Synthesis and characterisation of metal oxyhydroxide and oxide nanomaterials

In this work, a range of nanomaterials have been synthesised based on metal oxyhydroxides MO(OH), where M=Al, Co, Cr, etc. Through a self-assembly hydrothermal route, metal oxyhydroxide nanomaterials with various morphologies were successfully synthesised: one dimensional boehmite (AlO(OH)) nanofibres, zero dimensional indium hydroxide (In(OH)3) nanocubes and chromium oxyhydroxide (CrO(OH)) nanoparticles, as well as two dimensional cobalt hydroxide and oxyhydroxide (Co(OH)2 & CoO(OH)) nanodiscs. In order to control the synthetic nanomaterial morphology and growth, several factors were investigated including cation concentration, temperature, hydrothermal treatment time, and pH. Metal ion doping is a promising technique to modify and control the properties of materials by intentionally introducing impurities or defects into the material. Chromium was successfully applied as a dopant for fabricating doped boehmite nanofibres. The thermal stability of the boehmite nanofibres was enhanced by chromium doping, and the photoluminescence property was introduced to the chromium doped alumina nanofibres. Doping proved to be an efficient method to modify and functionalize nanomaterials. The synthesised nanomaterials were fully characterised by X-ray diffraction (XRD), transmission electron microscopy (TEM) combined with selected area electron diffraction (SAED), scanning electron microscopy (SEM), BET specific surface area analysis, X-ray photoelectron spectroscopy (XPS) and thermo gravimetric analysis (TGA). Hot-stage Raman and infrared emission spectroscopy were applied to study the chemical reactions during dehydration and dehydroxylation. The advantage of these techniques is that the changes in molecular structure can be followed in situ and at the elevated temperatures.

Assembly and self-organization of nanomaterials

The increasing interest in nanoscience and nanotechnology has prompted intense investigations into appropriate fabrication techniques. Self-organized, bottom-up growth of nanomaterials using plasma nanofabrication techniques1–10 has proven to be one of the most promising approaches for the construction of precisely tailored nanostructures (i.e., quantum dots,11–13 nanotubes,14–17 nanowires,18–20 etc.) arrays. Thus the primary aim of this chapter is to show how plasmas may be used to achieve a high level of control during the self-organized growth of a range of nanomaterials, from zero-dimensional quantum dots (Section 15.2) to one- and two-dimensional nanomaterials (Section 15.3) to nanostructured films (Section 15.4)...

Crystal structures and hydrogen-bonding in the co-crystalline adducts of 3,5-dinitrobenzoic acid with 4-aminosalicylic acid and 2-hydroxy-3-(1H-indol-3-yl)propenoic acid

The structures of the cocrystalline adducts of 3,5-dinitrobenzoic acid (3,5-DNBA) with 4-aminosalicylic acid (PASA), the 1:1 partial hydrate, C7H4N2O6 .C7H7NO3 . 2H2O, (I) and 2-hydroxy-3-(1H-indol-3-yl)propenoic acid (HIPA) and the 1:1:1 d6-dimethylsulfoxide solvate, C7H4N2O6 . C11H9NO3 . C2D6OS, (II) are reported. The crystal substructure of (I) comprises two centrosymmetric hydrogen-bonded R2/2(8) homodimers, one with 3,5-DNBA, the other with PASA, and an R2/2(8) 3,5-DNBA-PASA heterodimer. In the crystal, inter-unit amine N-H...O and water O-H...O hydrogen bonds generate a three-dimensional supramolecular structure. In (II), the asymmetric unit consists of the three constituent molecules which form an essentially planar cyclic hydrogen-bonded heterotrimer unit [graph set R2/3(17)] through carboxyl, hydroxy and amino groups. These units associate across a crystallographic inversion centre through the HIPA carboxylic acid group in an R2/2~(8) hydrogen-bonding association, giving a zero-dimensional structure lying parallel to (100). In both structures, pi--pi interactions are present [minimum ring centroid separations: 3.6471(18)A in (I) and 3.5819(10)A in (II)].

Population of computational rabbit-specific ventricular action potential models for investigating sources of variability in cellular repolarisation

Variability is observed at all levels of cardiac electrophysiology. Yet, the underlying causes and importance of this variability are generally unknown, and difficult to investigate with current experimental techniques. The aim of the present study was to generate populations of computational ventricular action potential models that reproduce experimentally observed intercellular variability of repolarisation (represented by action potential duration) and to identify its potential causes. A systematic exploration of the effects of simultaneously varying the magnitude of six transmembrane current conductances (transient outward, rapid and slow delayed rectifier K(+), inward rectifying K(+), L-type Ca(2+), and Na(+)/K(+) pump currents) in two rabbit-specific ventricular action potential models (Shannon et al. and Mahajan et al.) at multiple cycle lengths (400, 600, 1,000 ms) was performed. This was accomplished with distributed computing software specialised for multi-dimensional parameter sweeps and grid execution. An initial population of 15,625 parameter sets was generated for both models at each cycle length. Action potential durations of these populations were compared to experimentally derived ranges for rabbit ventricular myocytes. 1,352 parameter sets for the Shannon model and 779 parameter sets for the Mahajan model yielded action potential duration within the experimental range, demonstrating that a wide array of ionic conductance values can be used to simulate a physiological rabbit ventricular action potential. Furthermore, by using clutter-based dimension reordering, a technique that allows visualisation of multi-dimensional spaces in two dimensions, the interaction of current conductances and their relative importance to the ventricular action potential at different cycle lengths were revealed. Overall, this work represents an important step towards a better understanding of the role that variability in current conductances may play in experimentally observed intercellular variability of rabbit ventricular action potential repolarisation.

Stochastic kinetics of ribosomes: Single motor properties and collective behavior

Syntheses of protein molecules in a cell are carried out by ribosomes.A ribosome can be regarded as a molecular motor which utilizes the input chemical energy to move on a messenger RNA (mRNA) track that also serves as a template for the polymerization of the corresponding protein. The forward movement, however, is characterized by an alternating sequence of translocation and pause. Using a quantitative model, which captures the mechanochemical cycle of an individual ribosome, we derive an exact analytical expression for the distribution of its dwell times at the successive positions on the mRNA track. Inverse of the average dwell time satisfies a Michaelis-Menten-type'' equation and is consistent with the general formula for the average velocity of a molecular motor with an unbranched mechanochemical cycle. Extending this formula appropriately, we also derive the exact force-velocity relation for a ribosome. Often many ribosomes each synthesizes a copy of the same protein. We extend the model of a single ribosome by incorporating steric exclusion of different individuals on the same track. We draw the phase diagram of this model of ribosome traffic in three-dimensional spaces spanned by experimentally controllable parameters. We suggest new experimental tests of our theoretical predictions.

Synthesis, Structure, and Transformation Studies in a Family of Inorganic-Organic Hybrid Framework Structures Based on Indium

Eight new open-framework inorganic-organic hybrid compounds based on indium have been synthesized employing hydrothermal methods. All of the compounds have InO6, C2O4, and HPO3/HPO4/SO4 units connected to form structures of different dimensionality Thus, the compounds have zero- (I), two- (II, III, IV, V, VII, and VIII), and three-dimensionally (VI) extended networks. The formation of the first zero-dimensional hybrid compound is noteworthy In addition, concomitant polymorphic structures have been observed in the present study. The molecular compound, I, was found to be reactive, and the transformation studies in the presence of a base (pyridine) give rise to the polymorphic structures of II and III, while the addition of an acid (H3PO3) gives rise to a new indium phosphite with a pillared layer structure (T1). Preliminary density functional theory calculations suggest that the stabilities of the polymorphs are different, with one of the forms (II) being preferred over the other, which is consistent with the observed experimental behavior. The oxalate units perform more than one role in the present structures. Thus, the oxalate units connect two In centers to satisfy the coordination requirements as well as to achieve charge balance in compounds II, IV, and VI. The terminal oxalate units observed in compounds I, IV, and V suggest the possibility of intermediate structures. Both in-plane and out-of-plane connectivity of the oxalate units were observed in compound VI. The 31 compounds have been characterized by powder X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and P-31 NMR studies.

Coordination polymers and hybrid networks of different dimensionalities formed by metal sulfites

In our effort to explore the use of the sulfite ion to design hybrid and open-framework materials, we have been able to prepare, under hydrothermal conditions, zero-dimensional [Zn(C12H8N2)(SO3)]center dot 2H(2)O, I (a = 7.5737(5) angstrom, b = 10.3969(6) angstrom, c = 10.3986(6) angstrom, alpha = 64.172(1)degrees, beta = 69.395(1)degrees, gamma = 79.333(1)degrees, Z = 2, and space group P (1) over bar), one-dimensional [Zn-2(C12H8N2)(SO3)(2)(H2O)], II (a = 8.0247(3) angstrom, b = 9.4962(3) angstrom, c = 10.2740(2) A, alpha = 81.070(1)degrees, beta = 80.438(1)degrees, gamma = 75.66(5)degrees, Z = 2, and space group P (1) over bar), two-dimensional [Zn-2(C10H8N2)(SO3)(2)]center dot H2O, III (a = 16.6062(1) angstrom, b = 4.7935(1) angstrom, c = 19.2721(5) angstrom, beta = 100.674(2)degrees, Z = 4, and space group C2/c), and three-dimensional [Zn-4(C6H12N2)(SO3)(4)(H2O)(4)], IV (a = 11.0793(3) angstrom, c = 8.8246(3) angstrom, Z = 2, and space group P42nm), of which the last three are coordination polymers. A hybrid open-framework sulfite-sulfate of the composition [C2H10N2][Nd(SO3)(SO4)(H2O)](2), V (a = 9.0880(3) angstrom, b = 6.9429(2) angstrom, c = 13.0805(5) A, beta = 91.551(2)degrees, Z = 2, and space group P2(1)/c), with a layered structure containing metal-oxygen-metal bonds has also been described.

Selection and thermodynamic analysis of a turbocharger for a producer gas-fuelled multi-cylinder engine

The current work addresses the use of producer gas, a bio-derived gaseous alternative fuel, in engines designed for natural gas, derived from diesel engine frames. Impact of the use of producer gas on the general engine performance with specific focus on turbo-charging is addressed. The operation of a particular engine frame with diesel, natural gas and producer gas indicates that the peak load achieved is highest with diesel fuel (in compression ignition mode) followed by natural gas and producer gas (both in spark ignite mode). Detailed analysis of the engine power de-rating on fuelling with natural gas and producer gas indicates that the change in compression ratio (migration from compression to spark ignited mode), difference in mixture calorific value and turbocharger mismatch are the primary contributing factors. The largest de-rating occurs due to turbocharger mismatch. Turbocharger selection and optimization is identified as the strategy to recover the non-thermodynamic power loss, identified as the recovery potential (the loss due to mixture calorific value and turbocharger mismatch) on operating the engine with a fuel different from the base fuel. A turbocharged after-cooled six cylinder, 5.9 l, 90 kWe (diesel rating) engine (12.2 bar BMEP) is available commercially as a naturally aspirated natural gas engine delivering a peak load of 44.0 kWe (6.0 bar BMEP). The engine delivers a load of 27.3 kWe with producer gas under naturally aspirated mode. On charge boosting the engine with a turbocharger similar in configuration to the diesel engine turbocharger, the peak load delivered with producer gas is 36 kWe (4.8 bar BMEP) indicating a de-rating of about 60% over the baseline diesel mode. Estimation of knock limited peak load for producer gas-fuelled operation on the engine frame using a Wiebe function-based zero-dimensional code indicates a knock limited peak load of 76 kWe, indicating the potential to recover about 40 kWe. As a part of the recovery strategy, optimizing the ignition timing for maximum brake torque based on both spark sweep tests and established combustion descriptors and engine-turbocharger matching for producer gas-fuelled operation resulted in a knock limited peak load of 72.8 kWe (9.9 bar BMEP) at a compressor pressure ratio of 2.30. The de-rating of about 17.0 kWe compared to diesel rating is attributed to the reduction in compression ratio. With load recovery, the specific biomass consumption reduces from 1.2 kg/kWh to 1.0 kg/kWh, an improvement of over 16% while the engine thermal efficiency increases from 28% to 32%. The thermodynamic analysis of the compressor and the turbine indicates an isentropic efficiency of 74.5% and 73%, respectively.

Confining Dirac electrons on a topological insulator surface using potentials and a magnetic field

We study the effects of extended and localized potentials and a magnetic field on the Dirac electrons residing at the surface of a three-dimensional topological insulator like Bi2Se3. We use a lattice model to numerically study the various states; we show how the potentials can be chosen in a way which effectively avoids the problem of fermion doubling on a lattice. We show that extended potentials of different shapes can give rise to states which propagate freely along the potential but decay exponentially away from it. For an infinitely long potential barrier, the dispersion and spin structure of these states are unusual and these can be varied continuously by changing the barrier strength. In the presence of a magnetic field applied perpendicular to the surface, these states become separated from the gapless surface states by a gap, thereby giving rise to a quasi-one-dimensional system. Similarly, a magnetic field along with a localized potential can give rise to exponentially localized states which are separated from the surface states by a gap and thereby form a zero-dimensional system. Finally, we show that a long barrier and an impurity potential can produce bound states which are localized at the impurity, and an ``L''-shaped potential can have both bound states at the corner of the L and extended states which travel along the arms of the potential. Our work opens the way to constructing wave guides for Dirac electrons.

In-cylinder investigations and analysis of a SI gas engine fuelled with H-2 and CO rich syngas fuel: Sensitivity analysis of combustion descriptors for engine diagnostics and control

The sensitivity of combustion phasing and combustion descriptors to ignition timing, load and mixture quality on fuelling a multi-cylinder natural gas engine with bio-derived H-2 and CO rich syngas is addressed. While the descriptors for conventional fuels are well established and are in use for closed loop engine control, presence of H-2 in syngas potentially alters the mixture properties and hence combustion phasing, necessitating the current study. The ability of the descriptors to predict abnormal combustion, hitherto missing in the literature, is also addressed. Results from experiments using multi-cylinder engines and numerical studies using zero dimensional Wiebe function based simulation models are reported. For syngas with 20% H-2 and CO and 2% CH4 (producer gas), an ignition retard of 5 +/- 1 degrees was required compared to natural gas ignition timing to achieve peak load of 72.8 kWe. It is found that, for syngas, whose flammability limits are 0.42-1.93, the optimal engine operation was at an equivalence ratio of 1.12. The same methodology is extended to a two cylinder engine towards addressing the influence of syngas composition, especially H-2 fraction (varying from 13% to 37%), on the combustion phasing. The study confirms the utility of pressure trace derived combustion descriptors, except for the pressure trace first derivative, in describing the MBT operating condition of the engine when fuelled with an alternative fuel. Both experiments and analysis suggest most of the combustion descriptors to be independent of the engine load and mixture quality. A near linear relationship with ignition angle is observed. The general trend(s) of the combustion descriptors for syngas fuelled operation are similar to those of conventional fuels; the differences in sensitivity of the descriptors for syngas fuelled engine operation requires re-calibration of control logic for MBT conditions. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Uma Simulação computacional do passeio aleatório simples

Em 1828 foi observado um fenômeno no microscópio em que se visualizava minúsculos grãos de pólen mergulhados em um líquido em repouso que mexiam-se de forma aleatória, desenhando um movimento desordenado. A questão era compreender este movimento. Após cerca de 80 anos, Einstein (1905) desenvolveu uma formulação matemática para explicar este fenômeno, tratado por movimento Browniano, teoria cada vez mais desenvolvida em muitas das áreas do conhecimento, inclusive recentemente em modelagem computacional. Objetiva-se pontuar os pressupostos básicos inerentes ao passeio aleatório simples considerando experimentos com e sem problema de valor de contorno para melhor compreensão ao no uso de algoritmos aplicados a problemas computacionais. Foram explicitadas as ferramentas necessárias para aplicação de modelos de simulação do passeio aleatório simples nas três primeiras dimensões do espaço. O interesse foi direcionado tanto para o passeio aleatório simples como para possíveis aplicações para o problema da ruína do jogador e a disseminação de vírus em rede de computadores. Foram desenvolvidos algoritmos do passeio aleatório simples unidimensional sem e com o problema do valor de contorno na plataforma R. Similarmente, implementados para os espaços bidimensionais e tridimensionais,possibilitando futuras aplicações para o problema da disseminação de vírus em rede de computadores e como motivação ao estudo da Equação do Calor, embora necessita um maior embasamento em conceitos da Física e Probabilidade para dar continuidade a tal aplicação.

Rank-preserving geometric means of positive semi-definite matrices

The generalization of the geometric mean of positive scalars to positive definite matrices has attracted considerable attention since the seminal work of Ando. The paper generalizes this framework of matrix means by proposing the definition of a rank-preserving mean for two or an arbitrary number of positive semi-definite matrices of fixed rank. The proposed mean is shown to be geometric in that it satisfies all the expected properties of a rank-preserving geometric mean. The work is motivated by operations on low-rank approximations of positive definite matrices in high-dimensional spaces.© 2012 Elsevier Inc. All rights reserved.

On-line policy optimisation of Bayesian spoken dialogue systems via human interaction

A partially observable Markov decision process has been proposed as a dialogue model that enables robustness to speech recognition errors and automatic policy optimisation using reinforcement learning (RL). However, conventional RL algorithms require a very large number of dialogues, necessitating a user simulator. Recently, Gaussian processes have been shown to substantially speed up the optimisation, making it possible to learn directly from interaction with human users. However, early studies have been limited to very low dimensional spaces and the learning has exhibited convergence problems. Here we investigate learning from human interaction using the Bayesian Update of Dialogue State system. This dynamic Bayesian network based system has an optimisation space covering more than one hundred features, allowing a wide range of behaviours to be learned. Using an improved policy model and a more robust reward function, we show that stable learning can be achieved that significantly outperforms a simulator trained policy. © 2013 IEEE.

Electronic structure and optical gain saturation of InAs1-xNx/GaAs quantum dots

The electronic band structures and optical gains of InAs1-xNx/GaAs pyramid quantum dots (QDs) are calculated using the ten-band k . p model and the valence force field method. The optical gains are calculated using the zero-dimensional optical gain formula with taking into consideration of both homogeneous and inhomogeneous broadenings due to the size fluctuation of quantum dots which follows a normal distribution. With the variation of QD sizes and nitrogen composition, it can be shown that the nitrogen composition and the strains can significantly affect the energy levels especially the conduction band which has repulsion interaction with nitrogen resonant state due to the band anticrossing interaction. It facilitates to achieve emission of longer wavelength (1.33 or 1.55 mu m) lasers for optical fiber communication system. For QD with higher nitrogen composition, it has longer emission wavelength and less detrimental effect of higher excited state transition, but nitrogen composition can affect the maximum gain depending on the factors of transition matrix element and the Fermi-Dirac distributions for electrons in the conduction bands and holes in the valence bands respectively. For larger QD, its maximum optical gain is greater at lower carrier density, but it is slowly surpassed by smaller QD as carrier concentration increases. Larger QD can reach its saturation gain faster, but this saturation gain is smaller than that of smaller QD. So the trade-off between longer wavelength, maximum optical, saturation gain, and differential gain must be considered to select the appropriate QD size according to the specific application requirement. (C) 2009 American Institute of Physics. [DOI 10.1063/1.3143025]

A new method to fabricate InGaN quantum dots by metalorganic chemical vapor deposition

A new method to form nanoscale InGaN quantum dots using MOCVD is reported, This method is much different from a method. which uses surfactant or the Stranski-Krastannow growth mode. The dots were formed by increasing the energy barrier for adatoms, which are hopping by surface passivation, and by decreasing the growth temperature. Thus, the new method can be called as a passivation-low-temperature method. Regular high-temperature GaN films were grown first and were passivated. A low-temperature thin layer of GaN dot was then deposited on the surface that acted as the adjusting layer. At last the high-density InGaN dots could be fabricated on the adjusting layer. Atomic force microscopy measurement revealed that InGaN dots were small enough to expect zero-dimensional quantum effects: The islands were typically 80 nm wide and 5 nm high. Their density was about 6 x 10(10) cm(-2). Strong photoluminescence emission from the dots is observed at room temperature, which is much stronger than that of the homogeneous InGaN film with the same growth time. Furthermore, the PL emission of the GaN adjusting layer shows 21 meV blueshift compared with the band edge emission of the GaN due to quantum confine effect. (C) 2002 Elsevier Science B.V. All rights reserved.