119 research outputs found

    Methyl 3,5-bis­[(4-hydroxy­methyl-2-methoxy­phen­oxy)meth­yl]benzoate

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    In the title compound, C26H28O8, the central aromatic ring forms dihedral angles of 24.32 (11) and 80.19 (7)° with the two adjoining vanillyl alcohol rings. In the crystal, O—H⋯O hydrogen bonds connect the mol­ecules, forming a hydrogen-bonded sheet-like motif extended in the ab plane

    Optimized Continuous Application of Hyperpolarized Xenon to Liquids

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    International audienceIn recent years, NMR with hyperpolarized (HP) xenon inside functionalized host structures (e.g. cryptophanes) have become a potential candidate for the direct observation of metabolic processes (i.e. molecular imaging). A critical issue for real applications is the dissolution of the HP-gas in the liquid which contains the host. In this work, we present recent developments for an improved and controlled dissolution of HP-Xe in liquids using hollow fiber membranes and different compressor systems. The designed apparatus consists of a compressor and a membrane unit. The compressor provides HP-129 Xe continuously at small adjustable pressures and in a polarization-preserving way. The membrane unit enables a molecular solution of the HP-gas in aqueous liquids, avoiding the formation of bubbles or even foams. Two different types of compressors were tested in terms of function and useful materials. Special emphasis was put on a systematic reduction of transfer losses in the gas and liquid phase. In order to optimize the system parameters, several physical models were developed to describe the transport and the losses of nuclear polarization. Finally, the successful implementation was demonstrated in several experiments. HP-Xe was dissolved in an aqueous cryptophane-A-(OCH 2 COOH) 6 solution, and stable Xe signals could be measured over 35 min, only limited by the size of the gas reservoir. Such long and stable Version 6 21.10.2019 BN experimental conditions enabled the study of chemical exchange of xenon between cryptophane and water environments even for a time-consuming 2D NMR-experiment. The good signal stability over the measurement time allowed an exact determination of the residence time of the Xe-atom inside the cryptophane, resulting in an average residence time of 42.9 ± 3.3 ms

    Apparent Alkyl Transfer and Phenazine Formation via an Aryne Intermediate

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    Treatment of chlorotriaryl derivatives 3a and 3d or fluorotriaryl derivatives 3b and 3e with potassium diisopropylamide afforded alkyl-shifted phenazine derivatives 5a/5b, rather than the expected 9-membered triazaorthocyclophane 2a. The phenazine derivatives were isolated in 78–98% yield depending on the halogen and alkyl group present. In the absence of the halogen (chloro or fluoro), the apparent alkyl shift proceeds more slowly and cannot proceed via the intermediacy of the aryne intermediate. Mechanistic possibilities include intramolecular nucleophilic attack on an aryne intermediate leading to a zwitterionic intermediate and alkyl transfer via a 5-endo-tet process, or via a Smiles rearrangement

    The Chemokine CXCL12 Is Essential for the Clearance of the Filaria Litomosoides sigmodontis in Resistant Mice

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    Litomosoides sigmodontis is a cause of filarial infection in rodents. Once infective larvae overcome the skin barrier, they enter the lymphatic system and then settle in the pleural cavity, causing soft tissue infection. The outcome of infection depends on the parasite's modulatory ability and also on the immune response of the infected host, which is influenced by its genetic background. The goal of this study was to determine whether host factors such as the chemokine axis CXCL12/CXCR4, which notably participates in the control of immune surveillance, can influence the outcome of the infection. We therefore set up comparative analyses of subcutaneous infection by L. sigmodontis in two inbred mouse strains with different outcomes: one susceptible strain (BALB/c) and one resistant strain (C57BL/6). We showed that rapid parasite clearance was associated with a L. sigmodontis-specific CXCL12-dependent cell response in C57BL/6 mice. CXCL12 was produced mainly by pleural mesothelial cells during infection. Conversely, the delayed parasite clearance in BALB/c mice was neither associated with an increase in CXCL12 levels nor with cell influx into the pleural cavity. Remarkably, interfering with the CXCL12/CXCR4 axis in both strains of mice delayed filarial development, as evidenced by the postponement of the fourth molting process. Furthermore, the in vitro growth of stage 4 filariae was favored by the addition of low amounts of CXCL12. The CXCL12/CXCR4 axis thus appears to have a dual effect on the L. sigmodontis life cycle: by acting as a host-cell restriction factor for infection, and as a growth factor for worms

    Metallo-cryptophanes decorated with Bis-N-heterocyclic carbene ligands: self-assembly and guest uptake into a nonporous crystalline lattice

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    Pd3L2 metallo-cryptophane cages with cyclotriveratrylene-type L ligands can be stabilized by use of a bis-N-heterocyclic carbene as an auxiliary cis-protecting ligand, while use of more common protecting chelating ligands such as ethylenediamine saw a Pd3L2 to Pd6L8 rearrangement occur in solution. The crystalline Pd3L2 complexes act as sponges, taking up 1,2-dichorobenzene or iodine in a single-crystal-to-single-crystal fashion despite not exhibiting conventional porosity

    Xenon@cryptophane Complexes as New Contrast Agents for Resonance Magnetic Imaging

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    Chiroptical Properties of Enantiopure Cryptophane Derivatives

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    Understanding the Unusual Properties of the cryptophane-222 skeleton

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