: Studied by Virtual Screening and Experimental Validation.

Recent Pat Anticancer Drug Discov

January 2025

Department of Biochemistry and Molecular Biology, Shantou University Medical College, Shantou, 515041, PR China.

Background: Lysyl oxidase-like 2 (LOXL2) is a metalloenzyme that catalyzes oxidative deamination ε-amino group of lysine. It has been found that LOXL2 is a promotor for the metastasis and invasion in kinds of tumors. Previous studies show that disulfide bonds are important components in LOXL2, and their bioactivity can be regulated by those bonds.

View Article and Find Full Text PDF

MXenes quantum dots (QDs), including NbC, NbCO, and NbCF, are emerging materials with exceptional structural, electronic, and optical properties, making them highly suitable for biomedical applications. This study investigates the structural optimization, stability, electronic properties, and drug-loading potential of these QDs using fluorouracil (Flu) as a model drug. Structural analyses show that the functionalization of NbC with O and F atoms enhances stability, with binding energies (BEs) of 7.

View Article and Find Full Text PDF

Investigation of serotonin-receptor interactions, stability and signal transduction pathways via molecular dynamics simulations.

Biophys Chem

December 2024

Department of Chemistry and Center for Atomic, Molecular, Optical Sciences and Technologies (CAMOST), Indian Institute of Science, Education and Research (IISER) Tirupati, Yerpedu Mandal, Tirupati 517619, India. Electronic address:

Serotonin-receptor binding plays a key role in several neurological and biological processes, including mood, sleep, hunger, cognition, learning, and memory. In this article, we performed molecular dynamics simulation to examine the key residues that play an essential role in the binding of serotonin to the G-protein-coupled 5-HT receptor (5HTR) via electrostatic interactions. Key residues for electrostatic interactions were identified via bond distance analysis and frustration analysis methods.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!