Applicability of partition ratios, mercuric chloride complexes, and chromatographic behavior for the identification of carotenoids

Partition ratios and M50 values of different carotenoids in hexaneaqueous methanol were determined. Mercuric chloride complexes of 14 epoxy carotenoids were prepared and their absorption maxima in acetone were estimated. The difference in chromatographic behavior of carotenoid epoxides on alumina and magnesium oxide-Celite columns is discussed. It is shown that the magnesium oxide-Celite column behaves as a reverse-phase chromatographic column to alumina column.

Evaluation of solute-solvent interactions from solvent blue-shifts of n → π* transitions of C=O, C=S, NO2 and N=N groups: hydrogen bond energies of various donor-acceptor systems

Effects of non-polar, polar and proton-donating solvents on the n → π* transitions of C=O, C=S, NO2 and N=N groups have been investigated. The shifts of the absorption maxima in non-polar and polar solvents have been related to the electrostatic interactions between solute and solvent molecules, by employing the theory of McRAE. In solvents which can donate protons the solvent shifts are mainly determined by solute-solvent hydrogen bonding. Isobestic points have been found in the n → π* bonds of ethylenetrithio-carbonate in heptane-alcohol and heptane-chloroform solvent systems, indicating the existence of equilibria between the hydrogen bonded and the free species of the solute. Among the different proton-donating solvents studied water produces the largest blue-shifts. The blue-shifts in alcohols decrease in the order 2,2,2-trifluoroethanol, methanol, ethanol, isopropanol and t-butanol, the blue-shift in trifluoroethanol being nearly equal to that in water. This trend is exactly opposite to that for the self-association of alcohols. It is suggested that electron-withdrawing groups not merely decrease the extent of self-association of alcohols, but also increase the ability to donate hydrogen bonds. The approximate hydrogen-bond energies for several donor-acceptor systems have been estimated. In a series of aliphatio ketones and nitro compounds studied, the blue-shifts and consequently the hydrogen bond energies decrease with the decrease in the electron-withdrawing power of the alkyl groups. It is felt that electron-withdrawing groups render the chromophores better proton acceptors, and the alcohols better donors. A linear relationship between n → π* transition frequency and the infrared frequency of ethylenetrithiocarbonate has been found. It is concluded that stabilization of the electronic ground states of solute molecules by electrostatic and/or hydrogen-bond interactions determines the solvent shifts.

Studies on phosphorus oxychloride and aluminium chloride complex

1. Anhydrous aluminium chloride reacts with phosphorus oxychloride to give a complex with a composition AlCl3.2 POCl3 which can be prepared in the form of a free flowing powder. 2. The phosphorus oxychloride-aluminium chloride complex in nitrobenzene dissociates into AlCl3.POCl3 and POCl3 as indicated by the cryoscopic measurements. 3. The solution of the complex in nitrobenzene has a higher specific conductivity than the corresponding electrical conductivities of individual components. Similar higher electrical conductance is observed when the two components are mixed in nitrobenzene in different proportions. 4.When a solution of anhydrous aluminium chloride in nitrobenzene is titrated conductometrically against a solution of phosphorus oxychloride in nitrobenzene, a limiting value in the conductivity is reached at point corresponding to the molecular composition, the components in the ratio of 1:2 AlCl3: POCl3 in solution. 5. The absorption maxima of the complex in nitrobenzene solution differ from the absorption maximum of the individual components.

Electronic absorption spectra of selenocarbonyl and thiocarbonyl compounds

Electronic absorption spectra of a variety of thiocarbonyl and selenocarbonyl compounds have been compared to point out their similarities. Interesting correlations between the absorption maxima and electronegativities of substituents in both the seleno- and thio-carbonyl compounds have been reported.

A mathematical programming approach to optimal Markovian switching of Poisson arrival streams to queueing systems

Motivated by certain situations in manufacturing systems and communication networks, we look into the problem of maximizing the profit in a queueing system with linear reward and cost structure and having a choice of selecting the streams of Poisson arrivals according to an independent Markov chain. We view the system as a MMPP/GI/1 queue and seek to maximize the profits by optimally choosing the stationary probabilities of the modulating Markov chain. We consider two formulations of the optimization problem. The first one (which we call the PUT problem) seeks to maximize the profit per unit time whereas the second one considers the maximization of the profit per accepted customer (the PAC problem). In each of these formulations, we explore three separate problems. In the first one, the constraints come from bounding the utilization of an infinite capacity server; in the second one the constraints arise from bounding the mean queue length of the same queue; and in the third one the finite capacity of the buffer reflect as a set of constraints. In the problems bounding the utilization factor of the queue, the solutions are given by essentially linear programs, while the problems with mean queue length constraints are linear programs if the service is exponentially distributed. The problems modeling the finite capacity queue are non-convex programs for which global maxima can be found. There is a rich relationship between the solutions of the PUT and PAC problems. In particular, the PUT solutions always make the server work at a utilization factor that is no less than that of the PAC solutions.

Magnetotransport of Dirac fermions on the surface of a topological insulator

We study the properties of Dirac fermions on the surface of a topological insulator in the presence of crossed electric and magnetic fields. We provide an exact solution to this problem and demonstrate that, in contrast to their counterparts in graphene, these Dirac fermions allow relative tuning of the orbital and Zeeman effects of an applied magnetic field by a crossed electric field along the surface. We also elaborate and extend our earlier results on normal-metal-magnetic film-normal metal (NMN) and normal-metal-barrier-magnetic film (NBM) junctions of topological insulators [S. Mondal, D. Sen, K. Sengupta, and R. Shankar, Phys. Rev. Lett. 104, 046403 (2010)]. For NMN junctions, we show that for Dirac fermions with Fermi velocity vF, the transport can be controlled using the exchange field J of a ferromagnetic film over a region of width d. The conductance of such a junction changes from oscillatory to a monotonically decreasing function of d beyond a critical J which leads to the possible realization of magnetic switches using these junctions. For NBM junctions with a potential barrier of width d and potential V-0, we find that beyond a critical J, the criteria of conductance maxima changes from chi=eV(0)d/h upsilon(F)=n pi to chi=(n+1/2)pi for integer n. Finally, we compute the subgap tunneling conductance of a normal-metal-magnetic film-superconductor junctions on the surface of a topological insulator and show that the position of the peaks of the zero-bias tunneling conductance can be tuned using the magnetization of the ferromagnetic film. We point out that these phenomena have no analogs in either conventional two-dimensional materials or Dirac electrons in graphene and suggest experiments to test our theory.

Ba3ZnTa2-xNbxO9 and Ba3MgT2-xNbxO9: synthesis, structural and dielectric studies

Oxides of the families Ba3ZnTa2-xNbxO9 and Ba3MgTa2-xNbxO9 were obtained by the solid state reaction route at 1573 K and were found to crystallize in the disordered (cubic) perovskite structure. In Ba3ZnTa2-xNbXO9 and Ba3MgTa2-xNbxO9 the entire range (0 less than or equal to x less than or equal to 1) of solid solutions could be synthesized. The dielectric constant decreases with increase in frequency for all compositions in the range 40 Hz to 100 kHz (epsilon (r) varies from 16 to 22). The dielectric loss (D) shows a broad maximum for both Ba3ZnTa2-xNbxO9 and Ba3MgTa2-xNbxO9. The maxima is centered around 2 kHz in the former and near 10 kHz in the latter. (C) 2001 Elsevier Science Ltd. All sights reserved.

Steric effects on the ultraviolet absorption of 1,2-enedioic and related systems

1,2-Enedioic systems, being sterically perturbed from planarity do not show the effect of the extended conjugation expected of a (formal) trienic entity. In the absence of a model which approximates to a uniplanar situation, the strategy of replacing an ester group in the enedioates by a cyano (for which less stringent steric demand may be presumed) and noting the correction concomitant to this replacement was adopted to arrive at a notional figure for the position of maximal absorption in the planar enedioates. From this the conclusion, subject to substantiation by molecular mechanical or quantum chemical calculations, was drawn that even the E-isomeric and comparatively less substituted enedioates are highly sterically perturbed. An alternative to an earlier explanation of the bathochromic shift of absorption maxima encountered in the 5-cyclic ene-ester and ene-nitrile, relative to the 6-cyclic analogues (observed also with the enedioates and cyanovinyl ester systems), seen later to have been based on unwarranted premises, has been advanced. A comment on the absorption characteristics of enedioic anhydrides has been appended.

Studies on the phase transitions in thiourea

Thiourea (CS(NH2)2) is one of the few examples of molecular crystals exhibiting ferroelectric properties. The dielectric constant along the ferroelectric axis [100] shows maxima at 169, 177 and 202 K. An inflection point occurs at 170.5 KZ Following Goldsmith and White the phases are named as I (F.E. below 169 K), II (A.F.E. 169 K

High-temperature dielectric response in pulsed laser deposited Bi1.5Zn1.0Nb1.5O7 thin films

Cubic pyrochlore Bi1.5Zn1.0Nb1.5O7 thin films were deposited by pulsed laser ablation on Pt(200)/SiO2/Si at 500, 550, 600, and 650 degrees C. The thin films with (222) preferred orientation were found to grow at 650 degrees C with better crystallinity which was established by the lowest full-width half maxima of similar to 0.38. The dielectric response of the thin films grown at 650 degrees C have been characterized within a temperature range of 270-650 K and a frequency window of 0.1-100 kHz. The dielectric dispersion in the thin films shows a Maxwell-Wagner type relaxation with two different kinds of response confirmed by temperature dependent Nyquist plots. The ac conduction of the films showed a varied behavior in two different frequency regions. The power law exponent values of more than 1 at high frequency are explained by a jump-relaxation-model. The possibility of grain boundary related large polaronic hopping, due to two different power law exponents and transformation of double to single response in Nyquist plots at high temperature, has been excluded. The ``attempt jump frequency'' obtained from temperature dependent tangent loss and real part of dielectric constants, has been found to lie in the range of their lattice vibronic frequencies (10(12)-10(13) Hz). The activation energy arising from a large polaronic hopping due to trapped charge at low frequency region has been calculated from the ac conduction behavior. The range of activation energies (0.26-0.59. eV) suggests that the polaronic hopping at low frequency is mostly due to oxygen vacancies. (C) 2010 American Institute of Physics. doi:10.106311.3457335]

Biomimetic synthesis of silver nanoparticles by Citrus limon (lemon) aqueous extract and theoretical prediction of particle size

In the present study silver nanoparticles were rapidly synthesized at room temperature by treating silver ions with the Citrus limon (lemon) extract The effect of various process parameters like the reductant con centration mixing ratio of the reactants and the concentration of silver nitrate were studied in detail In the standardized process 10(-2) M silver nitrate solution was interacted for 411 with lemon Juice (2% citric acid concentration and 0 5% ascorbic acid concentration) in the ratio of 1 4(vol vol) The formation of silver nanoparticles was confirmed by Surface Plasmon Resonance as determined by UV-Visible spectra in the range of 400-500 nm X ray diffraction analysis revealed the distinctive facets (1 1 1 200 220 2 2 2 and 3 1 1 planes) of silver nanoparticles We found that citric acid was the principal reducing agent for the nanosynthesis process FT IR spectral studies demonstrated citric acid as the probable stabilizing agent Silver nanoparticles below 50 nm with spherical and spheroidal shape were observed from transmission electron microscopy The correlation between absorption maxima and particle sizes were derived for different UV-Visible absorption maxima (corresponding to different citric acid concentrations) employing MiePlot v 3 4 The theoretical particle size corresponding to 2% citric acid concentration was corn pared to those obtained by various experimental techniques like X ray diffraction analysis atomic force microscopy and transmission electron microscopy (C) 2010 Elsevier B V All rights reserved

A Comparative Study of the Effect of Metallic Au and ReO3 Nanoparticles on the Performance of Silicon Solar Cells

The influence of gold (similar to 35 nm diameter) as well as ReO3 (similar to 17 nm diameter) nanoparticles placed atop silicon photovoltaic devices on absorption and photocurrent generation has been investigated. The nanoparticles improve the power transmission into the semiconductor and consequently, the photocurrent response at wavelengths corresponding to plasmon absorption. An increase in short circuit current up to 4.5% under simulated solar irradiation was observed with the ReO3 nanoparticles, while the gold nanoparticles showed enhancements up to 6.5%. The increase in photocurrent is observed at wavelengths corresponding to the maxima in the surface plasmon resonance absorption spectra. (C) 2010 The Japan Society of Applied Physics

Atmospheric boundary-layer across Hadley and Ferrel cells over the Indian Ocean

A Southern Ocean Pilot cruise covering the latitudes from 10 degrees N to 56 degrees S in the open Indian Ocean was carried out during January February 2004. Surface and upper air data collected during this cruise are reported here. It is shown that the broad features of the atmosphere, in particular that of temperature, follow the tropical and mid-latitude weather expected during January February in this region. However, the atmospheric boundary-layer shows large variations, both in its height and structure between tropics and high latitudes. Strong influence of the surface heat flux on boundary layer structure is clearly seen. Humidity field reveals several local maxima and minima, suggesting a laminated atmosphere with air from different sources moving almost unmixed in adjacent layers.

Metal-Insulator Transitions in Anion-Excess LaMnO3+? Controlled by the Mn4+ Content

LaMnO3+? samples with Mn4+ content up to 50% have been prepared by different methods. The structure of LaMnO3+? changes from orthorhombic to cubic (via rhombohedral) with increase in the Mn4+ content. LaMnO3+? samples containing greater than 20% Mn4+ are ferromagnetic and show resistivity maxima at a temperature Tt which is close to the ferromagnetic Curie temperature. The resistivity maximum is due to the occurrence of a metal-insulator transition. In samples heated to the same temperature, the value of Tt increases with % Mn4+. For a given sample, Tt increases with the temperature of heat treatment due to the increase in particle size. The onset of ferromagnetism in LaMnO3+? accompanied by an insulator-metal transition is similar to that found in La1-xCaxMnO3 and La1-xSrxCoO3.

Photoluminescence enhancement and quenching in metal-semiconductor quantum dot hybrid arrays

Hybrid monolayer arrays of metal and semiconductor quantum dots have been prepared to study the exciton-plasmon interaction. We observed crossover from strong quenching to enhancement in photoluminescence of the quantum dots as a function of the emission wavelength for fixed interparticle spacings. Remarkably, the enhancement is observed even for extremely short separation at which strong quenching has been observed and predicted earlier. A significant redshift in emission maxima is also observed for quantum dots with quenched emission. The possible role of collective phenomena as well as strong interactions in such ordered hybrid arrays in controlling the emission is discussed. (C) 2011 American Institute of Physics. doi:10.1063/1.3553766]