Macrotricyclic quaternary tetraammonium receptors: halide anion recognition and interfacial activity at an aqueous interface. A molecular dynamics investigation

We report a molecular dynamics study of the halide inclusion complexes X(-) subset L(4+) of a macrotricyclic tetrahedral receptor L(4+) built from four quaternary ammonium sites connected by six (CH(2))(n) chains. The hydrophilic/hydrophobic character of the complexes is investigated at a water/chloroform interface, represented explicitly and, despite their +3 charge and "spherical" shape, they are found to display amphiphilic behavior and to concentrate at the interface. The more lipophilic N-substituted CH(2)phi derivative, as well as less charged models are more surface active than the N-Me substituted host. In relation with the Hofmeister series, I(-) exo neutralizing counterions are compared with Cl(-) anions and are found to sit closer to the interface, which becomes more neutral. The "macrocyclic interfacial effect" is investigated by a comparison of L(4+) complexes with their acyclic counterparts. Finally, we address the question of anion binding selectivity by L(4+) and its L(1) (4+) and L(2) (4+) topological isomers. F(-) is too small for these three hosts, while I(-) is too big. According to free energy perturbation calculations, Cl(-) is preferred to Br(-), but somewhat more by L(1) (4+) than by L(4+).     

Effect of the homogeneity of the column set on the performance of a simulated moving bed unit. II. Experimental study

Previous studies of the simulated moving bed (SMB) process assume identical characteristics of all the columns incorporated in a given unit. Due to the practical impossibility to manufacture identical columns, numerical applications of the theory to modeling and optimization use for each of the needed column parameter the average value for the entire column set. In this study, the effects of these simplifications on the actual productivity of the SMB process are evaluated by making exact calculations, i.e., by taking the differences in the porosity values into account. We apply a revised set of separation conditions previously introduced and derived from the equilibrium theory. Earlier theoretical results are compared to experimental results obtained in the study of the enantiomeric separation of Tr?ger's base on Chiralpak AD. Due to the nonLangmuirian character of the adsorption isotherms of these two compounds on the packing material used, the separation area cannot be determined analytically. As an alternative, a reliable numerical algorithm was used to scan a wider region and to define the separation area. The form of this area depends on the applied porosity values. A UV detector and a laser polarimeter located at one node of the SMB monitor on-line the internal concentration profiles. Excellent agreement between the calculated and the experimentally determined concentration profiles was obtained under nonlinear conditions. The influence of column-to-column variations on the performance of the SMB process was found to be more significant under nonlinear than under linear conditions.     

Retrosynthetic analysis of fullerene C(60): structure, stereochemistry, and calculated stability of C(30) fragments.

The total number of possible retrosynthetic bisections of C(60) leads to nine different isometric C(30) fragments. These molecules include five chiral units, four of which derive from partitions corresponding to four distinct "Coupes du Roi". The energies, curvatures, and homodesmotic stabilization energies of the C(30) fragments are evaluated at the ab initio 6-31G level.     

Chromium (II) chloride : a new reagent for cross-aldol reactions

The proposed cross aldolization of α-bromoketones with aldehydes in presence of Chromium (II) chloride is an excellent stereospecific reaction. One exception to the stereospecific orientation is reported.     

Stabilité élastique des structures unidimensionnelles

In this paper, we consider the problem of stability of one-dimensional structures and give a general formulation by means of the energy method. We propose then a numerical method of deriving the critical rate requiring eigenvalues of a sequence of small matrices rather than of a big one.

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Cet article est le résumé d'une thèse présentée à l'Ecole Polytechnique de l'Université de Lausanne [17]. Je tiens à exprimer ma vive gratitude au ProfesseurCh. Blanc, directeur de l'Institut de Mathématiques Appliquées, dont les conseils et encouragements m'ont été très précieux.     

Perhydro dioxazepines-1,5,3 : Methode generale de synthese

Perhydrodioxazepines-1,5,3 are obtained by reacting a primary amine with a 1,2-diol and paraformaldehyde.     

Proprietes magnetiques et electriques de la phase Ca2MnO4−xFx

The magnetic properties of the antiferromagnetic Ca₂MnO_4?x solid solution (0?x?0,30) are essentially characterized by a weak ferromagnetism with a maximum value for x = 0,20. Spin canting results from the competition between the antiferromagnetic super-exchange couplings and the double exchange ferromagnetic interactions due to the presence of manganese in oxidation states + III and + IV. It seems independent of the site of fluorine in the framework. The variation of Weiss constant and ordering temperature withx is also discussed. Electrical conductivity results from a hopping mechanism between Mn³⁺ and Mn⁴⁺ ions. The electrical conductivity presents a maximum when x = 0.10, corresponding to an activation energy minimum.