Synthesis of novel chromogenic azocalix[4]arenemonoquinones and their binding with alkali metal cations

Five new chromogenic azocalix[4]arenemonoquinones have been synthesized, characterized and examined for their interaction with alkali metal cations (Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺) by UV-visible spectroscopic and cyclic voltammetric techniques. It has been determined that 4a selectively exhibits a significant bathochromic shift in its UV-visible spectrum on interaction with potassium ion in comparison to its treatment with other alkali metal cations. The binding stoichiometry of 4a and potassium ion was established to be 1:1 with an association constant of 3.27 × 10⁴ M^?1. Cyclic voltammetric experiments in 4:1 dichloromethane-acetonitrile also revealed a significant anodic shift (ΔE _(1/1′) = 115 mV) of the original redox waves of 4a on interaction with potassium ion.     

Analysis of large and non-standard geometry samples of ancient potteries by internal monostandard neutron activation analysis using in situ detection efficiency

The k ₀-based internal monostandard neutron activation analysis (IM-NAA) method was used for the analysis of 30 large and non-standard geometry ancient pottery samples obtained from Buddhist sites of Andhra Pradesh, India. One freshly finished pottery and a sun-drenched pottery were also analyzed for comparison. Samples were irradiated in thermal column facility of Apsara reactor and also in graphite reflector position of critical facility of Bhabha Atomic Research Centre. Radioactive assay was carried out using a 40% relative efficiency HPGe detector coupled to MCA. Concentration ratios of 15 elements with respect to Sc were determined. The La/Ce values as well as statistical cluster analysis utilizing concentration ratios of elements were used for grouping/provenance of the potteries.     

ortho‐Phenylenediamine: An Effective Spacer to Build Highly Magnetic Fe3O4/Au Nanocomposites

1,2‐Diaminobenzene, popularly known as ortho‐phenylenediamine (PDA), is found to be a prototype spacer for the deposition of gold nanoparticles on the surfaces of Fe₃O₄ microspheres. Upon carbonization with PDA, the morphology of the product changes significantly, and the resulting nanocomposites exhibit enhanced magnetism beyond the saturation value of Fe₃O₄. The Fe₃O₄/Au nanocomposites show good surface‐enhanced Raman spectroscopy activity with a detection limit of 10^?15 M .     

Positron annihilation studies of poly(N‐isopropyl acrylamide) gel in mixed solvents

Positron annihilation lifetime spectroscopy was used to characterize the reentrant volume‐phase‐transition behavior of poly(N‐isopropyl acrylamide) hydrogel in an ethanol/water mixed solvent. The polymer gel was synthesized with γ irradiation. The ortho‐positronium lifetime (τ₃) in the gel slowly increased with an increase in the ethanol content in the mixed solvent. τ₃ was not influenced by the volume phase transition. The ortho‐positronium intensity decreased with the collapse of the gel in an approximately 10% ethanol/water mixture. When swelled in pure ethanol, τ₃ initially increased with the solvent amount in the gel, showing the destruction of intramolecular hydrogen bonding and the relaxation of polymer chains. The lower critical solution temperature of the gel in the 10% ethanol/water mixture was lower than that in pure water, and τ₃ for various solvent contents showed behavior similar to that seen in pure solvent. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1028–1036, 2002     

Estimation of thorium intake due to consumption of vegetables by inhabitants of high background radiation area by INAA

A study was conducted to estimate the thorium concentration in locally grown vegetables in high background radiation area (HBRA) of southern coastal regions of India. Locally grown vegetables were collected from HBRA of southern coastal regions of India. Thorium concentration was quantified using instrumental neutron activation analysis. The samples were irradiated at CIRUS reactor and counted using a 40% relative efficiency HPGe detector coupled to MCA. The annual intake of thorium was evaluated using the consumption data provided by National Nutrition Monitoring Board. The daily intake of ²³²Th from the four food categories (green leafy vegetables, others vegetables, roots and tubers, and fruits) ranged between 0.27 and 5.352?mBq?d^?1. The annual internal dose due to ingestion of thorium from these food categories was 46.8?×?10^?8 for female and 58.6?×?10^?8?Sv?y^?1 for male.     

Determination of thorium concentrations in soil and sand samples using instrumental neutron activation analysis

Thorium along with its daughter products present in the soil is one of the major contributors to the external gamma dose in the environment. To establish the dose levels, quantification of thorium contents in soil samples is very important. As a part of pre-operational environmental radiological surveillance, a total of 23 soil and six sand samples were collected from different locations around the proposed nuclear power plant site of Jaitapur, Maharashtra. Thorium concentrations in these samples were determined by instrumental neutron activation analysis (INAA). Samples were irradiated with neutrons in Apsara reactor at a neutron flux of?~5?×?10¹¹ cm^?2 s^?1 and radioactive assay was carried out using high resolution gamma ray spectrometry. Relative method of INAA was used for quantification of thorium utilizing 311.9?keV gamma ray of ²³³Pa, the daughter product of ²³³Th. The concentrations of thorium in the soil and sand samples were in the ranges of 4.0?C18.8 and 1.2?C6.2?mg?kg^?1 respectively.     

Determination of concentration of iodine in grass and cow milk by NAA methods using reactor neutrons

Instrumental and preconcentration methods of neutron activation analysis (NAA) have been standardized for the determination of concentration of iodine in grass and cow milk samples, respectively. To study the transfer of iodine from grass to milk, known quantity of grass spiked with potassium iodide solution was fed to a cow. The spiked grass samples and milk samples, obtained from the cow after the ingestion of spiked grass, were collected. Iodine was separated from the milk samples chemically using Dowex 1X8 anion exchange resin. Spiked grass and ion exchange resin samples were neutron irradiated and radioactive assay was carried out using a 45?% relative efficiency HPGe detector coupled to an 8k channel analyzer. Iodine concentrations in spiked grass samples were found to be in the range of 1,487?C2,002?mg?kg^?1. Concentration of iodine in milk after 12?h of feeding the cow with spiked grass was 871?±?56???g?L^?1 which was reduced to 334?±?32???g?L^?1 after 48?h.     

Characterization of pneumatic fast transfer system irradiation position of KAMINI reactor for k 0-based NAA

The pneumatic fast transfer system position at KAMINI reactor, Indira Gandhi Centre for Atomic Research, India was characterized by determining the epithermal neutron flux shape factor (α) and the sub-cadmium to epithermal neutron flux ratio (f) for k ₀-based Neutron Activation Analysis (k ₀-NAA). For determination of α value, bare, Cd-ratio and Cd-cover methods were employed using dual and multi monitors namely Au, Zr and Zn. For calculation of f, Au and Zr monitors were used in the case of bare method and Au monitor was used for cadmium ratio and cadmium cover methods. The determined α-value of PFTS indicated a hard epithermal neutron spectrum and the f value indicated about 96 % thermal neutron component. For validation of k ₀-NAA method, reference materials namely NIST SRM 1646a (Estuarine Sediment) and BCS Nb-stabilized Stainless Steel (BCS/SS No.261/1) were analyzed. The percentage errors of the determined concentration values of elements were within ±5 % with respect to the certified values and the Z-score values at 95 % confidence level were within ±2 in most of the cases.     

Calix[4]arene-based ditopic receptors for simultaneous recognition of fluoride and cobalt(II) ions

A series of calix[4]arene based ditopic receptors possessing bipyridyl and hydrazone units have been synthesized and evaluated for ionic recognition. It has been observed that the synthesized derivatives function as allosteric receptors for simultaneous recognition of Co²⁺and F^? ions through non-covalent interactions. Significant bathochromic shifts in the UV–visible spectrum with a profound colour change promise their use to engineer novel applications.     

Microwave promoted methylation of plant polysaccharides

O-Methylation is of outstanding importance in structural polysaccharide chemistry. A novel method for the methylation of polysaccharides using microwave (MW) irradiation is described. Seed gum from Cyamopsis tetragonolobus (Guar) was fully methylated with dimethyl sulphate and sodium hydroxide using 100% microwave power for 4 min in 68% yield. The completely methylated seed gum thus obtained was hydrolyzed by 70% formic acid followed by 0.5N H₂SO₄ under full microwave power for 1.16 and 1.66 min, respectively. The partially methylated monosaccharides were separated and identified.