Sensitive Liquid Chromatography-Tandem Mass Spectrometry Method for the Determination of Olanzapine in Human Urine

A sensitive and selective liquid chromatographic-tandem mass spectrometric (LC-MS-MS) method was developed to determine olanzapine (OLZ) in human urine. After solid-phase extraction with SPE cartridge, the urine sample was analysed on a C-18 column (Symmetry 3.5 mu m, 50 x 4.6 mm i.d) interfaced with a triple quadrupole tandem mass spectrometer. Positive electrospray ionization was employed as the ionization source. The mobile phase consisted of ammonium acetate (pH 7.8)-acetonitrile (10:90, v/v). The method was linear over a concentration range of 1-100 ngml(-1). The lower limit of quantitation was 1 ngml(-1). The intra-day and inter-day relative standard deviation across three validation runs over the entire concentration range was < 11.5 %. The accuracy determined at three concentrations (8.0, 50.0 and 85.0 ngml(-1) OLZ) was within +/- 1.21 % in terms of relative errors.

Study of n-ZnO/p-Si (100) thin film heterojunctions by pulsed laser deposition without buffer layer

ZnO/Si heterojunctions were fabricated by growing ZnO thin films on p-type Si (100) substrate by pulsed laser deposition without buffer layers. The crystallinity of the heterojunction was analyzed by high resolution X-ray diffraction and atomic force microscopy. The optical quality of the film was analyzed by room temperature (RT) photoluminescence measurements. The high intense band to band emission confirmed the high quality of the ZnO thin films on Si. The electrical properties of the junction were studied by temperature dependent current-voltage measurements and RT capacitance-voltage (C-V) analysis. The charge carrier concentration and the barrier height (BH) were calculated, to be 5.6x10(19) cm(-3) and 0.6 eV respectively from the C-V plot. The BH and ideality factor, calculated using the thermionic emission (TE) model, were found to be highly temperature dependent. We observed a much lower value in Richardson constant, 5.19x10(-7)A/cm(2) K-2 than the theoretical value (32 A/cm(2) K-2) for ZnO. This analysis revealed the existence of a Gaussian distribution (GD) with a standard deviation of sigma(2)=0.035 V. By implementing the GD to the TE, the values of BH and Richardson constant were obtained as 1.3 eV and 39.97 A/cm(2) K-2 respectively from the modified Richardson plot. The obtained Richardson constant value is close to the theoretical value for n-ZnO. These high quality heterojunctions can be used for solar cell applications. (C) 2012 Elsevier B.V. All rights reserved.

Phase inversion in agitated liquid-liquid dispersions: Anomalous effect of electrolyte

An imbalance between breakup and coalescence of drops in turbulent liquid-liquid dispersions leads to inversion of phases the dispersed phase becomes continuous and vice versa. An increase in the rate of coalescence of drops is expected to decrease the dispersed phase fraction at which inversion occurs. In the present work, we increased the rate of coalescence of drops by adding electrolyte to pure liquid-liquid dispersions. The experiments carried out for three representative liquid-liquid systems show that contrary to the expectation the addition of an electrolyte increases the dispersed phase fraction at which inversion occurs for both, oil-in-water and water-in-oil dispersions. The step-down experiments confirm that the addition of the electrolyte increases the rate of coalescence of drops in lean dispersions under the same conditions, thereby confirming an anomalous effect of the presence of an electrolyte on the stability of dispersions. (C) 2012 Elsevier Ltd. All rights reserved.

Ionic conductivity of bis(2-cyanoethyl) ether-lithium salt and poly(propylether imine)-lithium salt liquid electrolytes

We report here a multiple-nitrile based lithium-salt liquid electrolyte. The ionic conductivity of poly (propyl ether imine) (abbreviated as PETIM) lithium salt dendrimer liquid electrolyte was observed to be a function of dendrimer generation number, n=0 (monomer)-3. While the highest room temperature ionic conductivity value (similar to 10(-1) Sm-1) was recorded for the bis-2cyanoethyl ether monomer (i.e. zeroth generation; G(0)-CN), conductivity decreased progressively to lower values (similar to 10(-3) Sm-1) with increase in generation number (G(1)-CN -> G(3)-CN). The G(0)-CN and higher dendrimer generations showed high thermal stability (approximate to 150 to 200 degrees C), low moisture sensitivity and tunable viscosity (similar to 10(-2) (G(0)-CN) to 3 (G(3)-CN) Pa s). The linker ether group was found to be crucial for ion transport and also eliminated a large number of detrimental features, chiefly moisture sensitivity, chemical instability associated typically with prevalent molecular liquid solvents. Based on the combination of several beneficial physicochemical properties, we presently envisage that the PETIM dendrimers especially the G(0)-CN electrolytes hold promise as electrolytes in electrochemical devices such as lithium-ion batteries.

Factors Affecting Laser-Excited Photoluminescence from ZnO Nanostructures

The role of defects on laser-excited photoluminescence of various ZnO nanostructures has been investigated. The study shows that defects present in ZnO nanostructures, specially Zn-related defects play a crucial role in determining the laser-excited photoluminescence intensity (LEI). ZnO nanoparticles as well as nanorods (NR) annealed in oxygen atmosphere exhibit remarkable enhancement in LEI. A similar enhancement is also shown by Al-doped ZnO NR. © 2012 Springer Science+Business Media, LLC.

Vapor-liquid-solid growth of Si nanowires: A kinetic analysis

A steady state kinetic model has been developed for the vapor-liquid-solid growth of Si whiskers or nanowires from liquid catalyst droplets. The steady state is defined as one in which the net injection rate of Si into the droplet is equal to the ejection rate due to wire growth. Expressions that represent specific mechanisms of injection and ejection of Si atoms from the liquid catalyst droplet have been used and their relative importance has been discussed. The analysis shows that evaporation and reverse reaction rates need to be invoked, apart from just surface cracking of the precursor, in order to make the growth rate radius dependent. When these pathways can be neglected, the growth rate become radius independent and can be used to determine the activation energies for the rate limiting step of heterogeneous precursor decomposition. The ejection rates depend on the mechanism of wire growth at the liquid-solid interface or the liquid-solid-vapor triple phase boundary. It is shown that when wire growth is by nucleation and motion of ledges, a radius dependence of growth rate does not just come from the Gibbs-Thompson effect on supersaturation in the liquid, but also from the dependence of the actual area or length available for nucleation. Growth rates have been calculated using the framework of equations developed and compared with experimental results. The agreement in trends is found to be excellent. The same framework of equations has also been used to account for the diverse pressure and temperature dependence of growth rates reported in the literature. © 2012 American Institute of Physics.

Vaporization and collision modeling of liquid fuel sprays in a co-axial fuel and air pre-mixer

Droplet collision occurs frequently in regions where the droplet number density is high. Even for Lean Premixed and Pre-vaporized (LPP) liquid sprays, the collision effects can be very high on the droplet size distributions, which will in turn affect the droplet vaporization process. Hence, in conjunction with vaporization modeling, collision modeling for such spray systems is also essential. The standard O'Rourke's collision model, usually implemented in CFD codes, tends to generate unphysical numerical artifact when simulations are performed on Cartesian grid and the results are not grid independent. Thus, a new collision modeling approach based on no-time-counter method (NTC) proposed by Schmidt and Rutland is implemented to replace O'Rourke's collision algorithm to solve a spray injection problem in a cylindrical coflow premixer. The so called ``four-leaf clover'' numerical artifacts are eliminated by the new collision algorithm and results from a diesel spray show very good grid independence. Next, the dispersion and vaporization processes for liquid fuel sprays are simulated in a coflow premixer. Two liquid fuels under investigation are jet-A and Rapeseed Methyl Esters (RME). Results show very good grid independence in terms of SMD distribution, droplet number distribution and fuel vapor mass flow rate. A baseline test is first established with a spray cone angle of 90 degrees and injection velocity of 3 m/s and jet-A achieves much better vaporization performance than RME due to its higher vapor pressure. To improve the vaporization performance for both fuels, a series of simulations have been done at several different combinations of spray cone angle and injection velocity. At relatively low spray cone angle and injection velocity, the collision effect on the average droplet size and the vaporization performance are very high due to relatively high coalescence rate induced by droplet collisions. Thus, at higher spray cone angle and injection velocity, the results expectedly show improvement in fuel vaporization performance since smaller droplet has a higher vaporization rate. The vaporization performance and the level of homogeneity of fuel-air mixture can be significantly improved when the dispersion level is high, which can be achieved by increasing the spray cone angle and injection velocity. (C) 2012 Elsevier Ltd. All rights reserved.

Factors Affecting Laser-Excited Photoluminescence from ZnO Nanostructures

The role of defects on laser-excited photoluminescence of various ZnO nanostructures has been investigated. The study shows that defects present in ZnO nanostructures, specially Zn-related defects play a crucial role in determining the laser-excited photoluminescence intensity (LEI). ZnO nanoparticles as well as nanorods (NR) annealed in oxygen atmosphere exhibit remarkable enhancement in LEI. A similar enhancement is also shown by Al-doped ZnO NR.

Lipopeptides from the Banyan Endophyte, Bacillus subtilis K1: Mass Spectrometric Characterization of a Library of Fengycins

Mass spectrometric analysis of a banyan endophyte, Bacillus subtilis K1, extract showing broad spectrum antifungal activity revealed a complex mixture of lipopeptides, iturins, surfactins, and fengycins. Fractionation by reversed-phase high performance liquid chromatography (HPLC) facilitated a detailed analysis of fengycin microheterogeneity. Matrix assisted laser desorption ionization (MALDI) and electrospray ionization (ESI) mass spectrometric studies permitted the identification of several new fengycin variants. Four major sites of heterogeneity are identified: (1) N-terminus beta-hydroxy fatty acid moiety, where chain length variation and the presence of unsaturation occur, (2) position 6 (Ala/Val/Ile/Leu), (3) position 10 (Val/Ile) within the macrocyclic ring, and (4) Gln to Glu replacement at position 8, resulting in fengycin variants that differ in mass by 1 Da. Diagnostic fragment ions provide a quick method for localizing the sites of variation in the macrocycle or the linear segment. Subsequent establishment of the sequences is achieved by MS/MS analysis of linear fengycin species produced by hydrolysis of the macrocyclic lactone. Unsaturation in the fatty acid chain and the presence of linear precursors in the B. subtilis K1 extract are also established by mass spectrometry. The anomalous distribution of intensities within isotopic multiplets is a diagnostic for Gln/Glu replacements. High resolution mass spectrometry facilitates the identification of fengycin species differing by 1 Da by localizing the variable position (Gln(8)/Glu(8)) in the fengycin variants.

Scaling Analysis of Solidification of Liquid Aluminum Alloy Flowing on Cooling Slope

Among all methods of metal alloy slurry preparation, the cooling slope method is the simplest in terms of design and process control. The method involves pouring of the melt from top, down an oblique and channel shaped plate cooled from bottom by counter flowing water. The melt, while flowing down, partially solidifies and forms columnar dendrites on plate wall. These dendrites are broken into equiaxed grains and are washed away with melt. The melt, together with the equiaxed grains, forms semisolid slurry collected at the slope exit and cast into billets having non-dendritic microstructure. The final microstructure depends on several process parameters such as slope angle, slope length, pouring superheat, and cooling rate. The present work involves scaling analysis of conservation equations of momentum, energy and species for the melt flow down a cooling slope. The main purpose of the scaling analysis is to obtain a physical insight into the role and relative importance of each parameter in influencing the final microstructure. For assessing the scaling analysis, the trends predicted by scaling are compared against corresponding numerical results using an enthalpy based solidification model with incorporation of solid phase movement.

Direct ultrafast laser written C-band waveguide amplifier in Er-doped chalcogenide glass

This paper reports the fabrication and characterization of an ultrafast laser written Er-doped chalcogenide glass buried waveguide amplifier; Er-doped GeGaS glass has been synthesized by the vacuum sealed melt quenching technique. Waveguides have been fabricated inside the 4 mm long sample by direct ultrafast laser writing. The total passive fiber-to-fiber insertion loss is 2.58 +/- 0.02 dB at 1600 nm, including a propagation loss of 1.6 +/- 0.3 dB. Active characterization shows a relative gain of 2.524 +/- 0.002 dB/cm and 1.359 +/- 0.005 dB/cm at 1541 nm and 1550 nm respectively, for a pump power of 500 mW at a wavelength of 980 nm. (C) 2012 Optical Society of America

Degradation studies of organic acids in commercially packed fruit juices: A reverse phase high performance liquid chromatographic approach

Organic acids are important constituents of fruit juices. They render tartness, flavour and specific taste to fruit juices. Shelf life and stability of fruit juices are important factors, which determine their nutritional quality and freshness. In this view, the effect of storage on the concentration of organic acids in commercially packed fruit juices is studied by reverse phase high performance liquid chromatography (RP-HPLC). Ten packed fruit juices from two different brands are stored at 30 C for 24, 48 and 72 hours. A reverse phase high performance liquid chromatographic method is used to determine the concentration of oxalic, tartaric, malic, ascorbic and citric acid in the fruit juices during storage. The chromatographic analysis of organic acids is carried out using mobile phase 0.5% (w/v) ammonium dihydrogen orthophosphate buffer (pH 2.8) on C18 column with UV-Vis detector. The results show that the concentration of organic acids generally decreases in juices under study with the increase in storage time. All the fruit juices belonging to tropicana brand underwent less organic acid degradation in comparison to juices of real brand. Orange fruit juice is found to be least stable among the juices under study, after the span of 72 hours. Amongst all the organic acids under investigation minimum stability is shown by ascorbic acid followed by malic and citric acid.

Breakup and coalescence characteristics of a hollow cone swirling spray

This paper deals with an experimental study of the breakup characteristics of water emanating from hollow cone hydraulic injector nozzles induced by pressure-swirling. The experiments were conducted using two nozzles with different orifice diameters 0.3 mm and 0.5 mm and injection pressures (0.3-4 MPa) which correspond to Rep = 7000-26 000. Two types of laser diagnostic techniques were utilized: shadowgraph and phase Doppler particle anemometry for a complete study of the atomization process. Measurements that were made in the spray in both axial and radial directions indicate that both velocity and average droplet diameter profiles are highly dependent on the nozzle characteristics, Weber number and Reynolds number. The spatial variation of diameter and velocity arises principally due to primary breakup of liquid films and subsequent secondary breakup of large droplets due to aerodynamic shear. Downstream of the nozzle, coalescence of droplets due to collision was also found to be significant. Different types of liquid film breakup were considered and found to match well with the theory. Secondary breakup due to shear was also studied theoretically and compared to the experimental data. Coalescence probability at different axial and radial locations was computed to explain the experimental results. The spray is subdivided into three zones: near the nozzle, a zone consisting of film and ligament regime, where primary breakup and some secondary breakup take place; a second zone where the secondary breakup process continues, but weakens, and the centrifugal dispersion becomes dominant; and a third zone away from the spray where coalescence is dominant. Each regime has been analyzed in detail, characterized by timescale and Weber number and validated using experimental data. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4773065]

Bubble size measurement and error analysis in a gas liquid ejector

Bubble size in a gas liquid ejector has been measured using the image technique and analysed for estimation of Sauter mean diameter. The individual bubble diameter is estimated by considering the two dimensional contour of the ellipse, for the actual three dimensional ellipsoid in the system by equating the volume of the ellipsoid to that of the sphere. It is observed that the bubbles are of oblate and prolate shaped ellipsoid in this air water system. The bubble diameter is calculated based on this concept and the Sauter mean diameter is estimated. The error between these considerations is reported. The bubble size at different locations from the nozzle of the ejector is presented along with their percentage error which is around 18%.

Strategies for the Synthesis of Graphene, Graphene Nanoribbons, Nanoscrolls and Related Materials

Single-layer graphene (SLG), the 3.4 angstrom thick two-dimensional sheet of sp(2) carbon atoms, was first prepared in 2004 by mechanical exfoliation of graphite crystals using the scotch tape technique. Since then, SLG has been prepared by other physical methods such as laser irradiation or ultrasonication of graphite in liquid media. Chemical methods of synthesis of SLG are more commonly used; the most popular involves preparation of single-layer graphene oxide followed by reduction with a stable reagent, often assisted by microwave heating. This method yields single-layer reduced graphene oxide. Other methods for preparing SLG include chemical vapour deposition over surfaces of transition metals such as Ni and Cu. Large-area SLG has also been prepared by epitaxial growth over SIC. Few-layer graphene (FLG) is prepared by several methods; arc discharge of graphite in hydrogen atmosphere being the most convenient. Several other methods for preparing FLG include exfoliation of graphite oxide by rapid heating, ultrasonication or laser irradiation of graphite in liquid media, reduction of few-layer graphene oxide, alkali metal intercalation followed by exfoliation. Graphene nanoribbons, which are rectangular strips of graphene, are best prepared by the unzipping of carbon nanotubes by chemical oxidation or laser irradiation. Many graphene analogues of inorganic materials such as MoS2, MoSe2 and BN have been prepared by mechanical exfoliation, ultrasonication and by chemical methods involving high-temperature or hydrothermal reactions and intercalation of alkali metals followed by exfoliation. Scrolls of graphene are prepared by potassium intercalation in graphite or by microwave irradiation of graphite immersed in liquid nitrogen.