Synthesis and spatial structure of new chiral dopants from allobetuline series for cholesteric liquid-crystal compositions

Structural Chemistry - New series of chiral dopants for cholesteric liquid-crystal compositions were synthesized on the base of 2-substituted allobetuline derivatives, and their steric structure...     

Resolution of enantiomers of [α-hydroxy-(o-chlorophenyl)methyl]phosphinic acid via diastereomeric salt formation with enantiopure 1-phenylethylamines

The resolution of racemic α-hydroxy-H-phosphinic acid with enantiopure 1-phenylethylamines via diastereomeric salt formation was investigated. X-Ray crystallographic analysis of the salt revealed that (R)-1-phenylethylamine to be efficient resolving agent for obtaining a single enantiomer of [α-hydroxy-(o-chlorophenyl)methyl]phosphinic acid. Resolving racemic α-hydroxy-H-phosphinic acid with (S)-2-phenylethylamine also gave access to (S)-α-hydroxyalkylphosphinic acid in good yield.     

7-β- and 10-β-Hydroxylated congeners of CAF-603; elucidation of absolute configuration of CAF-603 family,and their SAR studies in the anti-fungal activity

Novel 7-β- and 10-β-hydroxylated congeners of CAF-603 (4 and 5, respectively) were isolated from Trichoderma crassum. Relative configuration of 4 was determined by NOE experiments. Stereochemistry of 7-β-hydroxy group in 5 was established by a combination of vicinal ³J_H–H analyses and quantum chemical calculations. Absolute configurations of 4 and 5 were established by observing the Cotton effects of their bis(2-naphthoate) esters. T. crassum also produce known CAF-603 (1), 14-hydroxy and 8,9-β-epoxy derivatives (2 and 3, respectively). Present study first established the absolute configuration of CAF-603 family by taking their biosyntheses into account. Preliminary biological experiments revealed that the molecular target strictly recognizes the β-side of the cycloheptane ring.     

The effect of melt flow index, melt flow rate, and particle size on the thermal degradation of commercial high density polyethylene powder

The powder of EX5 grade of high density polyethylene—without any additives—manufactured by Amirkabir petrochemical company was separated by shaker equipment. The separated powder of average diameter ~25, ~62.5, ~87.5, ~112.5, ~137.5, ~175 and the particles >200 μm was tested by a thermogravimetric (TG) analysis instrument in nitrogen atmosphere and heating rates of 10, 20, and 30 °C min^?1. In addition, the separated powders were analyzed by a melt flow index (MFI) instrument, and the viscosity average molecular mass (M _v) of the powders was tested by a viscometer. Kinetic evaluations were performed by Friedman and Kissinger analysis methods and apparent activation energy for the overall degradation of the powders was determined. The effects of molecular mass, MFI, MFR, and particle size on the degradation TG curve, derivative thermogravimetry curve breadth, and activation energy of thermal degradation were considered. The results showed that the M _v of EX5 pipe grade produced by two serial reactors is increased by increasing of the particle size and, MFI is decreased with a little deviation by particle size increasing. The particle size has no obvious effect on the melt flow rate (MFR), and MFR as function of molecular mass distribution does not change very much. The results showed that the powder with bigger particles and higher molecular mass moderately increases the activation energy and shifts the degradation curve to the higher temperatures.     

A Proline-Based Aminophosphinic Acid Ligand and It’s Vanadyl Complex: Synthesis,Characterization and In Vitro Inhibitory Effects on α-Amylase And α-Glucosidase

Abstract

A proline-based aminophosphinic acid ligand and it's vanadium complex have been synthesized and characterized by spectroscopic techniques. The inhibitory activity on pancreatic α-amylase and Baker's yeast α-glucosidase has been examined in vitro. The novel complex showed more inhibitory potency against pancreatic α-amylase and Baker's yeast α-glucosidase compared to acarbose as an antidiabetic drug.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Quantification of Competing H3PO4 Versus HPO3 + H2O Neutral Losses from Regioselective 18O-Labeled Phosphopeptides

Abundant neutral losses of 98 Da are often observed upon ion trap CID-MS/MS of protonated phosphopeptide ions. Two competing fragmentation pathways are involved in this process, namely, the direct loss of H₃PO₄ from the phosphorylated residue and the combined losses of HPO₃ and H₂O from the phosphorylation site and from an additional site within the peptide, respectively. These competing pathways produce product ions with different structures but the same m/z values, potentially limiting the utility of CID-MS³ for phosphorylation site localization. To quantify the relative contributions of these pathways and to determine the conditions under which each pathway predominates, we have examined the ion trap CID-MS/MS fragmentation of a series of regioselective ¹⁸O-phosphate ester labeled phosphopeptides prepared using novel solution-phase amino acid synthesis and solid-phase peptide synthesis methodologies. By comparing the intensity of the –100 Da (–H₃PO₃ ¹⁸O) versus –98 Da (–[HPO₃ + H₂O]) neutral loss product ions formed upon MS/MS, quantification of the two pathways was achieved. Factors that affect the extent of formation of the competing neutral losses were investigated, with the combined loss pathway predominantly occurring under conditions of limited proton mobility, and with increased combined losses observed for phosphothreonine compared with phosphoserine-containing peptides. The combined loss pathway was found to be less dominant under ion activation conditions associated with HCD-MS/MS. Finally, the contribution of carboxylic acid functional groups and backbone amide bonds to the water loss in the combined loss fragmentation pathway was determined via methyl esterification and by examination of a phosphopeptide lacking side-chain hydroxyl groups.

High-performance supercapacitors based on an ionic liquid-derived nanofibrillated mesoporous carbon

This article reports the superior specific capacitance, energy, and power density of a nanofibrillated mesoporous carbon derived from an ionic liquid source (IFMC). It was concluded that high specific capacitance and good electrical conductivity were originated from contribution of nitrogen content of IFMC, also the interesting nanofibrillated structure. A specific capacitance of 235 F g^?1 at a high discharge current of 5 A g^?1 was estimated for IFMC-based electrode which is higher than the most reported capacitance for carbon materials. An excellent performance of the nanofibrillated mesoporous carbon along with proper concentration of nitrogen constituent in the carbonaceous framework is indicative for important effects of tuning the carbon nanostructure for energy storage applications.