paramagnetic

Biological phosphates can coordinate metal ions and their complexes are common in living systems. Dynamics of mutual oxygen atom exchange in the tetrahedral group in complexes has not been investigated. Here, we present a direct experimental proof of the exchange ("phosphonate rotation") in model Ln(III) complexes of monophosphonate H4dota analogue which alters phosphorus atom chirality of coordinated phosphonate monoester. Combination of macrocycle-based isomerism with P-based chirality leads to several diastereoisomers...

Transition and rare earth metals serve as indispensable raw materials across a broad spectrum of technological applications. However, their utilization is frequently linked to substantial waste production. Consequently, the recycling and recovery of these metals from end-of-life products or metal-contaminated aqueous environments hold significant importance within the framework of a circular economy. In our investigation, we employed synthetic mesoporous silica monoliths, synthesized via the sol-gel method and functionalized with chelating groups, for the efficient recovery of metal ions from aqueous matrices...

The spinels ZnAl1.99- x Ho x Cr0.01 O4 (with x = 0 and 0.001) were synthesized using a solid-state method, and various techniques were employed for their characterization. X-ray diffraction (XRD) analysis confirmed a cubic spinel structure with the Fd 3̄ m space group for both spinels. The morphology and homogeneity of the chemical composition were determined using scanning electron microscopy (SEM) and energy dispersive X-ray analysis. Raman and infrared vibrational spectroscopy techniques were also employed for analysis...

We designed [VO(bdhb)] ( 1 ') as a new electronic qubit containing an oxovanadium(IV) ion ( S = 1/2) embraced by a single bis(β-diketonato) ligand [H2 bdhb = 1,3-bis(3,5-dioxo-1-hexyl)benzene]. The synthesis afforded three different crystal phases, all of which unexpectedly contain dimers with formula [(VO)2 (bdhb)2 ] ( 1 ). A trigonal form ( 1 h ) with a honeycomb structure and 46% of solvent-accessible voids quantitatively transforms over time into a monoclinic solvatomorph 1 m and minor amounts of a triclinic solventless phase ( 1 a )...

Molecular lanthanide (Ln) complexes are promising candidates for the development of next-generation quantum technologies. High-symmetry structures incorporating integer spin Ln ions can give rise to well-isolated crystal field quasi-doublet ground states, i.e., quantum two-level systems that may serve as the basis for magnetic qubits. Recent work has shown that symmetry lowering of the coordination environment around the Ln ion can produce an avoided crossing or clock transition within the ground doublet, leading to significantly enhanced coherence...

The chemical shielding tensor for a paramagnetic system has been derived from the macroscopically observed magnetization using the perturbation theory. An approach to calculate the paramagnetic chemical shifts in transition metal systems based on the spin-only magnetic susceptibility directly evaluated from the ab initio Hilbert space of the electronic Zeeman Hamiltonian has been discussed. Computationally, several advantages are associated with this approach: (a) it includes the state-specific paramagnetic Curie (first-order) and Van Vleck (second-order) contributions of the paramagnetic ion to the paramagnetic chemical shifts; (b) thus it avoids the system-specific modeling and evaluating effectively in terms of the electron paramagnetic resonance (EPR) spin Hamiltonian parameters of the magnetic moment of the paramagnetic ion formulated previously; (c) it can be utilized both in the point-dipole (PD) approximation (in the long-range) and with the quantum chemical (QC) method based the hyperfine tensors (in the short-range)...

Actinides are inherently radioactive; thus, ionizing radiation is emitted by these elements can have profound effects on its surrounding chemical environment through the formation of free radical species. While previous work has noted that the presence of free radicals in the system impacts the redox state of the actinides, there is little atomistic understanding of how these metal cations interact with free radicals. Herein, we explore the effects of radiation (UV and γ) on three U(VI) trinitrate complexes, M[UO2(NO3)3] (where M = K+, Rb+, Cs+), and their respective nitrate salts in the solid state via electron paramagnetic resonance (EPR) and Raman spectroscopy paired with Density Functional Theory (DFT) methods...

Reactive oxygen species (ROS) are highly unstable oxygen-containing molecules. Their chemical instability makes them extremely reactive and gives them the ability to react with important biological molecules such as proteins, nucleic acids, and lipids. Superoxide anions are important ROS generated by the reduction of molecular oxygen reduction (i.e., acquisition of one electron). Despite their initial implication exclusively in aging, degenerative, and pathogenic processes, their participation in important physiological responses has recently become apparent...

Understanding and tuning epitaxial complex oxide films are crucial in controlling the behavior of devices and catalytic processes. Substrate-induced strain, doping, and layer growth are known to influence the electronic and magnetic properties of the bulk of the film. In this study, we demonstrate a clear distinction between the bulk and surface of thin films of La0.67 Sr0.33 MnO3 in terms of chemical composition, electronic disorder, and surface morphology. We use a combined experimental approach of X-ray-based characterization methods and scanning probe microscopy...

Photocatalytic water splitting using covalent organic frameworks (COFs) is a promising approach for harnessing solar energy. However, challenges such as slow kinetic dynamics in the photocatalytic oxygen evolution reaction (OER) and COFs' self-oxidation hinder its progress. In this study, an enamine-based COF coordinated is introduced with cobalt dichloride, CoCl2 (CoCl2 -TpBPy). The coordination of cobalt ions with bipyridines in CoCl2 -TpBPy enhances charge-carrier separation and migration, leading to effective photocatalytic OER...

Ferroelectric polymers are of great interest due to their intrinsic processing capabilities, superior to classic inorganic ferroelectric materials. For example, polyvinylidene fluoride (PVDF) and derivatives have been incorporated into multiple device architectures for information storage and transfer. Here we report an additional advantage of organic ferroelectrics as their flexibility allows for the preparation of composites with spin crossover (SCO) probes to tune their ferroelectric parameters by external stimuli...

Given the presence of emerging pollutants at low concentrations in water bodies, which are inevitably affected by background substances during the removal process. In this study, we synthesized molecularly imprinted catalysts (Cu/Ni-MOFs@MIP) based on bimetallic metal-organic frameworks for the targeted degradation of ciprofloxacin (CIP) in advanced oxidation processes (AOPs). The electrostatic interaction and functional group binding of CIP with specific recognition sites on Cu/Ni-MOFs@MIP produced excellent selective recognition (Qmax was 14...

Metronidazole (MNZ), a commonly used antibiotic, poses risks to water bodies and human health due to its potential carcinogenic, mutagenic, and genotoxic effects. In this study, mesoporous cobalt-manganese layered double hydroxides (Cox Mny -LDH) with abundant oxygen vacancies (Ov ) were successfully synthesized using the co-precipitation method and used to activate calcium sulfite (CaSO3 ) with slight soluble in water for MNZ degradation. The characterization results revealed that Co2 Mn-LDH had higher specific areas and exhibited good crystallinity...

The enhancement of charge separation and utilization efficiency in both the bulk phase and interface of semiconductor photocatalysts, as well as the expansion of light absorption range, are crucial research topics in the field of photocatalysis. To address this issue, twinned Cd0.5 Zn0. 5S (T-CZS) homojunctions consisting of wurtzite Cd0.5 Zn0.5 S (WZ-CZS) and zinc blende Cd0.5 Zn0.5 S (ZB-CZS) were synthesized via a hydrothermal method to facilitate the bulk-phase charge separation. Meanwhile, Cu2-x Se with localized surface plasmon resonance effect (LSPR) generated by Cu vacancies was also obtained through a hydrothermal process...

Nitric oxide (NO) is a key signalling molecule released by vascular endothelial cells that is essential for vascular health. Low NO bioactivity is associated with cardiovascular diseases, such as hypertension, atherosclerosis, and heart failure and NO donors are a mainstay of drug treatment. However, many NO donors are associated with the development of tolerance and adverse effects, so new formulations for controlled and targeted release of NO would be advantageous. Herein, we describe the design and characterisation of a novel NO delivery system via the reaction of acidified sodium nitrite with thiol groups that had been introduced by cysteamine conjugation to porous graphene oxide nanosheets, thereby generating S-nitrosated nanosheets...

In cancer diagnostics, magnetic resonance imaging (MRI) uses contrast agents to enhance the distinction between the target tissue and background. Several promising approaches have been developed to increase MRI sensitivity, one of which is Overhauser dynamic nuclear polarization (ODNP)-enhanced MRI (OMRI). In this study, a macromolecular construct based on human serum albumin and nitroxyl radicals (HSA-NIT) was developed using a new synthesis method that significantly increased the modification to 21 nitroxide residues per protein...

The administration of magnetic resonance imaging (MRI) contrast agents (CAs) has been conducted since 1988 by clinicians to enhance the clarity and interpretability of MR images. CAs based on gadolinium chelates are the clinical standard used worldwide for the diagnosis of various pathologies, such as the detection of brain lesions, the visualization of blood vessels, and the assessment of soft tissue disorders. However, due to ongoing concerns associated with the safety of gadolinium-based contrast agents, considerable efforts have been directed towards developing contrast agents with better relaxivities, reduced toxicity, and eventually combined therapeutic modalities...

Dinitrosyl iron complexes (DNICs) stabilize nitric oxide in cells and tissues and constitute an important form of its storage and transportation. DNICs may comprise low-molecular-weight ligands, e.g., thiols, imidazole groups in chemical compounds with low molecular weight (LMWDNICs), or high-molecular-weight ligands, e.g., peptides or proteins (HMWDNICs). The aim of this study was to investigate the role of low- and high-molecular-weight ligands in DNIC formation. Lysosomal and proteasomal proteolysis was inhibited by specific inhibitors...

Nowadays, super nitrogen-doped biochar (SNBC) material has become one of the most promising metal-free catalysts for activating peroxymonosulfate (PMS) to degrade organic pollutants. To understand the evolution of SNBC properties with fabrication conditions, a variety of SNBC materials were prepared and characterized by elemental analysis, N2 adsorption-desorption, scanning electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction...

Inspired by the potential of alkoxides as weak-field ligands and their ability to bridge, we report herein a series of high-spin iron complexes supported by a bis-alkoxide framework Ph Dbf . A diiron complex [Fe2 (Ph Dbf)2 ] ( 1a ) is obtained upon metalation of the ligand, whereas addition of substituted pyridines affords five-coordinate mononuclear iron complexes [(R-Py)2 Fe(Ph Dbf)] ( 2a - 4a , R = H, p - t Bu, p -CF3 ). The potential for nuclearity control of the metal complexes via auxiliary ligands is highlighted by the formation of asymmetric diiron species [( p -CF3 -Py)Fe2 (Ph Dbf)2 ] ( 5a ) and [( m -CF3 -Py)Fe2 (Ph Dbf)2 ] ( 6a ) with trifluoromethyl substituted pyridines, while electron-rich pyridines only produced monomeric species...