Electrogenerated Fe(I) Porphyrins: Efficient Electrocatalysts for Reductive Dechlorination of DDT in N,N′‐Dimethylformamide

Two iron(I) porphyrins were electrogenerated and then utilized as catalysts for the reductive dechlorination of 1,1‐bis(4‐chlorophenyl)‐2,2,2‐trichloroethane (DDT) in N,N′‐dimethylformamide. No reaction is observed between DDT and the Fe(III) or Fe(II) forms of the porphyrin, but the electrogenerated Fe(I) porphyrin efficiently catalyzes the electroreduction of DDT to give (1,1‐bis(4‐chlorophenyl)‐2,2‐dichloroethane) DDD, (1,1‐bis(4‐chlorophenyl)‐2,2‐dichloroethylene) DDE and (1,1‐bis(4‐chlorophenyl)‐2‐dichloroethane) DDMU as determined by GC‐MS analysis. The reductive dechlorination was monitored by electrochemistry, controlled potential electrolysis and spectroelectrochemistry and a mechanism for the reaction involving the reduced porphyrins and DDT is proposed. Comparisons are also made between the catalytic properties of metalloporphyrins containing iron, cobalt and manganese central metal ions under the same solution conditions.     

Stereocontrolled Organocatalytic Strategy for the Synthesis of Optically Active 2,3‐Disubstituted cis‐2,3‐Dihydrobenzofurans

An intramolecular, organocatalyzed Michael addition has been developed to obtain biologically important 2,3‐disubstituted cis‐2,3‐dihydrobenzofurans. By using mandelic acid salts of primary aminocatalysts, derived from cinchona alkaloids, the intramolecular cyclization reaction has been developed to proceed in high yield, with moderate to good diastereoselectivity, and up to 99 % ee. Based on the absolute configuration of the formed 2,3‐disubstituted‐cis‐2,3‐dihydrobenzofurans and by considering the observed substrate scope restrictions, a mechanistic rationalization has been presented.     

Comparison of a mixed least-squares formulation using different approximation spaces

The main goal of the present work is the comparison of the performance of a least-squares mixed finite element formulation where the solution variables (displacements and stresses) are interpolated using different approximation spaces. Basis for the formulation is a weak form resulting from the minimization of a least-squares functional, compare e.g. [1]. As suitable functions for standard interpolation polynomials of Lagrangian type are chosen. For the conforming discretization of the Sobolev space vector-valued Raviart-Thomas interpolation functions, see also [2], are used. The resulting elements are named as P_mP_k and RT_mP_k. Here m (stresses) and k (displacements) denote the approximation order of the particular interpolation function. For the comparison we consider a two-dimensional cantilever beam under plain strain conditions and small strain assumptions. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Diagnostic cellular organization features extracted from autofluorescence images

Depth-resolved NADH autofluorescence images are shown to differentiate between normal and precancerous engineered tissues. An inverse power law behavior of the power spectral density (PSD) of these images is observed, indicating a self-affine organization of mitochondrial NADH at length scales 1-10 microm. Power exponents of the PSD functions vary significantly with tissue depth and precancerous state, giving insight into the morphological changes associated with precancerous lesions and providing substantial potential for noninvasive clinical diagnosis of squamous epithelial lesions and tumors.     

Nanoscale Organolanthanum Clusters: Nuclearity-Directing Role of Cyclopentadienyl and Halogenido Ligands

Tetramethylaluminato/halogenido(X) ligand exchange reactions in half-sandwich complexes [Cp^RLa(AlMe₄)₂] are feasible in non-coordinating solvents and provide access to large coordination clusters of the type [Cp^RLaX₂]_x. Incomplete exchange reactions generate the hexalanthanum clusters [Cp^R₆La₆X₈(AlMe₄)₄] (Cp^R=Cp*=C₅Me₅, X=I; Cp^R=Cp′=C₅H₄SiMe₃, X=Br, I). Treatment of [Cp*La(AlMe₄)₂] with two equivalents Me₃SiI gave the nonalanthanum cluster [Cp*LaI₂]₉, while the exhaustive reaction of [Cp′La(AlMe₄)₂] with the halogenido transfer reagents Me₃GeX and Me₃SiX (X=I, Br, Cl) produced a series of monocyclopentadienyl rare-earth-metal clusters with distinct nuclearity. Depending on the halogenido ion size the homometallic clusters [Cp′LaCl₂]₁₀ and [Cp′LaX₂]₁₂ (X=Br, I) could be isolated, whereas different crystallization techniques led to the aggregation of clusters of distinct structural motifs, including the desilylated cyclopentadienyl-bridged cluster [(μ-Cp)₂Cp′₈La₈I₁₄] and the heteroaluminato derivative [Cp′₁₀La₁₀Br₁₈(AlBr₂Me₂)₂]. The use of the Cp′ ancillary ligand facilitates cluster characterization by means of NMR spectroscopy.     

Comparison of electron spin resonance probe and dielectric relaxation in physically and chemically crosslinked polymers

Dielectric relaxation spectroscopy in the frequency range from 10⁻² Hz to 10⁶ Hz and electron spin resonance (ESR) experiments are employed to study the dynamics in chemically and physically crosslinked networks. As examples for physically crosslinked networks ortho- and para-cresol novolacs were investigated. Dielectrically these materials show low-temperature β- and high-temperature α-relaxation. Both relaxation regions differ for both types of novolacs. This is also reflected by the ESR measurements and is discussed in terms of different hydrogen bonds found to be stronger in para-cresol novolac. For the chemically crosslinked poly(triallyl isocyanurate) only a β-peak is found by the dielectric measurements. Also in the ESR experiment the slow motion regime is characterized up to high temperatures. This means that the segmental motion is strongly suppressed by chemical crosslinking. Nevertheless the obtained change in the formal T_50G value can be used to characterize the glass transition in highly crosslinked systems by the ESR method.