Fullerene-C60-modified electrode as a sensitive voltammetric sensor for detection of nandrolone--an anabolic steroid used in doping

The electrochemical behaviour of nandrolone is investigated by cyclic, differential pulse and square-wave voltammetry in phosphate buffer system at fullerene-C₆₀-modified electrode. The modified electrode shows an excellent electrocatalytic activity towards the oxidation of nandrolone resulting in a marked lowering in the peak potential and considerable improvement of the peak current as compared to the electrochemical activity at the bare glassy carbon electrode. The oxidation process is shown to be irreversible and diffusion-controlled. A linear range of 50 μM to 0.1 nM is obtained along with a detection limit and sensitivity of 0.42 nM and 0.358 nA nM⁻¹, respectively, in square-wave voltammetric technique. A diffusion coefficient of 4.13 × 10⁻⁸ cm² s⁻¹ was found for nandrolone using chronoamperometry. The effect of interferents, stability and reproducibility of the proposed method were also studied. The described method was successfully employed for the determination of nandrolone in human serum and urine samples. A cross-validation of observed results by GC-MS indicates that the results are in good agreement with each other.     

Steroidal alkaloids from Holarrhena antidysenterica (L.) WALL

Chemical investigations on the stem bark of Holarrhena antidysenterica resulted in the isolation of a new steroidal alkaloid designated as holadysenterine (1), together with three known steroidal alkaloids, conessine (2), isoconessimine (3) and kurchessine (4). Their structures were elucidated on the basis of 1D- and 2D-NMR techniques and high-resolution mass spectrometry.     

Application of Doehlert design in optimizing the determination of degraded products of nerve agents by ion-pair liquid chromatography electrospray ionization tandem mass spectrometry

A qualitative method was developed for the determination of degraded products of nerve agents by using ion-pair liquid chromatography electrospray ionization tandem mass spectrometry (IP-LC-ESI-MS(n)). Generally, alkylphosphonic acids (APAs) and O-alkyl alkylphosphonic acids (AAPAs) give deprotonated molecular ion [M-H](-) in negative mode. Interestingly, first time we obtained the molecular radical anion [M](.-) of phosphonic acids in negative mode by using tri-n-butyl amine as an ion-pairing agent. We interpreted this observation as an indication of electrochemical reduction of phosphonic acids in electrospray needle. Three variables such as sheath gas flow, electrospray needle voltage and pH of the mobile phase were investigated to enhance the molecular radical anion [M](.-) signal of each analyte. The Doehlert design was used to obtain the region in which the optimum value of such variables is simultaneously achieved. Limit of detection achieved was 0.5 microg mL(-1) for AAPAs and 10 microg mL(-1) for APAs. Excellent precision was observed with less than 8.61% RSD. Finally, the method was applied for the detection of ethyl methylphosphonic in aqueous extract of soil sample.     

Growth of highly oriented crystalline polyaniline films by self-organization

Silicon substrates with (100) orientation were modified with amino-silane self-assembled monolayer (SAM) to provide amino (NH(2)) moieties at the substrate surface. Self-organization of polyaniline during chemical polymerization, on this modified surface, leads to the growth of highly oriented films at the substrate-polymer interface. The morphology studied using scanning electron microscopy and atomic force microscopy revealed the formation of polymer film with well faceted pyramidal crystallites. XPS and FTIR spectroscopy were used to analyze the chemical structure of the film. X-ray diffraction measurements show the crystalline nature of the polyaniline, whose lattice parameters are in agreement with the reported values. This study underlines the importance of a SAM in deciding the structure and morphology of the deposited polymer.     

In situ derivatization hollow fiber mediated liquid phase microextraction of alkylphosphonic acids from water

Alkylphosphonic acids (APAs), particularly the methyl-, ethyl-, isopropyl- and n-propyl-phosphonic acids are important markers of extremely toxic nerve agents. Hence, their detection and identification is of vital importance to verification of chemical weapons convention (CWC). Verification analysis of CWC requires development of fast, reliable, simple and reproducible sample preparation methods of water and soil samples. Present investigation is focused on the optimization of alkylation of APAs in water with subsequent extraction of alkylated acids by hollow fiber liquid phase microextraction (HF-LPME). This simple and sensitive sample preparation of APAs from water offered better recoveries in comparison to conventionally used extraction technique. Under optimized conditions, the APAs were detected at the concentration of 0.5-0.75 microg/mL with S/N ratio > or = 5, whereas the LODs for alkyl APAs (monobasic APAs) were achieved up to 0.1 microg/mL. The developed method was finally tested with water samples supplied in 19th official proficiency test conducted by the OPCW.     

Thermocapillary convection in double-layer fluid structures within a two-dimensional open cavity

Thermocapillary convection within a differentially-heated open rectangular cavity containing two immiscible liquid layers is considered in the absence of gravitational effects. The temperature and flow fields in the two layers are computed using domain mapping in conjunction with a finite-difference scheme on a staggered grid. The melt-encapsulant and air-encapsulant interfaces are allowed to deform, with the contact lines pinned on the solid boundaries. The presence of a free surface at the top leads to increased convection in the encapsulant phase while retarding thermocapillary flow in the melt. The intensity of thermocapillary convection in the encapsulated layer is reduced as the viscosity of the encapsulant is increased or the thickness of the encapsulant layer is decreased. Choosing an encapsulant with a greater sensitivity of interfacial tension to temperature (as compared to that of the melt phase) can almost completely suppress thermocapillary convection in the melt. Deformations of the melt-encapsulant interface in an open cavity are found to be larger than those in a closed cavity with a rigid top surface, due to higher pressure gradients realized in the encapsulant phase. In contrast to interface deformation behavior reported earlier for a double-layer system in a closed cavity, the shape of the melt-encapsulant interface is qualitatively similar for all values of the viscosity ratio, with the interface dipping into the melt near the cold wall, and into the encapsulant near the hot wall. For the double-layers considered in this study, a free surface at the top of the encapsulant layer was found to be more effective than a rigid top in reducing the intensity of thermocapillary convection in the melt.     

Modeling the sorption kinetics of divalent metal ions onto mineral adsorbent using integral method

A mathematical model has been developed that could predict kinetic parameters for the adsorption of divalent cations (lead, copper and zinc) onto low-grade rock phosphate using experimental data. The experiments were conducted with the initial concentrations of metal ions ranging from 10 to 100 mg/L. The mathematical model is based on application of Freundlich isotherm to mass transfer across the film surrounding the adsorbent. A code in C programming is used to numerically integrate the model equation, and to obtain the best simulated values of Freundlich constants K, N, order of reaction n, and film transfer coefficient, alpha. It is observed that the adsorption of metal ions on rock phosphate is more sensitive to N,n, and alpha in comparison to K, and lead is adsorbed more favorably than copper and zinc.     

Exploring the Antibacterial and Antibiofilm Efficacy of Silver Nanoparticles Biosynthesized Using Punica granatum Leaves

The current research work illustrates an economical and rapid approach towards the biogenic synthesis of silver nanoparticles using aqueous Punica granatum leaves extract (PGL-AgNPs). The optimization of major parameters involved in the biosynthesis process was done using Box-Behnken Design (BBD). The effects of different independent variables (parameters), namely concentration of AgNO₃, temperature and ratio of extract to AgNO_3, on response viz. particle size and polydispersity index were analyzed. As a result of experiment designing, 17 reactions were generated, which were further validated experimentally. The statistical and mathematical approaches were employed on these reactions in order to interpret the relationship between the factors and responses. The biosynthesized nanoparticles were initially characterized by UV-vis spectrophotometry followed by physicochemical analysis for determination of particle size, polydispersity index and zeta potential via dynamic light scattering (DLS), SEM and EDX studies. Moreover, the determination of the functional group present in the leaves extract and PGL-AgNPs was done by FTIR. Antibacterial and antibiofilm efficacies of PGL-AgNPs against Gram-positive and Gram-negative bacteria were further determined. The physicochemical studies suggested that PGL-AgNPs were round in shape and of ~37.5 nm in size with uniform distribution. Our studies suggested that PGL-AgNPs exhibit potent antibacterial and antibiofilm properties.     

Analysis of thermal expansion coefficients under the effect of high temperature for minerals

A simple and straightforward method for the determination of thermal expansion is investigated and applied for four minerals of geophysical importance. The results obtained for four minerals such as Mg₂SiO₃, Al₂O₃, Grossular garnet and Pyrope garnet at different temperatures are found to be in excellent agreement with the experimental data. The simplicity of the method is discussed in the light of another method in high temperature research on minerals.