Thermal study of accumulation of conformational disorders in the self-assembled monolayers of C8 and C18 alkanethiols on the Au111 surface

The thermal stability of short alkanethiol CH(3)(CH(2))(7)SH (C(8)) and long C(18) self-assembled monolayers (SAMs) is investigated using grazing angle reflection-absorption infrared spectroscopy, cyclic voltammetry, and molecular dynamics simulation. We track the disordering of SAM by untilting and gauche defect accumulation with increasing temperature in the 300-440 K range, a range of interest to tribology. Molecular dynamics simulation with both fully covered and partially covered C(6), C(8), and C(18) monolayers brings out the morphological changes in the SAM, which may be associated with the observed thermal stability characteristics. The molecular dynamics simulations reveal that short-chain C(6) and C(8) alkanethiols are more defective at lower temperature than the long-chain C(18) alkanethiol. With increasing temperature disorder in the SAM, as reflected in both untilting and gauche defect accumulation, tends to saturate at temperatures below 360 K for short-chain SAMs such that any further increase in temperature, until desorption, does not lead to any significant change in conformational order. In contrast the disorder in the long-chain C(18) SAM increases monotonically with temperature beyond 360 K. Thus, in a practical range of temperature, the ability of a SAM to retain order with increasing thermal perturbations is governed by the state of disorder prior to heat treatment. This deduction derived from molecular dynamics simulation helps to rationalize the significant difference we have observed experimentally between the thermal response of short- and long-chain thiol molecules.     

Optimization of experimental conditions for composite biodiesel production from transesterification of mixed oils of Jatropha and Pongamia

India is looking at the renewable alternative sources of energy to reduce its dependence on import of crude oil. As India imports 70?% of the crude oil, the country has been greatly affected by increasing cost and uncertainty. Biodiesel fuel derived by the two step acid transesterification of mixed non-edible oils from Jatropha curcas and Pongamia (karanja) can meet the requirements of diesel fuel in the coming years. In the present study, different proportions of Methanol, Sodium hydroxide, variation of Reaction time, Sulfuric acid and Reaction Temperature were adopted in order to optimize the experimental conditions for maximum biodiesel yield. The preliminary studies revealed that biodiesel yield varied widely in the range of 75–95?% using the laboratory scale reactor. The average yield of 95?% was obtained. The fuel and chemical properties of biodiesel, namely kinematic viscosity, specific gravity, density, flash point, fire point, calorific value, pH, acid value, iodine value, sulfur content, water content, glycerin content and sulfated ash values were found to be within the limits suggested by Bureau of Indian Standards (BIS 15607: 2005). The optimum combination of Methanol, Sodium hydroxide, Sulfuric acid, Reaction Time and Reaction Temperature are established.     

Synthetic magnetic opals

We present studies of novel nanocomposites of BiNi impregnated into the structure of opals as well as inverse opals. Atomic force microscopy and high resolution elemental analyses show a highly ordered structure and uniform distribution of the BiNi filler in the matrix. These BiNi-based nanocomposites are found to exhibit distinct ferromagnetic-like ordering with transition temperature of about 675 K. As far as we know there exists no report in literature on any BiNi compound which is magnetic.     

Biginelli-type reaction: Efficient synthesis of 5-unsubstituted 3,4-dihydropyrimidin-2-ones and thiones from gem-dibromomethylarenes

In the present study, we are reporting a simple and efficient method for the one-pot synthesis of the biologically important heterocyclic molecules 5-unsubstituted 3,4-dihydropyrimidin-2-ones and thiones using gem-dibromomethylarenes, oxalacetic acid, and urea or thiourea. Gem-dibromomethylarenes are used as aldehyde equivalent for the efficient synthesis of 3,4-dihydropyrimidin-2-ones/thiones. This reaction offers advantages for the synthesis of these compounds, including ready availability of the starting materials, experimental simplicity and in good yields. Besides, the synthesized molecules are interesting for their biological and pharmacological actions.     

Studies on radon/thoron and their decay products in granite quarries around Bangalore city, India

The radon survey was performed in granite quarries around Bangalore rural district and Bangalore city as part of a lung cancer epidemiological study. Long duration measurements of indoor and outdoor radon, thoron and their progenies concentrations were made around granite quarries of Bangalore rural district by using Solid State Nuclear Track Detector (SSNTD, LR-115, Type-II Plastic track detector) during summer and winter period (2006–07). The increase of radioactivity in granite quarries and inhalation dose to workers and populations near the quarries have been summarized. The higher concentrations of radon and thoron in granite quarries suggest radiation health effects on workers and public around the quarries is higher than permissible levels. The results are presented and analyzed with reference to ICRP limits.     

A host-guest optical sensor for aliphatic amines based on lipophilic cyclodextrin

A host-guest optical sensor for the determination of aliphatic amines as exemplified by octylamine is proposed. It is based on the reversible fluorescence enhancement of heptakis(2,6-di-O-isobutyl)-β-cyclodextrin(DOB-β-CD) hosting tetraphenylporphyrin (TPP) immobilized in poly(vinyl chloride) (PVC) membrane by aliphatic amine extracted from aqueous phase into membrane phase. The optimum membrane contained 1.15 wt % TPP, 6.15 wt % DOB-β-CD as sensing reagent and other membrane materials. The fluorescence enhancement of the membrane resulted from the formation of a stable three-component complex among DOB-β-CD, TPP, and aliphatic amines. With the optimum conditions described, the fluorescence response of the sensor to octylamine shows a good correlation with the theoretically derived equation in the range 1.0 × 10^–6 to 8.0 × 10^–4 mol/L. The response characteristics including reversibility, response time, reproducibility and lifetime and selectivity of this optical device are also discussed in detail. This sensor has also been applied for the determination of octylamine in water samples containing interferents with satisfactory recovery.     

Disequilibrium of uranium series radionuclides in soil and plants of South India

Soil and plants of South India were analysed using standard methods for equilibrium state between radionuclides ²²⁶Ra, ²¹⁰Pb, and ²¹⁰Po of uranium series. A disequilibrium state was observed, with mean ²¹⁰Pb/²²⁶Ra, ²¹⁰Po/²²⁶Ra, and ²¹⁰Po/²¹⁰Pb as 21.71, 5.52, and 0.40; 10.01, 4.21, and 0.43; and 30.86, 9.34, and 0.35 in Coastal Karnataka, Malnad Karnataka, and Malnad Kerala, respectively. ²¹⁰Po/²¹⁰Pb in soil was 0.29, 0.30, and 0.49 respectively, for the three regions. Unsupported ²¹⁰Pb and ²¹⁰Po might have caused the observed disequilibrium state. The investigation helps to monitor radionuclide distribution and dynamics in soil and plants of the study area.

     

Separation and determination of process-related impurities of erlotinib using reverse-phase HPLC with a photo-diode array detector

A simple and rapid reverse-phase high-performance liquid chromatographic (HPLC) method for the simultaneous separation and determination of erlotinib and its process-related impurities in bulk drugs has been developed. Five process-related impurities of erlotinib have been separated on an Inerstsil ODS-3V (C18) column and detected at 254 nm using a photo diode array (PDA). This HPLC method was successfully applied to the analysis of erlotinib bulk drug. The recoveries of erlotinib and process-related impurities were in the range of 92.86-106.23%, and found to be specific, precise and reliable for the determination of unreacted raw materials, intermediates in the reaction mixtures and bulk drugs.     

Diblock copolymer membranes investigated by single-particle tracking

We report a study on particle diffusion in membranes formed from polystyrene-block-poly(2-(dimethylamino)ethyl methacrylate) (PS-b-PDMAEMA) diblock copolymers. The membranes were investigated by scanning electron microscopy and by single-particle tracking employing carboxy-functionalized polystyrene beads loaded with a fluorophore as spectroscopic probes. From the diffusion trajectories we extracted the domain size distribution of the membranes and the local diffusion coefficient of the beads as a function of the size of the beads. The single-particle tracking data revealed that the effective domain sizes of the membranes are reduced with respect to the domain sizes obtained from scanning electron microscopy, reflecting the confined diffusion of the probe particles due to interactions with the domain walls. This is corroborated by a clear correlation between the diffusion coefficient of an individual polystyrene bead and the size of the actual domain to which it is confined.