An improved approach to chiral cyclopentenone building blocks. Total synthesis of pentenomycin I and neplanocin A

An improved approach to enantiomerically pure hydroxylated cyclopentenones is reported here, which involves intramolecular nitrone cycloaddition of sugar-derived chiral pent-4-enals and hex-5-en-ones-2 followed by N-O bond cleavage, quaternization of the amine thus produced, and finally oxidative elimination of the amino group. Synthesis of pentenomycin I and neplanocin A is described following this methodology.     

The conformational analysis of aromatic methoxyl groups from carbon-13 chemical shifts and spin-lattice relaxation times

In a series of polymethoxy benzaldehydes and acetophenones it was found that diortho-substitution distorts the ArOCH₃ conformation. This distortion is accompanied by a downfield shift in the corresponding methoxyl ¹³C frequencies and an increase in their spin-lattice relaxation times.     

A New Class of “All‐Metal” Aromatic Hydrido‐Bridged Binary Coinage Metal Heterocycles. A DFT Study

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.     

Application of Chemoenzymatic Hydrolysis in the Synthesis of 2-Monoacylglycerols

The selective biocatalyzed synthesis of 2-monoacylglycerols (2-MAGs) through the use of commercially available immobilized Candida antarctica (Novozym435) and Rhizomucor miehei is explored. Reactions at room temperature result in the formation of a 2-MAG and a corresponding ethyl ester of the fatty acid with immobilized Candida antarctica within 2h with yields ranging from 36%-83%. Similar reaction conditions with immobilized Rhizomucor miehei yielded exclusively the 2-MAG after 24h with yields ranging from 37% to 88%. Yields vary on the acyl group at the sn-2 position and choice of enzyme involved.     

Amphiphilic diblock copolymer‐based multiagent photonic sensing scheme

Efficient functionalization of polymer optical fibers' (POF) surface by a novel block copolymer material toward the development of low‐cost multiagent sensors is presented. The employed poly(styrene sulfonate‐b‐tert‐butylstyrene) (SPS‐b‐PtBS) diblock copolymer possesses two blocks of distinctively different polarity and charge, the hydrophilic SPS which is sensitive to polar substances and the hydrophobic PtBS which is sensitive to organic solvents. The coexistence of two different blocks allows for the detection of a wide variety of agents, ranging from ammonia, and organic solvents, to biomolecules like lysozyme, at room temperature as opposed to alternative usually more complicated techniques, all with the sole use of one sensing medium. Copolymers' high glass transition temperature enables the formation of stable and environmentally robust overlayers. The sensing performance of the material is evaluated experimentally on the customizable platform of POFs, demonstrating fast response, high operational reversibility, and also reusability in successively different testing agents. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 46–54     

Statistical copolymers of methyl methacrylate and 2‐methacryloyloxyethyl ferrocenecarboxylate: Monomer reactivity ratios,thermal and electrochemical properties

Statistical copolymers of methyl methacrylate (MMA) with 2‐methacryloyloxyethyl ferrocenecarboxylate (MAEFC) were prepared by free radical polymerization. The reactivity ratios were estimated using the Fineman‐Ross, inverted Fineman‐Ross, Kelen‐Tüdos, and extended Kelen‐Tüdos graphical methods. Structural parameters of the copolymers were obtained by calculating the dyad monomer sequence fractions and the mean sequence length. The glass‐transition temperature (T_g) values of the copolymers were measured and examined by means of several theoretical equations, allowing the prediction of these T_g values. The thermal degradation behavior of the copolymers was also studied and compared with the respective homopolymers. Cyclic voltammetry was employed to study the electrochemical properties of the copolymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Assembly of quantum dots on peptide nanostructures and their spectroscopic properties

We present a chemical process for the decoration of self-assembled two-dimensional peptide fibrils with two different sizes of CdSe@ZnS core–shell quantum dots (Qdots) capped with trioctylphosphine oxide molecules. The attachment of the semiconducting nanoparticles to the fibrils is directed via disulfide bond between the quantum dot and cysteine aminoacids that are deliberately impeded in the peptide structures. A significant red shift in the emission spectra of the quantum dots is observed and attributed to the synergistic interaction between adjacent nanoparticles arranged on peptide film templates extending over hundreds of nanometers.     

Plasmonic response of ordered arrays of gold nanorods immersed within a nematic liquid crystal

We study theoretically the optical properties of a two-dimensional lattice of metallic (gold) nanorods immersed within a nematic liquid crystal (NLC) strongly anchored to the surface of the nanorods. The distribution of the director field of the NLC is found by minimising the corresponding total free energy via simulated annealing. Optical properties such as transmittance, reflectance and absorbance of the structure are found by employing a hybrid discrete-dipole approximation/layer-multiple-scattering technique. We show, in particular, that when the NLC is strongly anchored to the nanorods, light absorbance is more efficient compared to the case where the liquid crystal (LC) is aligned by application of an external field. Also, the alignment of the LC molecules via an external field leads to a significant shift of the surface-plasmon resonance of the gold nanorods relative to the strong-anchoring case, an effect which can be exploited in switching applications. We also report that the rate of light absorption is a non-monotonic function of the height of nanorods due to the guiding of EM waves taking place for long enough nanorods.