Synthesis, Stability and Relaxivity of TEEPO-Met : An Organic Radical as a Potential Tumour Targeting Contrast Agent for Magnetic Resonance Imaging

Cancer is a widespread and life-threatening disease and its early-stage diagnosis is vital. One of the most effective, non-invasive tools in medical diagnostics is magnetic resonance imaging (MRI) with the aid of contrast agents. Contrast agents that are currently in clinical use contain metals, causing some restrictions in their use. Also, these contrast agents are mainly non-specific without any tissue targeting capabilities. Subsequently, the interest has notably increased in the research of organic, metal-free contrast agents. This study presents a new, stable organic radical, TEEPO-Met, where a radical moiety 2,2,6,6-tetraethylpiperidinoxide (TEEPO) is attached to an amino acid, methionine (Met), as a potentially tumour-targeting moiety. We describe the synthesis, stability assessment with electron paramagnetic resonance (EPR) spectroscopy and relaxation enhancement abilities by an in vitro nuclear magnetic resonance (NMR) and phantom MRI studies of TEEPO-Met. The new compound proved to be stable notably longer than the average imaging time in conditions mimicking a biological matrix. Also, it significantly reduced the relaxation times of water, making it a promising candidate as a novel tumour targeting contrast agent for MRI.Peer reviewe

Alkyl-Substituted Aminobis(phosphonates) : Efficient Precipitating Agents for Rare Earth Elements, Thorium, and Uranium in Aqueous Solutions

The efficient and environmentally sustainable separation process for rare earth elements (REE), especially for adjacent lanthanoids, remains a challenge due to the chemical similarity of REEs. Tetravalent actinoids, thorium, and traces of uranium are also present in concentrates of REEs, making their separation relevant. This study reports six simple water-soluble aminobis(phosphonate) ligands, RN[CH2P(O)(OH)2]2 (1 R = CH2CH3, 2 R = (CH2)2CH3, 3 R = (CH2)3CH3, 4 R = (CH2)4CH3, 5 R = (CH2)5CH3, 6 R = CH2CH(C2H5)(CH2)3CH3) as precipitating agents for REEs, Th, and U, as well as gives insight into the coordination modes of the utilized ligands with REEs at the molecular level. Aminobis(phosphonates) 4–6 with longer carbon chains were found to separate selectively thorium, uranium, and scandium from REEs with short precipitation time (15 min) and excellent separation factors that generally range from 100 to 2000 in acidic aqueous solution. Ligands 1–6 also improved separation factors for adjacent lanthanoids in comparison to traditional oxalate precipitation agents. Importantly, precipitated metals can be recovered from the ligands with 3 molar HNO3 with no observed ligand decomposition enabling the possibility of recycling the ligands in the separation process. NMR-monitored pH titrations for 1 showed deprotonation steps at pKa 1.3, 5.55, and >10.5, which indicate that the ligands remain in a deprotonated [L]−1 form in the pH range of 0–4 used in the precipitation studies. 31P NMR titration studies between 1 and M(NO3)3 (M = Y, La, Lu) gave satisfactory fits for 1:3, 1:2, and 1:1 metal–ligand stoichiometries for Y, La, and Lu, respectively, according to an F-test. Therefore, aminobis(phosphonate) precipitation agents 1–6 are likely to form metal complexes with fewer ligands than traditional separation agents like DEHPA, which coordinates to REEs in 1:6 metal–ligand ratio.peerReviewe

Halogen-Bonded Mono-, Di-, and Tritopic N-Alkyl-3-iodopyridinium Salts

Halogen bonding interactions of 15 crystalline 3-iodopyridinium systems were investigated. These systems were derived from four N-alkylated 3-iodopyridinium salts prepared in this study. The experimental results in the solid state show that halogen bonding acts as a secondary intermolecular force in these charged systems but sustains the high directionality of interaction in the presence of other intermolecular forces. Halogen bonds donated by polytopic 3-iodopyridinium cations are also sufficient to enclose guest molecules inside the formed supramolecular cavities. The experimental data were supplemented by computational gas-phase and solid-state studies for selected halogen-bonded systems. Calculations of the model systems with the increasing number of halogen bond donors and acceptors showed the halogen bond strengths to be exaggerated for the smallest of model systems. The agreement between experimental and calculated structures improved for larger systems that were able to account for the influence of other intermolecular interactions. The best agreement between experimental and calculated structural parameters were found for solid-state calculations with periodic boundary conditions. Comparison of the halogen bond interaction strengths with the strength of other lattice interactions showed the halogen bonds to come second to electrostatic interactions in stabilizing the structures but having a major role in directing the packing of the solid-state structures.peerReviewe

Anion-driven encapsulation of cationic guests inside pyridine[4]arene dimers

Pyridine[4]arenes have previously been considered as anion binding hosts due to the electron-poor nature of the pyridine ring. Herein, we demonstrate the encapsulation of Me4N+ cations inside a dimeric hydrogen-bonded pyridine[4]arene capsule, which contradicts with earlier assumptions. The complexation of a cationic guest inside the pyridine[4]arene dimer has been detected and studied by multiple gas-phase techniques, ESI-QTOF-MS, IRMPD, and DT-IMMS experiments, as well as DFT calculations. The comparison of classical resorcinarenes with pyridinearenes by MS and NMR experiments reveals clear differences in their host–guest chemistry and implies that cation encapsulation in pyridine[4]arene is an anion-driven process.peerReviewe

Ergebnisbericht ueber Forschungs- und Entwicklungsarbeiten 1990, Institut fuer Kernphysik

Available from TIB Hannover: ZA 5141(4841) / FIZ - Fachinformationszzentrum Karlsruhe / TIB - Technische InformationsbibliothekSIGLEDEGerman

Asymmetric Ring Opening in Tetrazine‐based Ligand Affording a Tetranuclear Opto‐Magnetic Ytterbium Complex

We report the formation of a tetranuclear lanthanide cluster, [Yb 4 (bpzch) 2 (fod) 10 ] ( 1 ), which occurs from a serendipitous ring opening of the functionalized tetrazine bridging ligand, bpztz (3,6‐dipyrazin‐2‐yl‐1,2,4,5‐tetrazine) upon reacting with Yb(fod) 3 (fod ‐ = 6,6,7,7,8,8,8‐heptafluoro‐2,2‐dimethyl‐3,5‐octandionate). Compound 1 was structurally elucidated via single‐crystal X‐ray crystallography and subsequently magnetically and spectroscopically characterized to analyse its magnetisation dynamics and its luminescence behaviour. Computational studies validate the observed M J energy levels attained by spectroscopy and provides a clearer picture of the slow relaxation of the magnetisation dynamics and relaxation pathways. These studies demonstrate that 1 acts as a single‐molecule magnet (SMM) under an applied magnetic field in which the relaxation occurs via a combination of Raman, direct, and quantum tunnelling processes, a behaviour further rationalized analysing the luminescent properties. This marks the first lanthanide‐containing molecule that forms by means of an asymmetric tetrazine decomposition.peerReviewe

CCDC 1448294: Experimental Crystal Structure Determination

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures

Thermal expansion and magnetic properties of benzoquinone-bridged dinuclear rare-earth complexes

The synthesis and structural characterization of two benzoquinone-bridged dinuclear rare-earth complexes [BQ(MCl2·THF3)2] (BQ = 2,5-bisoxide-1,4-benzoquinone; M = Y (1), Dy (2)) are described. Of these reported metal complexes, the dysprosium analogue 2 is the first discrete bridged dinuclear lanthanide complex in which both metal centres reside in pentagonal bipyramidal environments. Interestingly, both complexes undergo significant thermal expansion upon heating from 120 K to 293 K as illustrated by single-crystal X-ray and powder diffraction experiments. AC magnetic susceptibility measurements reveal that 2 does not show the slow relation of magnetization in zero dc field. The absent of single-molecule behaviour in 2 arises from the rotation of the principal magnetic axis as compared to the pseudo-C5 axis of the pentagonal bipyramidal environment as suggested by ab initio calculations. The cyclic voltammetry and chemical reduction experiments demonstrated that complexes 1 and 2 can be reduced to radical species containing [BQ3˙-]. This study establishes efficient synthetic strategy to make bridged redox-active multinuclear lanthanide complexes with a pentagonal bipyramidal coordination environment that are potential precursors for single-molecule magnets.status: publishe

CCDC 1557624: Experimental Crystal Structure Determination

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures

CCDC 1448295: Experimental Crystal Structure Determination

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