Ion selectivity of crown ethers investigated by UV and IR spectroscopy in a cold ion trap

Electronic and vibrational spectra of benzo-15-crown-5 (B15C5) and benzo-18-crown-6 (B18C6) complexes with alkali metal ions, M(+)?B15C5 and M(+)?B18C6 (M = Li, Na, K, Rb, and Cs), are measured using UV photodissociation (UVPD) and IR-UV double resonance spectroscopy in a cold, 22-pole ion trap. We determine the structure of conformers with the aid of density functional theory calculations. In the Na(+)?B15C5 and K(+)?B18C6 complexes, the crown ethers open the most and hold the metal ions at the center of the ether ring, demonstrating an optimum matching in size between the cavity of the crown ethers and the metal ions. For smaller ions, the crown ethers deform the ether ring to decrease the distance and increase the interaction between the metal ions and oxygen atoms; the metal ions are completely surrounded by the ether ring. In the case of larger ions, the metal ions are too large to enter the crown cavity and are positioned on it, leaving one of its sides open for further solvation. Thermochemistry data calculated on the basis of the stable conformers of the complexes suggest that the ion selectivity of crown ethers is controlled primarily by the enthalpy change for the complex formation in solution, which depends strongly on the complex structure.     

Combinatorial synthesis and characterization of metal-open frameworks in mild and friendly conditions: application to CO₂ adsorption

Combinatorial screening using precipitation methods at room temperature can lead to a great diversity of carboxylate based Metal Organic Frameworks (MOFs) including already known or original porous solids. The investigation of the synthesis of MOFs in different solvent and solvent mixtures includes the use of solvents such as alcohols and tetrahydrofuran (THF) which would greatly facilitate large scale production. We also show the application of Principal Component Analysis (PCA) and clustering techniques on large libraries of XRD diffraction files in order to identify classes of similar phases and peculiar phases. The combinatorial screening of 105 samples in the La/btc system has led to the identification of two phases which are solvent depending. On the La(btc) compound, the CO? adsorption measurements reveal a guest-host interactions as supported by XRD phase transformation upon thermal treatment. The mass transport can be assigned to a "single file diffusion" regime due to the one dimensional channel porous structure associated to small pore size.     

Selective chemical imaging of static actin in live cells

We have characterized rationally designed and optimized analogues of the actin-stabilizing natural products jasplakinolide and chondramide C. Efficient actin staining was achieved in fixed permeabilized and non-permeabilized cells using different combinations of dye and linker length, thus highlighting the degree of molecular flexibility of the natural product scaffold. Investigations into synthetically accessible, non-toxic analogues have led to the characterization of a powerful cell-permeable probe to selectively image static, long-lived actin filaments against dynamic F-actin and monomeric G-actin populations in live cells, with negligible disruption of rapid actin dynamics.     

Critical slowing down exponents of mode coupling theory

A method is provided to compute the exponent parameter λ yielding the dynamic exponents of critical slowing down in mode coupling theory. It is independent from the dynamic approach and based on the formulation of an effective static field theory. Expressions of λ in terms of third order coefficients of the action expansion or, equivalently, in terms of six point cumulants are provided. Applications are reported to a number of mean-field models: with hard and soft variables and both fully connected and dilute interactions. Comparisons with existing results for the Potts glass model, the random orthogonal model, hard and soft-spin Sherrington-Kirkpatrick, and p-spin models are presented.     

DBS-Based Eutectogels: Organized Vessels to Perform the Michael Addition Reaction**

Supramolecular eutectogels were obtained from the gelation of 1,3 : 2,4-dibenzylidene-D-sorbitol (DBS) in cholinium chloride-based deep eutectic solvents (DES), differing for the nature of the hydrogen bond donor. Ethylene glycol, diethylene glycol, triethylene glycol, glycerol and urea were tested. Soft materials were fully characterized, determining critical gelation concentration, gel-sol transition temperatures and mechanical properties. Furthermore, to have information about the organization of the gelator in the tridimensional network, resonance light scattering, circular dichroism and microscopy investigations were performed. Eutectogels were used as organized “vessels” to perform the L-proline catalyzed Michael addition reaction. The probe reaction was carried out in gel phase and in DES solution. Data collected shed light on the effect that gel microenvironment exerts on the outcome of the reaction. In general, gel phases allowed having comparable or even better results than the ones collected in DES solution, with better results obtained in soft materials with the highest organization, as accounted for by the presence of larger aggregates and the occurrence of stronger intermolecular interactions. In turn, this accounts also for the effect of substrates structure that indicates that better yields could be obtained in the presence of more flexible nucleophile and dienones, having more extended π-surface.