Application of Ball Milling Technology to Carbohydrate Reactions: I. Regioselective Primary Hydroxyl Protection of Hexosides and Nucleoside by Planetary Ball Milling‡

Dry ball milling of hexosides with trityl chloride in the presence of DABCO or Na₂CO₃ has been found to result in their complete conversion to the respective 6‐O‐trityl ethers. Further wet grinding of the reaction mixture with Ac₂O in the presence of DMAP led to the respective fully protected hexosides in good to excellent yields after isolation. It has been found to be an effective one‐pot two‐step synthesis under solvent‐free condition. The speed of homogenization has been shown to highly influence the rate and outcome of the reaction, and commercially available planetary ball mill has been proved to be very convenient for carrying out the reaction under standardized and reproducible conditions.     

From beads-to-wires-to-fibers of tungsten oxide: electrochromic response

Suitable host lattice and morphology for easy intercalation and deintercalation process are crucial requirements for electrochromic device. In this investigation, the evolution of structural and morphological changes and their effect on electrochromic (EC) properties of spray-deposited WO₃ thin films are studied. Films of different morphologies were deposited from an ammonium tungstate precursor solution using a novel pulsed spray pyrolysis technique (PSPT) on tin-doped indium oxide (ITO) coated glass substrates by varying quantity of spraying solution. Interesting morphological transition from beads-to-wires-to-fibers as a function of quantity of sprayed solution has been demonstrated. The porosity, crystallinity and “open” structures in the films consisting of beads, wires, and fiber-like morphology enabled us to correlate these aspects to their EC performance. WO₃ films comprising wire-like morphology (20 cc spraying quantity) exhibited better EC properties both in terms of coloration efficiency (42.7 cm²/C) and electrochemical stability (10³ colored/bleached cycles) owing to their adequate open structure, porosity, and amorphicity, compared with the films having bead/fiber-like morphology.     

Energy relaxation method for chemical non‐equilibrium flow computations

In this paper, an algorithm for chemical non‐equilibrium hypersonic flow is developed based on the concept of energy relaxation method (ERM). The new system of equations obtained are studied using finite volume method with Harten–Lax–van Leer scheme for contact (HLLC). The original HLLC method is modified here to account for additional species and split energy equations. Higher order spatial accuracy is achieved using MUSCL reconstruction of the flow variables with van Albada limiter. The thermal equilibrium is considered for the analysis and the species data are generated using polynomial correlations. The single temperature model of Dunn and Kang is used for chemical relaxation. The computed results for a flow field over a hemispherical cylinder at Mach number of 16.34 obtained using the present solver are found to be promising and computationally (25%) more efficient. The present solver captures physically correct solution as the entropy conditions are satisfied automatically during the computations. Copyright © 2007 John Wiley & Sons, Ltd.     

Phase determination in holographic Moiré in presence of nonsinusoidal waveforms and random noise

This paper proposes a subspace parameter estimation method which besides allowing for accommodating multiple PZTs in an optical interferometer permits for extracting in real time values of phase shifts between data frames at each pixel point. The technique enables to freely choose values of phase shifts between 0 and π. A generalized phase measurement algorithm allows for computing multiple phase information present in the interferometer. The method facilitates the use of spherical beams, addresses errors arising from the miscalibration of the phase shifting devices, and is capable of handling nonsinusoidal waveforms in an effective manner. Numerical simulations demonstrate that phase distributions can be measured with high accuracy even in the presence of noise.     

Synthesis of ammonium [14C]thiocyanate

Ammonium [¹⁴C]thiocyanate was prepared from potassium [¹⁴C]cyanide with a radiochemical yield of 90%. [¹⁴C]hydrocyanic acid, generated from potassium [¹⁴C]cyanide by sulphuric acid, reacts with aqueous ammonia and elemental sulphur in the presence of trace amounts of ammonium sulphide to yield ammonium [¹⁴C]thiocyanate.     

Cavitation--a novel technique for making stable nano-suspensions

The purpose of the present study was to obtain nano-scale particles of styrene butadiene rubber. As SBR particles are elastic in nature, conventional methods of size reductions such as impacting, grinding are unable to achieve the final size. So, attempts have been made here to make the nano-particles of the SBR using cavitation technique. Both acoustic and hydrodynamic cavitation techniques have been employed and studied. Hydrodynamic cavitation has been proved to be more energy efficient than the acoustic cavitation on the basis of various parameters. The maximum production rate equivalent to 2 kg/h (solid processing) has been achieved in the newly developed hydrodynamic cavitation set-up (made in house). Similar to transient cavitation, stable cavitation has also been shown to contribute for reduction in the size of the material with very low variation in size. This technique has been proved successful for the size-reduction of the elastic material to nano-scale, thus it may also be used for the size-reduction of the other brittle and hard material by adjusting various cavitational parameters.     

Micromotor‐Based Energy Generation

A micromotor‐based strategy for energy generation, utilizing the conversion of liquid‐phase hydrogen to usable hydrogen gas (H₂), is described. The new motion‐based H₂‐generation concept relies on the movement of Pt‐black/Ti Janus microparticle motors in a solution of sodium borohydride (NaBH₄) fuel. This is the first report of using NaBH₄ for powering micromotors. The autonomous motion of these catalytic micromotors, as well as their bubble generation, leads to enhanced mixing and transport of NaBH₄ towards the Pt‐black catalytic surface (compared to static microparticles or films), and hence to a substantially faster rate of H₂ production. The practical utility of these micromotors is illustrated by powering a hydrogen–oxygen fuel cell car by an on‐board motion‐based hydrogen and oxygen generation. The new micromotor approach paves the way for the development of efficient on‐site energy generation for powering external devices or meeting growing demands on the energy grid.     

Understanding guest and pressure‐induced porosity through structural transition in flexible interpenetrated MOF by Raman spectroscopy

Interpenetrating metal organic frameworks are interesting functional materials exhibiting exceptional framework properties. Uptake or exclusion of guest molecules can induce sliding in the framework making it porous or non‐porous. To understand this dynamic nature and how framework interaction changes during sliding, metal organic framework (MOF) 508 {Zn(BDC)( 4,4′‐Bipy)_0.5 · DMF(H₂O)_0.5} was selected for study. We have investigated structural transformation in MOF‐508 under variable conditions of temperature, pressure and gas loading using Raman spectroscopy and substantiated it with IR studies and density functional theory (DFT) calculations. Conformational changes in the organic linkers leading to the sliding of the framework result in changes in Raman spectra. These changes in the organic linkers are measured as a function of high pressure and low temperature, suggesting that the dynamism in MOF‐508 framework is driven by ligand conformation change and inter‐linker interactions. The presence of Raman signatures of adsorbed CO₂ and its librational mode at 149 cm⁻¹ suggests cooperative adsorption of CO₂ in the MOF‐508 framework, which is also confirmed from DFT calculations that give a binding energy of 34 kJ/mol. Copyright © 2015 John Wiley & Sons, Ltd.     

Maintenance of residual activity of Bt toxin by using natural and synthetic dyes: a novel approach for sustainable mosquito vector control

Mosquito control protein from Bacillus thuringiensis gets inactivated with exposure to sunlight. To address this issue, the potential of synthetic and natural dye was investigated as sunlight protectants. Bt SV2 in absence of dyes when exposed to sunlight showed reduced effectiveness against the fourth instars of mosquito larvae. Whereas acriflavin, congo red and violacein were able to maintain 86.4%, 91.6% and 82.2% mosquito larvicidal efficacy of Bt SV2 against IVth instars larvae of Anopheles stephensi Meigen after exposure to sunlight. Similarly, beetroot dye, acriflavin, congo red and violacein maintained 98.4%, 97.1%, 90.8% and 70.7% larvicidal activities against Aedes aegypti Linnaeus after sunlight exposure. Prodigiosin was found to be the best photo-protectant by simultaneously protecting and enhancing Bt activity by 6.16% and 22.16% against A. stephensi and A. aegypti, respectively. Combination of dyes with Bt formulations can be a good strategy for mosquito control programmes in tropical and sub-tropical regions.