Molecular structure of the discotic liquid crystalline phase of hexa-peri-hexabenzocoronene/oligothiophene hybrid and their charge transport properties

Using atomistic molecular dynamics simulation, we study the discotic columnar liquid crystalline (LC) phases formed by a new organic compound having hexa-peri-Hexabenzocoronene (HBC) core with six pendant oligothiophene units recently synthesized by Nan Hu et al. Adv. Mater. 26, 2066 (2014)]. This HBC core based LC phase was shown to have electric field responsive behavior and has important applications in organic electronics. Our simulation results confirm the hexagonal arrangement of columnar LC phase with a lattice spacing consistent with that obtained from small angle X-ray diffraction data. We have also calculated various positional and orientational correlation functions to characterize the ordering of the molecules in the columnar arrangement. The molecules in a column are arranged with an average twist of 25 degrees having an average inter-molecular separation of similar to 5 angstrom. Interestingly, we find an overall tilt angle of 43 degrees between the columnar axis and HBC core. We also simulate the charge transport through this columnar phase and report the numerical value of charge carrier mobility for this liquid crystal phase. The charge carrier mobility is strongly influenced by the twist angle and average spacing of the molecules in the column. (C) 2015 AIP Publishing LLC.

Tungsten-based nanomaterials (WO3 & Bi2WO6): Modifications related to charge carrier transfer mechanisms and photocatalytic applications

Heterogeneous photocatalysis is an ideal green energy technology for the purification of wastewater. Although titania dominates as the reference photocatalyst, its wide band gap is a bottleneck for extended utility. Thus, search for non-TiO2 based nanomaterials has become an active area of research in recent years. In this regard, visible light absorbing polycrystalline WO3 (2.4-2.8 eV) and Bi2WO6 (2.8 eV) with versatile structure-electronic properties has gained considerable interest to promote the photocatalytic reactions. These materials are also explored in selective functional group transformation in organic reactions, because of low reduction and oxidation potential of WO3 CB and Bi2WO6 VB, respectively. In this focused review, various strategies such as foreign ion doping, noble metal deposition and heterostructuring with other semiconductors designed for efficient photocatalysis is discussed. These modifications not only extend the optical response to longer wavelengths, but also prolong the life-time of the charge carriers and strengthen the photocatalyst stability. The changes in the surface-bulk properties and the charge carrier transfer dynamics associated with each modification correlating to the high activity are emphasized. The presence of oxidizing agents, surface modification with Cu2+ ions and synthesis of exposed facets to promote the degradation rate is highlighted. In depth study on these nanomaterials is likely to sustain interest in wastewater remediation and envisaged to signify in various green energy applications. (C) 2015 Elsevier B.V. All rights reserved.

Injection barrier induced deviations in space charge limited conduction in doped poly(3-methylthiophene) based devices

The carrier density dependent current-voltage (J V) characteristics of electrochemically prepared poly(3-methylthiophene) (P3MeT) have been investigated in Pt/P3MeT/Al devices, as a function of temperature from 280 to 84 K. In these devices, the charge transport is found to be mainly governed by different transport regimes of space charge limited conduction (SCLC). In a lightly doped device, SCLC controlled by exponentially distributed traps (Vl+1 law, l > 1) is observed in the intermediate voltage range (0.5-2 V) at all temperatures. However, at higher bias (> 2 V), the current deviates from the usual Vl+1 law where the slope is found to be less than 2 of the logJ-logV plot, which is attributed to the presence of the injection barrier. These deviations gradually disappear at higher doping level due to reduction in the injection barrier. Numerical simulations of the Vl+1 law by introducing the injection barrier show good agreement with experimental data. The results show that carrier density can tune the charge transport mechanism in Pt/P3MeT/Al devices to understand the non-Ohmic behavior. The plausible reasons for the origin of injection barrier and the transitions in the transport mechanism with carrier density are discussed. (C) 2015 AIP Publishing LLC.

H2O-CH4 and H2S-CH4 complexes: a direct comparison through molecular beam experiments and ab initio calculations

New molecular beam scattering experiments have been performed to measure the total ( elastic plus inelastic) cross sections as a function of the velocity in collisions between water and hydrogen sulfide projectile molecules and the methane target. Measured data have been exploited to characterize the range and strength of the intermolecular interaction in such systems, which are of relevance as they drive the gas phase molecular dynamics and the clathrate formation. Complementary information has been obtained by rotational spectra, recorded for the hydrogen sulfide-methane complex, with a pulsed nozzle Fourier transform microwave spectrometer. Extensive ab initio calculations have been performed to rationalize all the experimental findings. The combination of experimental and theoretical information has established the ground for the understanding of the nature of the interaction and allows for its basic components to be modelled, including charge transfer, in these weakly bound systems. The intermolecular potential for H2S-CH4 is significantly less anisotropic than for H2O-CH4, although both of them have potential minima that can be characterized as `hydrogen bonded'.

Fusing the Navigation Information of Dual Foot-Mounted Zero-Velocity-Update-Aided Inertial Navigation Systems

A range constraint method viz. centroid method is proposed to fuse the navigation information of dual (right and left) foot-mounted Zero-velocity-UPdaTe (ZUPT)-aided Inertial Navigation Systems (INSs). Here, the range constraint means that the distance of separation between the position estimates of right and left foot ZUPT-aided INSs cannot be greater than a quantity known as foot-to-foot maximum separation. We present the experimental results which illustrate the applicability of the proposed method. The results show that the proposed method significantly enhances the accuracy of the navigation solution when compared to using two uncoupled foot-mounted ZUPT-aided INSs. Also, we compare the performance of the proposed method with the existing data fusion methods.

Continuum in the X-Z-Y Weak Bonds: Z= Main Group Elements

The Continuum in the variation of the X-Z bond length change from blue-shifting to red-shifting through zero-shifting in the X-Z---Y complex is inevitable. This has been analyzed by ab-initio molecular orbital calculations using Z= Hydrogen, Halogens, Chalcogens, and Pnicogens as prototypical examples. Our analysis revealed that, the competition between negative hyperconjugation within the donor (X-Z) molecule and Charge Transfer (CT) from the acceptor (Y) molecule is the primary reason for the X-Z bond length change. Here, we report that, the proper tuning of X-and Y-group for a particular Z-can change the blue-shifting nature of X-Z bond to zero-shifting and further to red-shifting. This observation led to the proposal of a continuum in the variation of the X-Z bond length during the formation of X-Z---Y complex. The varying number of orbitals and electrons available around the Z-atom differentiates various classes of weak interactions and leads to interactions dramatically different from the H-Bond. Our explanations based on the model of anti-bonding orbitals can be transferred from one class of weak interactions to another. We further take the idea of continuum to the nature of chemical bonding in general. (C) 2015 Wiley Periodicals, Inc.

NH3 adsorption on PtM (Fe, Co, Ni) surfaces: Cooperating effects of charge transfer, magnetic ordering and lattice strain

Adsorption of a molecule or group with an atom which is less electronegative than oxygen (0) and directly interacting with the surface is very relevant to development of PtM (M = 3d-transition metal) catalysts with high activity. Here, we present theoretical analysis of the adsorption of NH3 molecule (N being less electronegative than 0) on (111) surfaces of PtM (Fe, Co, Ni) alloys using the first principles density functional approach. We find that, while NH3-Pt interaction is stronger than that of NH3 with the elemental M-surfaces, it is weaker than the strength of interaction of NH3 with M-site on the surface of PtM alloy. (C) 2016 Published by Elsevier B.V.

Electrochemical, gravimetric and quantum chemical analysis of mild steel corrosion inhibition by colchicine in 1 M HCl medium

The inhibition effect of colchicine (CC) on mild steel (MS) corrosion in 1 M HCl solution has been investigated by electrochemical techniques such as electrochemical impedance spectroscopy, potentiodynamic polarization, chronoamperometry and also by the gravimetric method. Polarization studies showed that CC acts as mixed type corrosion inhibitor. The inhibitor adsorption process in the MS/CC/HCl system was studied at different temperatures (303-333 K). The adsorption of CC on MS surface is an exothermic process and obeys the Langmuir adsorption isotherm. Based on potential of zero charge values and quantum chemical parameters, the mechanism of adsorption has been proposed.

Counting zero kernel pairs over a finite field

Helmke et al. have recently given a formula for the number of reachable pairs of matrices over a finite field. We give a new and elementary proof of the same formula by solving the equivalent problem of determining the number of so called zero kernel pairs over a finite field. We show that the problem is, equivalent to certain other enumeration problems and outline a connection with some recent results of Guo and Yang on the natural density of rectangular unimodular matrices over F-qx]. We also propose a new conjecture on the density of unimodular matrix polynomials. (C) 2016 Elsevier Inc. All rights reserved.

Localized Charge Carrier Transport Properties of Zn1-x Ni (x) O/NiO Two-Phase Composites

We report the localized charge carrier transport of two-phase composite Zn1-x Ni (x) O/NiO (0 a parts per thousand currency sign x a parts per thousand currency sign 1) using the temperature dependence of ac-resistivity rho (ac)(T) across the N,el temperature T (N) (= 523 K) of nickel oxide. Our results provide strong evidence to the variable range hopping of charge carriers between the localized states through a mechanism involving spin-dependent activation energies. The temperature variation of carrier hopping energy epsilon (h)(T) and nearest-neighbor exchange-coupling parameter J (ij)(T) evaluated from the small poleron model exhibits a well-defined anomaly across T (N). For all the composite systems, the average exchange-coupling parameter (J (ij))(AVG) nearly equals to 70 meV which is slightly greater than the 60-meV exciton binding energy of pure zinc oxide. The magnitudes of epsilon (h) (similar to 0.17 eV) and J (ij) (similar to 11 meV) of pure NiO synthesized under oxygen-rich conditions are consistent with the previously reported theoretical estimation based on Green's function analysis. A systematic correlation between the oxygen stoichiometry and, epsilon (h)(T) and J (ij)(T) is discussed.

Visualisation of charge-transfer excitations in donor-acceptor molecules using the particle-hole map: a case study

Charge-transfer (CT) excitations are essential for photovoltaic phenomena in organic solar cells. Owing to the complexity of molecular geometries and orbital coupling, a detailed analysis and spatial visualisation of CT processes can be challenging. In this paper, a new detail-oriented visualisation scheme, the particle-hole map (PHM), is applied and explained for the purpose of spatial analysis of excitations in organic molecules. The PHM can be obtained from the output of a time-dependent density-functional theory calculation with negligible additional computational cost, and provides a useful physical picture for understanding the origins and destinations of electrons and holes during an excitation process. As an example, we consider intramolecular CT excitations in Diketopyrrolopyrrole-based molecules, and relate our findings to experimental results.

Biosensor with Total Internal reflection Imaging Ellipsometry

In order to monitor multiple protein reaction processes simultaneously, a biosensor based on imaging ellipsometry operated in the total internal reflection mode is proposed. It could be realised as an automatic analysis for protein interaction processes with real-time label-free method. Its principle and methodology as well as a demonstration for its applications are presented.

Evaluación de la sustitucion parcial o total de aceite de palma (Elaeis guinensis) por aceite de fritura como fuente de energía en la ración alimenticia de pollos de engorde

La presente investigación estuvo dirigida a determinar la viabilidad, que sobre el desempeño productivo del pollo de engorde, podía ejercer la sustitución parcial o total del porcentaje de aceite de palma (Elaeís guínensis, Jacq) por aceite de fritura como fuente de energía en la ración alimenticia. La sustitución parcial o total se hizo con base en el 6% de aceite que se incluye en la fórmula alimenticia, ajustada a los requerimientos de los pollos de engorde. El ensayo experimental fue realizado en la granja avícola "La Trinidad", propiedad de la empresa TIP-TOP INDUSTRIAL S.A. Se utilizaron 700 pollos de engorde para producción comercial, del híbrido Peterson-Hubbard, de un día de edad y mantenidos en evaluación durante un periodo de 42 días. Estos fueron distribuidos aleatoriamente en cuatro tratamientos, conformados cada uno de cinco unidades experimentales, y éstas a su vez con 35 pollos cada una, quedando de la forma siguiente: Tratamiento T1 (testigo): 6% aceite de palma; tratamiento T2 : 2% aceite de palma y 4% aceite de fritura; tratamiento T3: 1% aceite de palma y 5% aceite de fritura; tratamiento T4 : 6% aceite de fritura. El resto de los ingredientes que conformó la dieta alimenticia fue igual para todos los tratamientos; así como también el manejo de los pollos se realizó al igual que lo hace la Empresa para toda su producción. Las variables estudiadas fueron consumo de alimento, peso vivo final y conversión de alimento. Los resultados obtenidos a partir de estas variables fueron analizados a través de un Diseño Completamente Aleatorio y sometidos a la Prueba de Tukey, el que proporcionó la superioridad existente entre tratamientos. Se encontraron diferencias significativas (p<0.05) entre tratamientos para la variable conversión alimenticia, con índices de conversión para el final de período experimental, de 1.8050, 1.7829, 1.7550 y 1.7310 para los tratamientos T1, T2, T3 y T4, respectivamente. Las variables consumo acumulado de alimento y peso vivo final no presentaron diferencias estadísticas a un nivel de significancia de p<0.05. El análisis financiero demostró que el tratamiento T4 tiene un menor costo de alimentación, siendo este de C$3.35/kg peso vivo. Encontrándose los tratamientos T1.T2 y T3 con costos de C$3.8210, C$3.5624; y C$3.4527/kg peso vivo, respectivamente. El mayor beneficio neto por kilogramo de peso vivo lo obtuvo el tratamiento T4, con C$0.47. Siendo el beneficio neto para los tratamientos T2 y T3 de C$0.26 y C$ 0.37, respectivamente. La mortalidad presentada por los tratamientos T1, T2, T3, y T4 para el final del período experimental fue de 5.13, 3.99, 2.85 y 3.99 (%), respectivamente.