Reactivity of Cyclanols Towards Quinaldinium Fluorochromate Oxidation

The kinetics of oxidation of cyclanols, viz., cyclohexanol, cyclopentanol, cycloheptanol and cyclooctanol by quinaldinium fluorochromate has been studied in aqueous acid medium at 313 K (±0.1 K). The cyclanols were converted to the corresponding cyclic ketones. The order of reaction was found to be one with respect to oxidant and fractional with respect to the substrate and hydrogen ion concentrations. Increase in the percentage of acetic acid increases the rate of reaction. The reaction mixture shows the absence of any free radicals in the reaction, which has ruled out the possibility of a one-electron transfer during the addition of acrylonitrile. The reaction has been studied at four different temperatures and the activation parameters were calculated. From the observed kinetic results a suitable mechanism was proposed. The relative reactivity order was found to be cyclohexanol < cyclopentanol < cycloheptanol < cyclooctanol. This was explained on the basis of I-strain theory.     

Fluorescent non-linear chiral polymer chemosensor bonded alternatively with 1,4-diethynyl-2,5-dioctyloxybenzene and (R,R)-salen for Zn2+recognition

Stereoregular non-linear chiral main chain polymers 1a–b bonded alternatively with (R,R)-salen and 1,4-diethynyl-2,5-dioctyloxybenzene moieties have been synthesized using palladium catalyzed C–C cross-coupling and Schiff base formation reactions as the key steps. These polymers are soluble in common organic solvents, and act as an effective chemosensor for the detection of Zn²⁺ with respect to other metal ions with enhanced fluorescence. The CD spectra observed for the polymers 1a–b could be attributed to the helical secondary structure with a low degree of inter-strand interactions. This reduced inter-strand interaction has been ascertained from the titration of pyridine to the Zn(II)-polymer 1b complex, which results in minor changes in the fluorescence emission.     

Robust sampled‐data H∞ control for mechanical systems

This article addresses the issue of robust sampled‐data control for a class of uncertain mechanical systems with input delays and linear fractional uncertainties which appear in all the mass, damping, and stiffness matrices. Then, a novel Lyapunov–Krasovskii functional is constructed to obtain sufficient conditions under which the uncertain mechanical system is robustly, asymptotically stable with disturbance attenuation level about its equilibrium point for all admissible uncertainties. More precisely, Schur complement and Jenson's integral inequality are utilized to substantially simplify the derivation of the main results. In particular, a set of sampled‐data controller is designed in terms of the solution of certain linear matrix inequalities that can be solved effectively using available MATLAB software. Finally, a numerical example with simulation result is provided to show the effectiveness and less conservativeness of the proposed sampled‐data control scheme. © 2014 Wiley Periodicals, Inc. Complexity 20: 19–29, 2015     

Inverse problem for the reaction diffusion system by optimization method

In this paper, we study an inverse problem of reconstructing two time independent coefficients in the reaction diffusion system from the final measurement. First the given problem is transformed into an optimization problem by using optimal control framework and the existence of the minimizer for the control functional is established. Then we prove the stability estimate for two coefficients with the upper bound given by some Sobolev norms of the final measurement.     

Effect of solvent volume on the physical properties of undoped and fluorine doped tin oxide films deposited using a low-cost spray technique

Undoped and fluorine doped tin oxide films were deposited from starting solutions having different values of solvent volume (10-50 ml) by employing a low cost and simplified spray technique using perfume atomizer. X-ray diffraction studies showed that there was a change in the preferential orientation from (2 1 1) plane to (1 1 0) plane as the volume of the solvent was increased. The sheet resistance (R_sh) of undoped SnO₂ film was found to be minimum (13.58 KΩ/□) when the solvent volume was lesser (10 ml) and there was a sharp increase in R_sh for higher values of solvent volume. Interestingly, it was observed that while the R_sh increases sharply with the increase in solvent volume for undoped SnO₂ films, it decreases gradually in the case of fluorine doped SnO₂ films. The quantitative analysis of EDAX confirmed that the electrical resistivity of the sprayed tin oxide film was mainly governed by the number of oxygen vacancies and the interstitial incorporation of Sn atoms which in turn was governed by the impinging flux on the hot substrate. The films were found to have good optical characteristics suitable for opto-electronic devices.     

Characterization and sensing property studies of the Pt | Nafion electrode prepared by the chemical reduction method

A novel electrochemical hydrogen sensor which consists of a solid electrolyte polymer (SEP) and catalytic active electrode operating at room temperature was fabricated and investigated. Nafion is utilized as polymer proton conducting membrane onto which a catalytic electrode was deposited by anin-situ impregnation reduction (I-R) technique. In this work, Pt was selected as active catalyst for hydrogen oxidation and the deposition conditions were modified to optimise the parameters for application in hydrogen sensors and to improve the metal utilization so that the electrode loading could be reduced without loss of electrochemical performance. The hydrogen sensing characteristics with air as reference gas are reported. A maximum sensitivity of about 0.01 μA cm⁻² ppm⁻¹ was obtained. The response time was observed to be in the range of 10–50 seconds. The experimental results show that long term sensor stability exists at room temperature. The thin Pt films were characterized by XRD, infrared spectroscopy, optical microscopy, scanning electron microscopy and EDAX. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14–18, 2004.     

HPTLC analysis of Scoparia dulcis Linn (Scrophulariaceae) and its larvicidal potential against dengue vector Aedes aegypti

This study evaluates the larvicidal activity of Scoparia dulcis aqueous extract against dengue vector and determines its major chemical components. The extract was tested at various concentrations ranging from 0.1 to 2 mg/mL against Aedes aegypti larvae. The extracts displayed significant larvicidal efficacy against Ae. aegypt species after 24 h exposure revealing LC₅₀ of 3.3835 (mg/mL) and LC₉₀ of 5.7578 (mg/mL). Finger printing profile carried out by CAMAG automatic TLC sample applicator programmed through WIN CATS software revealed peaks with different R_f values for three different volumes injected: 16, 15 and 18 peaks were spotted for 3, 6 and 9 μL, respectively. Ascending order of R_f values was also ascertained for each peak recorded. This study clearly signifies that S. dulcis extract contains numerous compounds that are known to have larvicidal properties which clearly substantiates its efficacy on Ae. aegypti larvae.     

Hg(II) immobilized MWCNT graphite electrode for the anodic stripping voltammetric determination of lead and cadmium

The preparation of Hg(II)-modified multi walled carbon nanotube (MWCNT) by reaction of oxidized MWCNT with aqueous HgCl₂ was carried out. The Hg(II)-modified multi walled carbon nanotube (Hg(II)/MWCNT) dispersed in Nafion solution was used to coat the polished graphite electrode surface. The Hg(II)/MWCNT modified graphite electrode was held at a cathodic potential (−1.0 V) to reduce the coordinated Hg(II) to Hg forming nanodroplets of Hg. The modified electrode was characterized by FESEM/EDAX which provided useful insights on the morphology of the electrode. The SEM images showed droplets of Hg in the size of around 260 nm uniformly distributed on the MWCNT. Differential pulse anodic stripping voltammetry (DPASV) and electrochemical impedance spectroscopy were used to study the Hg(II) binding with MWCNT. Differential pulse anodic stripping voltammetry of ppb levels of cadmium and lead using the modified electrode yielded well-defined peaks with low background current under a short deposition time. Detection limit of 0.94 and 1.8 ng L⁻¹ were obtained following a 3 min deposition for Pb(II) and Cd(II), respectively. Various experimental parameters were characterized and optimized. High reproducibility was observed from the RSD values for 20 repetitive measurements of Pb(II) and Cd(II) (1.7 and 1.9%, respectively). The determination of Pb(II) and Cd(II) in tap water and Pb(II) in human hair samples was carried out. The above method of fabrication of Hg(II)/MWCNT modified graphite electrode clearly suggests a safe route for preparing Hg immobilized electrode for stripping analysis.     

Green synthesis of biogenic metal nanoparticles by terrestrial and aquatic phototrophic and heterotrophic eukaryotes and biocompatible agents

The size, shape and controlled dispersity of nanoparticles play a vital role in determining the physical, chemical, optical and electronic properties attributing its applications in environmental, biotechnological and biomedical fields. Various physical and chemical processes have been exploited in the synthesis of several inorganic metal nanoparticles by wet and dry approaches viz., ultraviolet irradiation, aerosol technologies, lithography, laser ablation, ultrasonic fields, and photochemical reduction techniques. However, these methodologies remain expensive and involve the use of hazardous chemicals. Therefore, there is a growing concern for the development of alternative environment friendly and sustainable methods. Increasing awareness towards green chemistry and biological processes has led to a necessity to develop simple, cost-effective and eco-friendly procedures. Phototrophic eukaryotes such as plants, algae, and diatoms and heterotrophic human cell lines and some biocompatible agents have been reported to synthesize greener nanoparticles like cobalt, copper, silver, gold, bimetallic alloys, silica, palladium, platinum, iridium, magnetite and quantum dots. Owing to the diversity and sustainability, the use of phototrophic and heterotrophic eukaryotes and biocompatible agents for the synthesis of nanomaterials is yet to be fully explored. This review describes the recent advancements in the green synthesis and applications of metal nanoparticles by plants, aquatic autotrophs, human cell lines, biocompatible agents and biomolecules.     

Diffusion dynamics and first passage time in a two-coupled pendulum system

We present the numerical investigation of diffusion process and features of first passage time (FPT) and mean FPT (MFPT) in a two-coupled damped and periodically driven pendulum system. The effect of amplitude of the external periodic force and phase of the force on diffusion constant, distribution of FPT, P(tFPT), and MFPT is analyzed. Normal diffusion is found. Diffusion constant is found to show power-law variation near intermittency and sudden widening crises while linear variation is observed in the quasiperiodic region. In the intermittency crisis the divergence of diffusion constant is similar to the divergence of mean bursting length. P(tFPT) of critical distances of state variable exhibit periodic multiple peaks with decaying amplitude. MFPT of critical distances also follows power-law variation. Diffusion constant and MFPT are sensitive to the phase factor of the periodic force.