Calix[4]arenes as Molecular Platforms for Magnetic Resonance Imaging (MRI) Contrast Agents

The novel amphipilic conjugate of a calix[4]arene with four Gd–1,4,7,10‐ tetra(carboxymethyl)‐1,4,7,10‐tetraazacyclododecane (DOTA) chelates has potential as a magnetic resonance imaging contrast agent, both in its monomeric and in its micellar form. The system, illustrated here with its nuclear magnetic relaxation profile, shows good relaxivities, thanks to its high rigidity.

     

NMR Characterization of Lanthanide(3+) Complexes of Tetraazatetrakisphosphinato and Tetraazatetra­kisphosphonato Ligands

The three‐dimensional structures in aqueous solution of the entire series of the Ln³⁺ complexes [Ln(DOTP*‐Et)]^? (formed from the free ligand P,P′,P″,P′′′‐[1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetrayltetrakis(methylene)]tetrakis[P‐ethylphosphinic acid] (H₄DOTP*‐Et) were studied by NMR techniques to rationalize the parameters governing the relaxivity of the Gd³⁺ complex and evaluate its potential as MRI contrast agent. From the ¹H‐ and ³¹P‐NMR lanthanide‐induced‐shift (LIS) values, especially of the [Yb(DOTP*‐Et)]^? complex, it was concluded that the [Ln(DOTP*‐Et)]^? complexes adopt in solution twisted square antiprismatic coordination geometries which change gradually their coordination‐cage structure along the lanthanide series. These complexes have no inner‐sphere‐H₂O coordination, and preferentially have the (R,R,R,R) configuration of the P‐atoms in the pendant arms. Self‐association was observed in aqueous solution for the tetraazatetrakisphosphonic acid ester complexes [Ln(DOTP*‐OEt)]^? (=[Ln(DOTP‐Et)]^?) and [Ln(DOTP*‐OBu)]^? (=[Ln(DOTP‐Bu)]^?) at and above 5 mM concentration, through analysis of ³¹P‐NMR, EPR, vapor‐pressure‐osmometry, and luminescence‐spectroscopic data. The presence of the cationic detergent cetylpyridinium chloride (CPC; but not of neutral surfactants) shifts the isomer equilibrium of [Eu(DOTP*‐OBu)]^? to the (S,S,S,S) form which selectively binds to the cationic micelle surface.     

Isonicotinamide self-association: the link between solvent and polymorph nucleation

We show that, in a controlled and reproducible way, specific solvents lead to specific polymorphic forms of isonicotinamide. We argue on the basis of Raman and FTIR spectroscopy that the hydrogen bonding in solution kinetically drives the nucleation towards a specific form. This generally may lead to good understanding and control of polymorphism and crystal nucleation.     

17O NMR and density functional theory study of the dynamics of the carboxylate groups in DOTA complexes of lanthanides in aqueous solution

The rotation of the carboxylate groups in DOTA (DOTA = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate) complexes of several lanthanide ions and Sc(3+) was investigated with density functional theory (DFT) calculations and with variable temperature (17)O NMR studies at 4.7-18.8 T. The data obtained show that the rotation is much slower than the other dynamic processes taking place in these complexes. The exchange between the bound and unbound carboxylate oxygen atoms for the largest Ln(3+) ions (La(3+)→Sm(3+)) follows a pathway via a transition state in which both oxygens of the carboxylate group are bound to the Ln(3+) ion, whereas for the smaller metal ions (Tm(3+), Lu(3+), Sc(3+)) the transition state has a fully decoordinated carboxylate group. The activation free energies show a steady increase from about 75 to 125-135 kJ·mol(-1) going from La(3+) to Lu(3+). This computed trend is consistent with the results of the (17)O NMR measurements. Fast exchange between bound and unbound carboxylate oxygen atoms was observed for the diamagnetic La-DOTA, whereas for Pr-, Sm-, Lu-, and Sc-DOTA the exchange was slow on the NMR time scale. The trends in the linewidths for the various metal ions as a function of the temperature agree with trends in the rates as predicted by the DFT calculations.     

Assessing Crystallisation Kinetics of Zr Metal–Organic Frameworks through Turbidity Measurements to Inform Rapid Microwave-Assisted Synthesis

Controlling the crystallisation of metal-organic frameworks (MOFs), network solids of metal ions or clusters connected by organic ligands, is often hindered by the significant number of synthetic variables inherent to their synthesis. Coordination modulation, the addition of monotopic competing ligands to solvothermal syntheses, can allow tuning of physical properties (particle size, porosity, surface chemistry), enhance crystallinity, and select desired phases, by modifying the kinetics of self-assembly, but its mechanism(s) are poorly understood. Herein, turbidity measurements were used to assess the effects of modulation on the solvothermal synthesis of the prototypical Zr terephthalate MOF UiO-66 and the knowledge gained was applied to its rapid microwave synthesis. The studied experimental parameters—temperature, reagent concentration, reagent aging, metal precursor, water content, and modulator addition—all influence the time taken for onset of nucleation, and subsequently allow microwave synthesis of UiO-66 in as little as one minute. The simple, low cost turbidity measurements align closely with previously reported in situ synchrotron X-ray diffraction studies, proving their simplicity and utility for probing the nucleation of complex materials while offering significant insights to the synthetic chemist.     

A functional form for the lower Lipschitz condition for the stable subordinator

Summary Consider a completely asymmetric stable process with characteristic exponent less than one. J. Hawkes (1971, Z. Wahrscheinlichkeitstheor. Verw. Geb.17, 23–32) proved a result for the lower Lipschitz condition. In the present paper a functional form for this result is proved.     

Towards targeted MRI: new MRI contrast agents for sialic acid detection

The detection of sialic acid in living systems is of importance for the diagnosis of several types of malignancy. We have designed and synthesized two new lanthanide ion ligands (L1 and L2) that are capable of molecular recognition of sialic acid residues. The basic structure of these ligands consists of a DTPA-bisamide (DTPA, diethylenetriamine pentaacetic acid) whose amide moieties each bear both a boronic function for interaction with the diol groups in the side chain of sialic acid, and a functional group that is positively charged at physiologic pH values and is designed to interact with the carboxylate anion of sialic acid. The relaxometric properties of the Gd3+ complexes of these two ligands were evaluated. The relaxivity of the GdL1 complex has a significant second-sphere contribution at pH values above the pKa of its phenylboronic acid moiety. The interaction of the Gd3+ complexes of L1 and L2 with each of several saccharides was investigated by means of a competitive fluorescent assay. The results show that both complexes recognize sialic acid with good selectivity in the presence of other sugars. The adduct formed by GdL2 with sialic acid has the higher conditional formation constant (50.43+/-4.61 M(-1) at pH 7.4). The ability of such complexes to recognize sialic acid was confirmed by the results of a study on the interaction of corresponding radiolabeled complexes (153SmL1 and 153SmL2) with C6 glioma rat cells. 153SmL2 in particular is retained on the cell surface in significant amounts.     

Magnetic properties and aromaticity of o-, m-, and p-benzyne

The relative aromaticities of the three singlet benzyne isomers, 1,2-, 1,3-, and 1,4-didehydrobenzenes have been evaluated with a series of aromaticity indicators, including magnetic susceptibility anisotropies and exaltations, nucleus-independent chemical shifts (NICS), and aromatic stabilization energies (all evaluated at the DFT level), as well as valence-bond Pauling resonance energies. Most of the criteria point to the o-benzyne相似文献   

Hydrogen storage in magnesium clusters: quantum chemical study

Magnesium hydride is cheap and contains 7.7 wt % hydrogen, making it one of the most attractive hydrogen storage materials. However, thermodynamics dictate that hydrogen desorption from bulk magnesium hydride only takes place at or above 300 degrees C, which is a major impediment for practical application. A few results in the literature, related to disordered materials and very thin layers, indicate that lower desorption temperatures are possible. We systematically investigated the effect of crystal grain size on the thermodynamic stability of magnesium and magnesium hydride, using ab initio Hartree-Fock and density functional theory calculations. Also, the stepwise desorption of hydrogen was followed in detail. As expected, both magnesium and magnesium hydride become less stable with decreasing cluster size, notably for clusters smaller than 20 magnesium atoms. However, magnesium hydride destabilizes more strongly than magnesium. As a result, the hydrogen desorption energy decreases significantly when the crystal grain size becomes smaller than approximately 1.3 nm. For instance, an MgH2 crystallite size of 0.9 nm corresponds to a desorption temperature of only 200 degrees C. This predicted decrease of the hydrogen desorption temperature is an important step toward the application of Mg as a hydrogen storage material.