Oxidation reactivity channels for 2-(pyridin-2-yl)-N,N-diphenylacetamides

Synthetic routes to 2-(pyridin-2-yl)-N,N-diphenylacetamide and 2-(6-methylpyridin-2-yl)-N,N-diphenyl-acetamide are described along with results from the chemical oxidation of these compounds with peracetic acid, m-chloroperbenzoic acid, and OXONE. In each case, oxidations generate four products in varying amounts depending on the oxidant and reaction conditions. Each product has been characterized by spectroscopic methods and the molecular structures of several of the new compounds have been confirmed by X-ray crystallography.     

Responsive thin hydrogel layers from photo-cross-linkable poly(N-isopropylacrylamide) terpolymers

The structural features and swelling properties of responsive hydrogel films based on poly(N-isopropylacrylamide) copolymers with a photo-cross-linkable benzophenone unit were investigated by surface plasmon resonance, optical waveguide mode spectroscopy, and atomic force microscopy. The temperature-dependent swelling behavior was studied with respect to the chemical composition of the hydrogel polymers containing either sodium methacrylate or methacrylic acid moieties. In the sodium methacrylate system, a refractive index gradient was found that was not present in the free acid gel. This refractive index gradient, perpendicular to the swollen hydrogel film surface, could be analyzed in detail by application of the reversed Wentzel-Kramers-Brillouin (WKB) approximation to the optical data. This novel approach to analyzing thin-film gradients with the WKB method presents a powerful tool for the characterization of inhomogeneous hydrogels, which would otherwise be very difficult to capture experimentally. In AFM images of the hydrogel layers, a macroscopic pore structure was observed that depended on the polymer composition as well as on the swelling history. This pore structure apparently prevents the often-observed skin barrier effect and leads to a quickly responding hydrogel.     

Struktur und Koordinationsverhalten des sterisch anspruchsvollen Phenylcycloarsoxans

Structure and Coordination Chemistry of Sterically Demanding Phenylcycloarsoxane Tetrameric phenylcycloarsoxane (C₆H₅AsO)₄ 1 exhibits a boat‐chair‐conformation in the solid state. Its reaction with CuI in benzonitrile leads to the formation of coordination polymers. [(CuI · C₆H₅CN){cyclo‐(C₆H₅AsO)₄}] ( 2 ) underlines the structure‐directing steric requirements of the phenyl side chains. Treatment of 1 with M(CO)₆ (M = Cr, Mo) confirms its capability to undergo metal‐mediated ring expansion. In [{M(CO)₃}₂{cyclo‐(C₆H₅AsO)₆}] with M = Cr ( 3 ) and M = Mo ( 4 ), twelve membered As–O‐rings are stabilised by the participation of alternating As atoms in the coordination spheres of opposite facial transition metal carbonyl fragments M(CO)₃.     

Operators associated with the Jacobi semigroup

The aim of this paper is to introduce some operators induced by the Jacobi differential operator and associated with the Jacobi semigroup, where the Jacobi measure is considered in the multidimensional case.In this context, we introduce potential operators, fractional integrals, fractional derivates, Bessel potentials and give a version of Carleson measures.We establish a version of Meyer’s multiplier theorem and by means of this theorem, we study fractional integrals and fractional derivates.Potential spaces related to Jacobi expansions are introduced and using fractional derivates, we give a characterization of these spaces. A version of Calderon’s Reproduction Formula and a version of Fefferman’s theorem are given.Finally, we present a definition of Triebel–Lizorkin spaces and Besov spaces in the Jacobi setting.     

Fast 3D coronary artery contrast-enhanced magnetic resonance angiography with magnetization transfer contrast, fat suppression and parallel imaging as applied on an anthropomorphic moving heart phantom

A magnetic resonance sequence for high-resolution imaging of coronary arteries in a very short acquisition time is presented. The technique is based on fast low-angle shot and uses fat saturation and magnetization transfer contrast prepulses to improve image contrast. GeneRalized Autocalibrating Partially Parallel Acquisitions (GRAPPA) is implemented to shorten acquisition time. The sequence was tested on a moving anthropomorphic silicone heart phantom where the coronary arteries were filled with a gadolinium contrast agent solution, and imaging was performed at varying heart rates using GRAPPA. The clinical relevance of the phantom was validated by comparing the myocardial relaxation times of the phantom's homogeneous silicone cardiac wall to those of humans. Signal-to-noise ratio and contrast-to-noise ratio were higher when parallel imaging was used, possibly benefiting from the acquisition of one partition per heartbeat. Another advantage of parallel imaging for visualizing the coronary arteries is that the entire heart can be imaged within a few breath-holds.     

Hyperbranched PEG by Random Copolymerization of Ethylene Oxide and Glycidol

The synthesis of hyperbranched poly(ethylene glycol) (hbPEG) in one step was realized by random copolymerization of ethylene oxide and glycidol, leading to a biocompatible, amorphous material with multiple hydroxyl functionalities. A series of copolymers with moderate polydispersity ( < 1.8) was obtained with varying glycidol content (3–40 mol‐%) and molecular weights up to 49 800 g mol⁻¹. The randomly branched structure of the copolymers was confirmed by ¹H and ¹³C NMR spectroscopy and thermal analysis (differential scanning calorimetry). MTS assay demonstrated low cell toxicity of the hyperbranched PEG, comparable to the highly established linear PEG.

     

Scaling and mesostructure of Carbopol dispersions

Rheological measurements were performed on aqueous dispersions of two commercial crosslinked polymer microgels, Carbopol Ultrez 10 and Carbopol ETD 2050, prepared over a wide range of concentration and pH. For all concentrations studied, both the yield stress and the elastic modulus initially increased dramatically with pH and displayed broad peaks at intermediate pH. This is consistent with the onset of jamming of the Carbopol particles due to a rapid increase in particle size caused by osmotic swelling in the presence of NaOH. Scaling of both yield stress and elasticity with concentration was observed only at higher concentrations, which we believe indicates a change from a percolated structure at low volume fractions to a space filling network of compressed particles at high volume fractions. This model is supported by confocal microscopy of fluorescently dyed Carbopol dispersions.