S-Alkylation en série hétérocyclique par catalyse par transfert de phase: thioalkyl-2-thiazoles,thioalkyl-2-Δ-4-thiazolines et thioalkyl-2-benzothiazoles

S-Alkylation in heterocyclic serie by phase transfer catalysis: 2-alkylthiothiazoles, 2-alkylthio-Δ-4-thiazolines and 2-alkylthiobenzothiazoles Some Δ-4-thiazoline-, thiazolidine-, and benzothiazoline-2-thiones have been S-alkylated by phase transfer catalysis; yields averaged 80 to 90%. With halogenated heterocyclic compounds of poor reactivity, the main reaction consisted in a dequaternization of the catalyst by the thiones acting as nucleophiles.     

Unexpected halogen substituent effects on the complex thermal relaxation of naphthopyrans after UV irradiation

The kinetics of the thermal fading of four halogenated naphthopyrans (NP) have been analyzed using NMR spectroscopy in CD(3)CN. Two photomerocyanines (TT and TC) were detected after UV irradiation. The main relaxation process TC --> NP was coupled with TT/TC isomerization. The activation parameters of the various processes were rationalized by considering electronegativity and polarizability of the halogen substituents and their selective solvation by the electronegative nitrogen of acetonitrile.     

Microwave study of proximity effects in superconductivity

The microwave surface resistance of a thin layer of copper in close contact with the surface of bulk lead is investigated. It is found that the basic ideas about proximity effects in superconductivity developed in recent years are capable of explaining the observed behaviour very satisfactorily. Our data give evidence of a complex excitation spectrum in the copper, with low energy excitations above a true gap and a group of high energy excitations which is usually observed in tunneling experiments. The response to a magnetic field shows that scattering at the free copper surface is diffuse. This leads at low fields, where a Meissner shielding current flows at the copper surface, to a decrease of the depairing energy by a large amount of first order in the vector potentialA instead of only a small second order amount. This also explains an initial decrease of the absorption when a weak magnetic field is applied. For fields over a large range below the critical field of lead superconductivity is effectively suppressed in copper. The data also give information on the increase of the penetration depth in lead because of the coating with copper and on the effective electron-electron interaction in copper: $$\lambda \to 2\lambda _L and (NV)_{Cu} \cong 0.05.$$      

Nova methodus adhibendi approximationem molecularium orbitalium ad plures iuxtapositas unitates

Résumé L'étude de la structure électronique d'une chaîne constituée par la répétition d'un motif polyatomique et l'interprétation des propriétés du polymère ainsi formé sont grandement facilités, s'il est possible de ramener les termes d'interaction entre unités voisines à un paramètre d'interaction unique. Ce problème a été traité en méthode des orbitales moléculaires par un procédé qui permet de tenir compte des modifications du monomère à l'intérieur du polymère et ne néglige que de faibles contributions.L'interaction entre deux monomèresi etj est représentée par la sous-matriceB _ij de dimensionn ×n formée par les termes non-diagonaux correspondants de la matrice-énergie. Par des transformations unitaires appropriées, il est possible de mettre sous forme diagonale les sousmatricesB _ij entre monomères voisins. En général, la diagonale de la matrice transformée contient un terme prépondérant qu'on peut considérer comme mesurant l'interaction (i, j). Une application numérique a été effectuée dans le cas d'un polymère fictif formé par des molécules H₂ et dans le cas d'un polymère peptidique formé par des groupements HNCO en interaction par l'intermédiaire de liaisons hydrogène. La validité des approximations introduites selon l'importance de l'interaction peut être vérifiée sur l'exemple d'un dimère dont les deux unités sont placées à des distances variables. Dans le cas d'un polymère les transformations effectuées conduisent à remplacer les orbitales atomiques du monomère par des orbitales s'étendant sur deux unités voisines; en prenant comme motif structural de la chaîne le monomère double formé par deux unités successives, on peut représenter l'interaction entre deux motifs adjacents par un seul terme.La réduction de la matriceB _ij à un seul terme fournit des bandes d'énergie dont la position est en très bon accord avec celles obtenues directement par les techniques classiques de calcul de l'état solide [7].

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The study of the electronic structure of a chain formed by repetition of polyatomic monomers and the interpretation of the resulting polymer are made much easier if the interaction terms relating to neighbouring units can be reduced to a single parameter. This problem has been treated in the MO scheme by a procedure which makes it possible to take into account the modifications of the monomer within the polymer and only neglects minor contributions.The interaction between two monomersi andj is represented by then ×n submatrixB _ij formed by the corresponding non diagonal terms of the energy matrix. By appropriate unitary transformations it is possible to bring the submatricesB _ij of neighbouring monomers to a diagonal form. In general, one of the diagonal elements thus obtained is much higher than the others, and can be taken as a measure of thei-j interaction. A numerical application has been made in the case of a fictitious polymer formed by H₂ molecules, and in the case of a polypeptide formed by HNCO groups interacting through hydrogen bonds. The validity of the approximations introduced for different values of interaction can be tested on a dimer whose units are placed at different distances. In the case of a polymer the transformations mentioned above require that the atomic orbitals of a monomer be replaced by orbitals extending over two neighbouring units. Taking as a new unit the corresponding pair of monomers, the interaction between the units can be represented by a single term. The reduction of theB _ij matrices to a single term each gives energy bands whose positions are in perfect agreement with those obtained directly by the classical techniques of solid-state physics [7].

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Zusammenfassung Das Studium der elektronischen Struktur von linearen Polymeren vereinfacht sich sehr, wenn die Wechselwirkung zwischen benachbarten Monomeren durcheinen Parameter beschrieben werden kann. Entsprechend wird im MO-Schema ein Verfahren entwickelt, das auf der Veränderung der Monomeren im Polymeren fußt.Die Wechselwirkung zwischen zwei Monomereni, j des Polymer wird durch eine aus Nichtdiagonalelementen der Hamiltonmatrix bestehende UntermatrixB _ij beschrieben. Für alle benachbarten Monomerenpaare lassen sich diese durch unitäre Transformationen diagonalisieren. I. a. ist eines der so erhaltenen Diagonalelemente vonB merklich größer und dient als Maß für die Wechselwirkung der beiden Monomeren. Angewendet wird die Methode auf ein fiktives Polymer aus H₂-Molekülen und auf ein Polymer aus durch H-Brücken verbundenen Peptidgruppen. Der Einfluß der Näherungen wird zunächst an einem Dinieren für verschiedene Abstände getestet.Im Falle eines Polymeren sind als Monomere Einheiten von zwei benachbarten Molekülen mit entsprechend ausgedehnten Orbitalen zu betrachten. Die Rechnung führt hier auf Energiebänder, deren Lage voll mit der nach klassischen Methoden der Festkörperphysik [7] erhaltenen übereinstimmt.

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Gratias agimus Cl. Vir.Raphaeli Del Re, qui nos, quod ad usum linguae latinae attinet, consilio benigne adiuvit.     

Proprietes electrogalvaniques et electroniques du sulfure d'argent β: Domaine d'existence

The study of electrogalvanic and electronic properties of the form β of silver sulfide has been performed on polycrystalline samples whose non stoichiometry is controled by coulometric titration with the cell Ag/RbAg₄I₅/Ag₂₊?S/Pt.The data obtained lead to the adoption of an electronic model according to which the Frenkel defects of the silver sublattice are completly ionized. The variation with temperature of the electronic properties near the stoichiometric composition between 23 and 176°C, the temperature of transition between the two forms β and α of Ag₂S, enables the forbidden gap E_i = (1,35?1,5 × 10^?3T) eV to be computed. The existence range has been drawn between 69°C and the α ? β transition temperature.The study of the ionic conductivity has made it possible to detect two ranges of preferential conduction and to determine the mechanism of migrations of the intersticial silver ions.     

Controlled conversion of isomers in a hybrid biphotochromic system

[reaction: see text] The photochromic performance of a hybrid system connecting naphthopyran and dithienylethene was investigated, and the photochemistry of eight different isomers was explored by choosing an appropriate wavelength of light.     

Interactions of ADP-stimulated human platelets with PEGylated polystyrene substrates prepared by surface amidation

A study primarily focused on the interactions between ADP-stimulated human platelets and PEGylated polystyrene substrates is described in this paper. The platelet–surface interactions were investigated using colorimetric acid phosphatase assay. Two types of amine-containing polymeric hydrogel materials based on poly(ethylene glycol) (PEG), H₂N–PEG–OCH₃ and H₂N–PEG–NH₂, were used to PEGylate polystyrene surfaces derivatized with maleic anhydride by amidation at alkaline pH. In addition, comparative studies using surfaces non-covalently adsorbed by bovine serum albumin (BSA) or fibrinogen (Fg) were also conducted. The assay results showed that no significant platelet adhesion was observed when PEGylated surfaces or BSA-coated surfaces were exposed to unstimulated gel-filtered platelets (GFP). However, upon ADP-stimulation, platelet adhesion to the surfaces under investigation in this study all increased to varying degrees. Most importantly, the results showed that polystyrene surfaces PEGylated using H₂N–PEG–NH₂ were most effective in resisting platelet adhesion when assays were performed using ADP-stimulated GFP. By PEGylating the surfaces of polystyrene microtiter wells via the amidation reaction described in this paper, it is demonstrated that (i) higher degree of surface PEGylation is favored at more alkaline pH and (ii) polystyrene substrates capable of more effectively resisting the adhesion of ADP-stimulated GFP can be obtained by the PEGylation reaction carried out at pH 9.1 using H₂N–PEG–NH₂.     

Embedding procedure for ab initio correlation calculations in group II metals

In order to apply ab initio wave-function-based correlation methods to metals, it is desirable to split the calculation into a mean-field part and a correlation part. Whereas the mean-field part (here Hartree-Fock) is performed in the extended periodic system, it is necessary to use for the correlation part local wave-function-based correlation methods in finite fragments of the solid. For these finite entities it is necessary to construct an embedding. The authors suggest an embedding scheme which has itself no metallic character but can mimic the metal in the internal region, where the atoms are correlated. With this embedding it is also possible to localize the metallic orbitals in the central part. The long-range nonadditive contributions of metallicity and correlation are treated with the method of increments. In this paper they present different ways to construct such an embedding and discuss the influence of the embedding on the correlation energy of the solid.