Are Methylaluminoxane Activators Sheets?

Density functional theory calculations on neutral sheet models for methylaluminoxane (MAO) indicate that these structures, containing 5-coordinate and 4-coordinate Al, are likely precursors to ion-pairs seen during the hydrolysis of trimethylaluminum (Me₃Al) in the presence of donors such as octamethyltrisiloxane (OMTS). Ionization by both methide ([Me]⁻) and [Me₂Al]⁺ abstraction, involving this donor, were studied by polarizable continuum model calculations in fluorobenzene (PhF) and o-difluorobenzene (DFB) media. These studies suggest that low MW, 5-coordinate sheets ionize by [Me₂Al]⁺ abstraction, while [Me]⁻ abstraction from Me₃Al-OMTS is the likely process for higher MW 4-coordinate sheets. Further, comparison of anion stabilities per mole of aluminoxane repeat unit (MeAlO)_n, suggest that anions such as [(MeAlO)₇(Me₃Al)₄Me]⁻=[ 7,4 ]⁻ are especially stable compared to higher homologues, even though their neutral precursors are unstable.     

Identification of the antioxidant principles of Polyalthia longifolia var. pendula using TEAC assay

Activity-guided fractionation of the ethanolic extract of the leaves of the Polyalthia longifolia var. pendula led to the identification of quercetin (1), quercetin-3-O-β-glucopyranoside (2), kaempferol-3-O-α-rhamnopyranosyl-(1 → 6)-β-galactopyranoside (3), kaempferol-3-O-α-rhamnopyranosyl-(1 → 6)-β-glucopyranoside (4), rutin (5) and allantoin (6) as the active constituents from the butanol fraction. Compounds 2-4 are reported for the first time from this natural source. Structures of the compounds were confirmed on the basis of their 1D and 2D NMR coupled with other spectroscopic methods. All the isolated compounds and the fractions were evaluated for their antioxidant potential using the TEAC assays and it was found that the activity of the active fraction was due to quercetin (1) and its glycosides (2 and 5), with TEAC values of 4.10, 1.91 and 2.38 mM, respectively, while the kaempferol glycosides were found to be inactive. This is the first study on the antioxidant activity of this plant species.     

Role of interstitial “caged” Fe in the superconductivity of FeTe1/2Se1/2

All samples are synthesized through a standard solid state reaction route and are quenched to room temperature systematically at 700 °C, 500 °C, 300 °C, and room temperature (RT); the samples are denoted 700Q, 500Q, 300Q, and RTQ, respectively. The structural, and magnetic properties are studied. Careful Rietveld analysis of the X-ray diffraction patterns revealed that all samples except 700Q crystallized in a single phase with space group P4/nmm; the amount of interstitial Fe (Fe_int) at the 2c site increased from 5% for RTQ to 8% for 500Q. Sample 700Q crystallized in the Fe₇Se₈ phase. The magnetization result revealed that RTQ and 300Q are superconducting at 10 K and 13 K, respectively, while 500Q and 700Q are not superconducting. Magnetic ordering was observed at around 125 K for all the samples. The prominence of in terms of effective moment is sufficiently higher for 500Q and 700Q than for RTQ and 300Q. Summarily, it is found that quenching-induced disorder affects the occupancy of interstitial Fe in FeTe_1/2Se_1/2 and thus both its superconducting and magnetic properties. Further, it clear that limited presence of interstitial Fe at 2c site is not completely contrary to the observation of superconductivity, because the 300Q sample possesses higher T_c (13 K) for higher Fe_int (6%) than the RTQ sample with relatively lower T_c (10 K) having lower Fe_int (5%). Further, the 500Q sample, with much higher Fe_int (8%), is non-superconducting.     

Synthesis and characterization of rigid rode shape homologous series: Effect of tail iodo group

Arylpiperazine derivatives referred in this article possessed antitumor activity, which were synthesized and crystallized through the gradual evaporation process. The molecular structures of 2-(4-(2-(4-phenylpiperazin-1-yl)ethyl)benzyl)isoindoline-1,3-dione (C27H27N3O2, 1), 2-(4-(2-(4-(4-bromophenyl)piperazin-1-yl)ethyl)benzyl)isoindoline-1,3-dione (C27H26BrN3O2, 2) and 2-(4-(2-(4-(4-chlorophenyl)piperazin-1-yl)ethyl)benzyl)isoindoline-1,3-dione (C27H26ClN3O2, 3) were determi-ned and described. π-π interactions were observed in the packing modes of three compounds, and compound 2 and 3 showed halogen interactions between molecules nearby, which were different from compound 1. The dihedral angle values, the bond lengths, bond angles and the parameters demonstrated that involvement of halogen atoms did affect the conformation, configuration and cell parameter of the compounds.     

An efficient chemoselective strategy for the preparation of (E)-cinnamic esters from cinnamaldehydes using heterogeneous catalyst and DDQ

An efficient chemoselective protocol is developed for the synthesis of (E)-cinnamic esters from substituted cinnamaldehydes or cinnamyl alcohols using a combination of DDQ and heterogeneous catalyst under microwave irradiation. The method showed remarkable selectivity for cinnamaldehydes over aliphatic and aromatic aldehydes, which is a novel finding. The results demonstrate that the developed protocol can be a useful synthetic tool for chemoselective esterification in total synthesis of complex organic compounds.     

An efficient synthesis of fluorine-containing substituted spiro[piperidine-4,4′-pyrano[3,2-c]quinoline]-3′-carbonitrile by nonconventional methods

A series of fluorine-containing substituted spiro[piperidine-4,4′-pyrano[3,2-c]quinolines] were synthesized through a rapid one-pot multi-component reaction under microwave irradiation and sonication. The method has the advantages of excellent yields (80-96%) and short reaction time (3-10 min). We provide a series of fluorinated quinoline derivatives interesting for biological screening tests.