Oxidative Deoximation with Sodium Perborate1

An efficient and convenient conversion of oximes to corresponding carbonyl compounds with sodium perborate in glacial acetic acid is reported.     

Spectral and electrochemical investigation of p-sulfonatocalix[4]arene-stabilized vitamin E aggregation

The host–guest interaction of α-tocopherol (vitamin E) with p-sulfonatocalix[4]arene (p-SC4) in solution state is studied using emission and cyclic voltammetric techniques. The lipid soluble α-tocopherol (α-T) forms a solid complex with p-SC4. FTIR and NMR spectral analysis of the solid complex reveals the tight packing of α-T inside the cavity of p-SC4. The structural deformation is confirmed by XRD analysis. SEM images differentiate the highly porous gel like structure of vitamin E aggregate and the solid structure of the host–guest complex prepared. NOESY spectra confirm the tight penetration of α-T within the hydrophobic cavity of p-SC4.     

Synthesis of a Novel Dispiroheterocyclic Framework via the Regioselective 1,3‐Dipolar Cycloaddition Reaction of Azomethine Ylides

2‐Arylidene‐1,3‐indanediones undergo regioselective 1,3‐dipolar cycloaddition with the azomethine ylide generated from acenaphthenequinone and sarcosine to afford a rare class of complex dispiropyrrolidines in good yield. Single‐crystal X‐ray crystal analysis of one of the products confirms the structure and regiochemistry of the cycloaddition.     

Distribution of trace elements in flowing surface waters: Effect of seasons and anthropogenic practices in India

This study reports the distribution of Cr, Ni, Cu and Pb in waters, sediments, macrophytes and fish of the Yamuna River’s patch in Delhi (India). This is one of the most polluted stretches of rivers in the world. Water from this river is used fosr irrigation, industrial and domestic purposes, including drinking water. The effects of season and anthropogenic practices were identified. Almost zero dissolved oxygen and high levels of lead and phosphate indicate the polluted state of the aquatic system. The enrichment factors in sediments (with respect to reference site) vary in the range of 0.60–82.9% (Cr), 1.40–90.5% (Ni), 1.00–85.3% (Cu) and 3.80–86.6% (Pb). The toxic effects due to Ni and Pb could frequently be visible in aquatic life as their values fall above the probable effect level (36 mg Kg^?1 for Ni and 91.3 mg Kg^?1 for Pb). The metal contents in the macrophyte (Eichhornia crassipes) and the fish (Oreochromis niloticus) generally increase in the summer season. Cu and Pb accumulate preferentially in E. crassipes. The fish from these waters is unsuitable for human consumption as the levels of Cr, Cu and Pb are above the recommended limits. Significant spatial variations in parameters of water and sediments were confirmed via one-way analysis of variance. The Pearson’s correlation analysis suggests a common source of some of the metals. Principal component analysis highlighted domestic, and industrial waste and coal-fired thermal power plants as the metal sources. This study might act as a benchmark for other investigations focused on similarly affected surface aquatic systems due to agricultural and industrial activities.     

Molecules relevant for organic photovoltaics: a range-separated density functional study

Accurate determination of both fundamental and optical gap is necessary for designing molecules relevant for organic photovoltaics. Here, we study how range-separated density functionals reproduce frontier orbital energies, HOMO (highest occupied molecular orbital)–LUMO (lowest unoccupied molecular orbital) gaps, and optical gaps for molecules relevant for organic photovoltaics. In this study, we consider 12 different range-separated density functional for computing HOMO energy, HOMO–LUMO gap, and optical gap which are compared with available experimental and reported GW values. We found that the reproduction of desired photovoltaic properties primarily depend on range separation parameter. Moreover, the tested functionals are comparable with OT-BNL functional.     

Chemometric and trend analysis of water quality of the South Chennai lakes: an integrated environmental study

In order to bring out the nature of the factors influencing lake water composition, multivariate statistical analysis and trend analysis were performed based on the hydrochemical data of the study area, namely, South Chennai. Change in land use pattern and settlements along the banks of the lakes alters the quality and quantity of the surface water. In the present study, the R‐mode factor analysis and cluster analysis were applied to the geochemical parameters of the water to identify the factors affecting the chemical composition of the lake water. Dendograms of both the seasons give three major clusters, reflecting the groups of unpolluted to moderately polluted, polluted, and heavily polluted stations. The movement of stations from one cluster to another clearly brings out the seasonal variation in the chemical composition of the lake water. The complex hydrochemical data of the surface water were interpreted by condensing them into three major factors. Factor score analysis was used successfully to delineate the stations under study and the role of the contributing factors, and the nature of factors responsible for the variation in chemical composition of the water has been clearly brought out. Results of trend analysis using ArcGIS clearly indicate that the trend in water quality is deteriorating at a faster rate in the eastern part of the study area. It is understood that although natural shifts probably can account for some of the variation, it is most likely that human activities play a major role in affecting the water quality on a regional scale. Copyright © 2014 John Wiley & Sons, Ltd.     

The Synthesis and Bioactivity of Dimethyl (2,3- Dihydrobenzo[b][1,4]Dioxin-6-Yl)(Aryl Amino)Methylphosphonates

Abstract

A new series of α-aminophosphonates have been synthesized by a one-pot three-component reaction of 2,3-dihydrobenzo[b][1,4]dioxine-6-carbaldehyde, various amines, and dimethyl phosphite by using nano-TiO₂ as a catalyst under solvent-free conditions at 50°C. The major advantages of the present method are high yields, short reaction times, recyclable catalyst, and solvent-free reaction conditions. Among these new structurally diversified set of α-aminophosphonates, dimethyl (2,3-dihydrobenzo[b][1,4]dioxin-6-yl)(3-nitrophenylamino) methylphosphonate and dimethyl (2,3-dihydrobenzo[b][1,4]dioxin-6-yl)(4-fluoro-3-nitro-phenyl-amino) methylphosphonate have shown higher antioxidant activity in diphenyl picryl hydrazyl (DPPH) scavenging, reducing power assay, and lipid peroxidation methods.     

Synthesis and Bioassay of Ethyl-2- (2-((Diethoxyphosphoryl) (Aryl) Methylamino)Thiazol-4-Yl)-2-(Methoxyimino)Acetates

Abstract

A simple, efficient, and environmentally benign methodology has been accomplished for the synthesis of α-aminophosphonates by one-pot three-component reaction of ethyl-2-amino-α-(methoxy-imino)-4-thiazoleacetate, aldehydes, and diethylphosphite by using Amberlyst-15 as catalyst at room temperature under solvent-free conditions. Their chemical structures were characterized by infrared (IR), NMR (¹H, ¹³C & ³¹P), mass spectral, and elemental analysis. All the title compounds were screened for radical-scavenging activity by 1,1-diphenyl-2-picrylhydrazyl (DPPH), nitic oxide (NO), and hydrogen peroxide (H₂O₂) methods.

Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental files: Additional text and figures.     

Physicochemical Characterization of Hydrated 4-Sulphonato-Calix[n]arenes: Thermal,Structural, and Sorption Properties

In this study, the thermal behavior of three hydrated water-soluble 4-sulphonato calix[n]arenes was investigated. The melting points, heats of fusion, and heats of solution of the calix[4]arene, calix[6]arene and calix[8]arene were 277, 262, and 270°C; 192, 242 and 351 kJ/mol; and 30, 58 and 63 kJ/mol, respectively. Lower heat of fusion, smaller increase in entropy and smaller heat of solution of the calix[4]arene compared to the calix[6]arene and calix[8]arene showed that less heat was required to break up the crystal lattice of the smaller macromolecule. This apparent anomaly is rationalized in terms of smaller cooperativity of interaction between the molecules of calix[4]arene in the crystal lattice, although the strength of the individual interactions is stronger as evidenced by the higher melting point. TGA analysis indicated that about 17–20% of water was associated with the calix[n]arenes. Both TGA and hot stage microscopy results indicated that upon heating these molecules underwent stepwise water loss. TGA kinetics showed that the 4-sulphonato-calix[8]arene lost water easier than the other two calixarenes. The moisture adsorption behavior of all calixarenes followed type II isotherms. For the same amount of material, the calix[6]arene adsorbed more moisture than the calix[4]arene and the calix[8]arene. Moreover, dehydrated less crystalline 4-sulphonic-calix[n]arenes powders are hydroscopic.