Chiral diphosphine ligands based on camphor: synthesis and applications in asymmetric hydrogenations

The synthesis of a novel class of atropisomer chiral diphosphine ligands with a bornene framework is described. The new ligands showed in Rh catalyzed asymmetric hydrogenation of α- and β-enamides very high ee’s (more than 99%).     

Formation of tetra(ethylene oxide) terminated Si-C linked monolayers and their derivatization with glycine: an example of a generic strategy for the immobilization of biomolecules on silicon

Surface modification with oligo(ethylene oxide) functionalized monolayers terminated with reactive headgroups constitutes a powerful strategy to provide specific coupling of biomolecules with simultaneous protection from nonspecific adsorption on surfaces for the preparation of biorecognition interfaces. To date, oligo(ethylene oxide) functionalized monolayer-forming molecules which can be activated for attachment of biomolecules but which can selectively form monolayers onto hydrogen terminated silicon have yet to be developed. Here, self-assembled monolayers (SAMs) containing tetra(ethylene oxide) moieties protected with tert-butyl dimethylsilyl groups were formed by thermal hydrosilylation of alkenes with single-crystal Si(111)-H. The protection group was used to avoid side reactions with the hydride terminated silicon surface. Monolayer formation was carried out using solutions of the alkene in the high-boiling-point solvent 1,3,5-triethylbenzene. The protecting group was removed under very mild acidic conditions to yield a free hydroxyl functionality, a convenient surface moiety for coupling of biological entities via carbamate bond formation. The chemical composition and structure of the monolayers before and after deprotection were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray reflectometry. To demonstrate the utility of this surface for covalent modification, two reagents were compared and contrasted for their ability to activate the surface hydroxyl groups for coupling of free amines, carbonyl diimidazole (CDI), and disuccinimidyl carbonate (DSC). Analysis of XP spectra before and after activation by CDI or DSC, and after subsequent reaction with glycine, provided quantitative information on the extent of activation and overall coupling efficiencies. CDI activated surfaces gave poor coupling yields under various conditions, whereas DSC mediated activation followed by aminolysis at neutral pH was found to be an efficient method for the immobilization of amines on tetra(ethylene oxide) modified surfaces.     

Organic–inorganic nanocomposites prepared from fluoro-aramid and silica

Fluoro-aramid-based sol/gel-derived nanocomposites were synthesized by condensing a mixture of 4,4′-(hexafluoro-isopropylidene)dianiline and 1,3-phenylenediamine with terephthaloylchloride (TPC) in dimethylacetamide. TPC was added in slight excess to produce amide chains with carbonyl chloride end groups and then replaced with alkoxy groups using aminophenyltrimethoxysilane to develop bonding with the silica network. Mechanical, dynamic mechanical thermal, water absorption and morphological measurements were carried out on the thin hybrid films. Increase in the tensile strength and modulus was observed as compared to pristine polyamide. The thermal decomposition temperature was found in the range of 400–500 °C. The water absorption was found to be reduced with higher silica content. The glass transition temperature and the storage moduli increased with increasing silica concentration. The maximum increase in the T _g value (345 °C) was observed with 20 wt% silica. Scanning electron microscopy revealed the uniform distribution of silica in the matrix with an average particle size ranging from 8 to 50 nm.     

Chiral methylbenzylammonium salts of aryldithiophosphonic acids containing glucofuranose,allofuranose, and galactopyranose diacetonide scaffolds

Abstract

New chiral methylbenzylammonium salts of aryldithiophosphonic acids containing glucofuranose, allofuranose, and galactopyranose diacetonide substituents were obtained using (S)-(–)-α-methylbenzylamine, (R)-(+)-α-methylbenzylamine, and (R,S)-(±)-α-methylbenzylamine. Salts obtained possess antimicrobial activity.     

New Developments on Operator Reverse AM-GM Inequality for Positive Linear Maps

Acta Mathematica Sinica, English Series - In this research article, we shall give some reverse Arithmetic-Geometric mean inequalities for unital positive linear maps on Hilbert space operators...     

Stereochemical features of the physical and chemical interactions of singlet oxygen with enecarbamates

Oxazolidinone-substituted enecarbamates represent a mechanistically rich system for the study of stereoelectronic, steric, and conformational effects on stereoselectivity and mode selectivity in (1)O(2) [2 + 2] and ene reactions. Photooxygenation of these enecarbamates with (1)O(2) leads to diastereomerically pure dioxetanes that decompose to yield an oxazolidinone carbaldehyde and one of the two enantiomers of methyldesoxybenzoin in enantiomeric excess. Stereoselectivity originates at the allylic stereocenter, a result supported by quenching studies, computational analysis, and deuterium solvent isotope effects. [reaction: see text]     

Ab-initio calculations of structural,electronic,and optical properties of Zn_3(VO_4)_2

The structural, electronic, and optical properties of Zn_3(VO_4)_2 are investigated using full potential linearized augmented plane wave(FP-LAPW) method within the framework of density functional theory(DFT). Various approaches are adopted to treat the exchange and correlation potential energy such as generalized gradient approximation(GGA),GGA+U, and the Tran–Blaha modified Becke–Johnson(TB-mBJ) potential. The calculated band gap of 3.424 eV by TB-mBJ is found to be close to the experimental result(3.3 eV). The optical anisotropy is analyzed through optical constants,such as dielectric function and absorption coefficient along parallel and perpendicular crystal orientations. The absorption coefficient reveals high absorption(1.5 × 10~(6) cm~(-1)) of photons in the ultraviolet region.     

Control of modulated vibration using an enhanced adaptive filtering algorithm based on model-based approach

Conventional adaptive filtering algorithms, typically limited to the control of single or multiple sinusoids, are not appropriate to control modulated vibrations, especially in the presence of rich side band structures. To overcome this deficiency, a new control algorithm is proposed that introduces a feedback loop with the model predictive sliding mode control (MPSMC) in the adaptive filtering system. Several amplitude and frequency modulation cases are first computationally studied, and conventional and proposed methods are comparatively evaluated in terms of estimation error, performance in time and frequency domains, stability, and uncertainty in the reference signal. To experimentally validate the proposed algorithm, an active strut (with longitudinal vibrations) is constructed. Overall, the proposed adaptive algorithm yields superior reductions at the main frequencies and at side bands; also, good attenuation is found on a broadband basis.