[4+3] Cycloaddition of Donor–Acceptor Cyclopropanes with Amphiphilic Benzodithioloimine as Surrogate for ortho‐Bisthioquinone

Donor–acceptor cyclopropanes were reacted with amphiphilic benzodithioloimine to give seven‐membered heterocycles with two sulfur atoms. Formally, this transformation can be regarded as a [4+3] cycloaddition reaction of the three‐membered ring and ortho‐bisthioquinone. The benzodithioloimine serves as a surrogate for this highly reactive diene. The structure of the products was confirmed by X‐ray crystallography. Broad signals in ¹³C NMR studies suggest that several conformers, slowly interconverting on the NMR timescale, are present at room temperature.     

A high-frequency apparatus for chromatographic recording and for titration

Summary A high-frequency device, using the Q-meter principle, has been tested. It is compared with a simple crystal oscillator. It was found that the stability is increased about 100 times. The new device can find application in chromatographic recording and for monitoring purposes. A titration cell with a defined cell-constant is also described.

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Zusammenfassung Ein Hochfrequenzgerät nach dem Q-Meter-Prinzip wurde getestet und mit einem einfachen Kristalloszillator verglichen. Die Stabilität des ersteren ist etwa 100fach größer. Das neue Gerät kann zur chromatographischen Registrierung und für Zwecke der Betriebsüberwachung verwendet werden. Eine Titrationszelle mit definierter Zellkonstante wurde gleichfalls beschrieben.

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Résumé On a mis à l'essai un dispositif haute-fréquence mettant en application le principe du compteur-Q. On le compare avec un oscillateur simple à cristal. On a trouvé que la stabilité est augmentée d'environ cent fois. Le nouveau dispositif peut trouver une application dans l'enregistrement chromatographique et pour des usages de contrôle. On décrit également une cuve de titrage avec une constante de cellule définie.

     

Light sensitivity and potential stability of electrically conducting polymers commonly used in solid contact ion-selective electrodes

The results of a systematic study of the light sensitivity and long-term potential stability (30 days) of poly(pyrrole) (PPy), poly(3-octylthiophene) (POT), poly(3,4-ethylenedioxythiophene) (PEDOT), poly(aniline) (PANI) and plasticised poly(vinyl chloride) (PVC) containing 20% (m/m) PANI are reported. Thin films were prepared either electrochemically or by the solution casting technique. This fundamental study is of importance because conducting polymers (CP) are commonly used as ion-to-electron transduction materials in all-solid-state solid contact ion-selective electrodes. The potential stability test done in 0.1 M KCl (pH 7.5) simulates the extreme situation when the CP-based SC becomes in direct contact with water. Films prepared of a nanodispersion of PANI showed both good potential stability and insensitivity to light even under illumination with very intensive light (>10⁵ lx). In contrary, it was observed that POT is very light-sensitive. Upon illumination with intensive light, the potential responses of POT films prepared by solution casting and electropolymerisation were 315 and 590 mV, respectively. A room light sensitivity of approximately −10 to −15 mV was observed for these films. The other CPs in this study were insensitive to room light (∼150 lx), but were light-sensitive under illumination with intensive light. The potential drift of PPy(Cl) is below −10 μV/h (3–30 days), whereas the other most stable CPs in this study had a slightly higher potential drift.     

Amorphous drug nanosuspensions. 1. Inhibition of Ostwald ripening

Amorphous drug nanosuspensions are prone to particle growth due to Ostwald ripening. By incorporating a second component of extremely low aqueous solubility, Ostwald ripening can be inhibited. These studies indicate that to inhibit ripening, the drug/inhibitor mixture (in the particles) must form a single phase. The drug/inhibitor mixture can be characterized by the interaction parameter chi using the Bragg-Williams theory, in which single phase mixtures are obtained for chi < 2. The chi parameter can be calculated from the (crystalline) solubility of the drug in the inhibitor, provided the inhibitor is a liquid, and the melting entropy and temperature of the drug.     

Gels of hydrophobically modified hydroxyethyl cellulose cross-linked by amylose. Competition with cyclodextrin

Previous work has shown that amylose (AM) can cross-link hydrophobically modified polymers by inclusion complexation, whereby thermoreversible cold-setting gels are formed. In this work, the competition between AM and cyclodextrin (CD) for the formation of inclusion complexes with hydrophobically modified hydroxyethyl cellulose (HMHEC) is investigated. A detailed study of viscosity, NMR self-diffusion, and chemical shifts of the two-component mixture, CD and HMHEC, was performed. The results imply that 2:1 (CD:polymer hydrophobe) complexes may be formed. The three-component mixtures, HMHEC/AM/CD, were investigated by rheology, NMR self-diffusion, and intensities of the NMR resonance peaks. The CD molecules competed efficiently with the AM molecules, as seen by a decreased storage modulus, an increased self-diffusion of AM and HMHEC, and increased NMR intensities of the HMHEC hydrophobes, as the concentration of CD increased in the solution. A high concentration of CD is needed in the mixtures to inhibit all interactions between HMHEC and AM, and it was shown that there still is an effect of AM at excess CD concentration in the mixtures.     

Grassmann algorithms for low rank approximation of matrices with missing values

The problem of approximating a matrix by another matrix of lower rank, when a modest portion of its elements are missing, is considered. The solution is obtained using Newton’s algorithm to find a zero of a vector field on a product manifold. As a preliminary the algorithm is formulated for the well-known case with no missing elements where also a rederivation of the correction equation in a block Jacobi-Davidson method is included. Numerical examples show that the Newton algorithm grows more efficient than an alternating least squares procedure as the amount of missing values increases.     

On Shalika models and <Emphasis Type="Italic">p</Emphasis>-adic <Emphasis Type="Italic">L</Emphasis>-functions

We use modular symbols to construct p-adic L-functions for cohomological cuspidal automorphic representations on GL(2n), which admit a Shalika model. Our construction differs from former ones in that it systematically makes use of the representation theory of p-adic groups.     

A New Green Thermoplastic Polymer with Improved Hydrophobic Character

Summary: A green thermoplastic polymer based on wheat flour was modified by the addition of a natural crosslinker genipin. Films of the polymer modified with different composition of genipin were prepared by extrusion. Free surface energy using contact angle method, moisture absorption test and hardness test were used to characterize the products. From moisture absorption and contact angle measurements, it was seen that for genipin amounts higher than 0.2% w/w, a hydrophobic character is achieved. Results obtained indicate enhancement in hydrophobic properties of the films.