Fused‐ring nitrogen and sulfur heterocycles by a tandem SN2‐michael addition reaction

A tandem S_N2‐Michael addition reaction has been developed for the synthesis of cis‐ and trans‐fused nitrogen and sulfur heterocycles from the cis and trans isomers of ethyl (±)‐(2E)‐3‐[2‐(iodomethyl)cyclo‐hexyl]‐2‐propenoate. Octahydro‐1H‐isoindole‐1‐acetic acid and octahydrobenzo[c]thiophene‐1‐acetic acid derivatives have been prepared and their stereochemistries elucidated using NMR and X‐ray crystallo‐graphic methods. Cyclization substrates for both the cis‐ and the trans‐fused rings are readily available in four steps from known compounds. Yields for the cyclization range from 80‐85% and stereochemical selec‐tivities with respect to the side chain vary from 12.5‐16:1 for the cis‐fused structures to 6‐7.5:1 for the trans‐fused structures. Steric interactions in the transition states for ring closure are proposed to rationalize the observed preferences.     

The synthesis of 1-(4-triethoxysilyl)phenyl)-4,4,4-trifluoro-1,3-butanedione, a novel trialkoxysilane monomer for the preparation of functionalized sol-gel matrix materials

The title compound, 1-(4-triethoxysilyl)phenyl)-4,4,4-trifluoro-1,3-butanedione, was synthesized in a three-step sequence starting from 2-(4-bromophenyl)propene. Containing both a trialkoxysilyl and a substituted 1,3-butanedione functional grouping within its structure, this new silane is a viable starting material for the preparation of functionalized sol-gel materials.     

Archaeal tetraether lipids

The extremely stable biomolecules manufactured by organisms from extreme environments are of great scientific and engineering interest in the development of robust and stable industrial biocatalysts. Identification of molecules that impart stability under extremes will also have a profound impact on our understanding of cellular survival. This review discusses isolation and characterization of archaeal tetraethers as well as target technologies for tetraether lipid application. The isolation and characterization of archaeal tetraether lipids has led to some interesting applications improving on ester lipid technologies. Potential applications include novel lubricants, gene-delivery systems, monolayer lipid matrices for sensor devices, and protein stabilization. Following this review, patent abstracts and additional literature pertaining to the isolation, characterization, and application of archaeal membrane lipids are listed.     

Coordination-Induced Band Gap Reduction in a Metal–Organic Framework

Herein, we report on the synthesis of a microporous, three-dimensional phosphonate metal–organic framework (MOF) with the composition Cu₃(H₅-MTPPA)₂ ⋅ 2 NMP (H₈-MTPPA=methane tetra-p-phenylphosphonic acid and NMP=N-methyl-2-pyrrolidone). This MOF, termed TUB1, has a unique one-dimensional inorganic building unit composed of square planar and distorted trigonal bipyramidal copper atoms. It possesses a (calculated) BET surface area of 766.2 m²/g after removal of the solvents from the voids. The Tauc plot for TUB1 yields indirect and direct band gaps of 2.4 eV and 2.7 eV, respectively. DFT calculations reveal the existence of two spin-dependent gaps of 2.60 eV and 0.48 eV for the alpha and beta spins, respectively, with the lowest unoccupied crystal orbital for both gaps predominantly residing on the square planar copper atoms. The projected density of states suggests that the presence of the square planar copper atoms reduces the overall band gap of TUB1, as the beta-gap for the trigonal bipyramidal copper atoms is 3.72 eV.     

Raman spectral analysis of renal tissue: a novel application

Renal cell carcinoma (RCC) accounts for 85% of all primary renal cancers. The definitive diagnosis of RCC relies exclusively on the subjective pathological interpretation of the surgical specimen. In this study, we aimed to analyze renal tissue using objective Raman spectroscopy (RS). We obtained 15 pairs of RCC (T) and corresponding normal renal parenchymal tissues (N) from our biobank. There are three subtypes of RCC: clear cell RCC (ccRCC), papillary RCC (pRCC), and chromophobe RCC (cRCC). Five pairs of tissue of each subtype were enrolled. Fresh‐frozen sliced tissues were used for the RS detection. The Raman spectra between T and N were compared and analyzed using partial least squares (PLS) regression. Data for a total of 55 T and 58 N analyzable RS samples were obtained. The spectra were normalized by dividing the intensity of the characteristic peak at 1003 cm⁻¹ using phenylalanine's Raman peak. After further analysis with PLS, the sensitivity and specificity for discriminating T from N were 95% and 93%, respectively. The RCC subtypes can be discriminated at an accuracy of 72% for ccRCC, 88% for cRCC, and 86% for pRCC. This study demonstrates the feasibility of analyzing renal tissue using RS. RS, with its advantages of easy and objective tissue assessment, may be applied to aid intraoperative decision making and pathological tissue assessment. Copyright © 2014 John Wiley & Sons, Ltd.