Permutation decoding for binary codes from lattice graphs

By finding explicit PD sets, we show that permutation decoding can be used for the binary code obtained from the row span over the field F₂ of an adjacency matrix of the lattice graph L₂(n) for any n?5.     

Modelling of closed-chain manipulators on an excavator vehicle

The main focus of this paper is to develop a physics-based model for a closed-chain manipulator in an excavator vehicle. The derivation of closed-chain manipulator dynamic equations with a structure similar to open-chain manipulator equations is an important research problem, particularly with reference to controller design. In this paper, an approach for deriving closed-chain manipulator equations with an open-chain structure, based on trigonometric t-formulae, is presented. Holonomic loop closure constraints are employed in order to derive the closed-chain mechanism dynamics from the reduced system dynamics. The closed-chain equations, with a structure similar to serial link equations, are presented. The model incorporates the dynamic properties of the manipulator and bucket. The dynamic model for the excavation system is validated against measured data obtained from a full-scale closed-chain excavator vehicle. A dynamic model is important for the design of control strategies for trajectory tracking, a key requirement for automating the excavation task. It is noted that even though the results presented in this paper are focused on a particular excavator vehicle, the research is generic and can be adapted to any closed-chain manipulator.     

Characteristics and properties of metal-to-ligand charge-transfer excited states in 2,3-bis(2-pyridyl)pyrazine and 2,2'-bypyridine ruthenium complexes. Perturbation-theory-based correlations of optical absorption and emission parameters with electrochemistry and thermal kinetics and related Ab initio calculations

The absorption, emission, and infrared spectra, metal (Ru) and ligand (PP) half-wave potentials, and ab initio calculations on the ligands (PP) are compared for several [L(n)()Ru(PP)](2+) and [[L(n)Ru]dpp[RuL'(n)]](4+) complexes, where L(n) and L'(n) = (bpy)(2) or (NH(3))(4) and PP = 2,2'-bipyridine (bpy), 2,3-bis(2-pyridyl)pyrazine (dpp), 2,3-bis(2-pyridyl)quinoxaline (dpq), or 2,3-bis(2pyridyl)benzoquinoxaline (dpb). The energy of the metal-to-ligand charge-transfer (MLCT) absorption maximum (hnu(max)) varies in nearly direct proportion to the difference between Ru(III)/Ru(II) and (PP)/(PP)(-) half-wave potentials, DeltaE(1/2), for the monometallic complexes but not for the bimetallic complexes. The MLCT spectra of [(NH(3))(4)Ru(dpp)](2+) exhibit three prominent visible-near-UV absorptions, compared to two for [(NH(3))(4)Ru(bpy)](2+), and are not easily reconciled with the MLCT spectra of [[(NH(3))(4)Ru]dpp[RuL(n)]](4+). The ab initio calculations indicate that the two lowest energy pi orbitals are not much different in energy in the PP ligands (they correlate with the degenerate pi orbitals of benzene) and that both contribute to the observed MLCT transitions. The LUMO energies calculated for the monometallic complexes correlate strongly with the observed hnu(max) (corrected for variations in metal contribution). The LUMO computed for dpp correlates with LUMO + 1 of pyrazine. This inversion of the order of the two lowest energy pi orbitals is unique to dpp in this series of ligands. Configurational mixing of the ground and MLCT excited states is treated as a small perturbation of the overall energies of the metal complexes, resulting in a contribution epsilon(s) to the ground-state energy. The fraction of charge delocalized, alpha(DA)(2), is expected to attenuate the reorganizational energy, chi(reorg), by a factor of approximately (1 - 4alpha(DA)(2) + alpha(DA)(4)), relative to the limit where there is no charge delocalization. This appears to be a substantial effect for these complexes (alpha(DA)(2) congruent with 0.1 for Ru(II)/bpy), and it leads to smaller reorganizational energies for emission than for absorption. Reorganizational energies are inferred from the bandwidths found in Gaussian analyses of the emission and/or absorption spectra. Exchange energies are estimated from the Stokes shifts combined with perturbation--theory-based relationship between the reorganizational energies for absorption and emission values. The results indicate that epsilon(s) is dominated by terms that contribute to electron delocalization between metal and PP ligand. This inference is supported by the large shifts in the N-H stretching frequency of coordinated NH(3) as the number of PP ligands is increased. The measured properties of the bpy and dpp ligands seem to be very similar, but electron delocalization appears to be slightly larger (10-40%) and the exchange energy contributions appear to be comparable (e.g., approximately 1.7 x 10(3) cm(-1) in [Ru(bpy)(2)dpp](2+) compared to approximately 1.3 x 10(3) cm(-1) in the bpy analogue).     

Investigating the effects of conductivity on zone overlap with EMMA: computer simulation and experiment

In this paper, we demonstrate, using both experiment and simulation, how sample zone conductivity can affect plug-plug mixing in small molecule applications of electrophoretically mediated microanalysis (EMMA). The effectiveness of in-line mixing, which is driven by potential, can vary widely with experimental conditions. Using two small molecule systems, the effects of local conductivity differences between analyte plugs, reagent plugs and the BGE on EMMA analyses are examined. Simul 5.0, a dynamic simulation program for CE systems, is used to understand the ionic boundaries and profiles that give rise to the experimentally obtained data for EMMA analyses for (i) creatinine determination via the Jaffe reaction, a reaction involving a neutral and an anion, and (ii) the redox reaction between gallate and 2,6-dichloroindophenol, two anions. Low sample conductivity, which is widely used in CE analyses, can be detrimental for in-line reactions involving a neutral reactant, as rapid migration of the ionic component across a low conductivity neutral zone results in poor reagent plug overlap and low reaction efficiency. Conversely, with two similarly charged reagents, a low conductivity sample plug is advantageous, as it allows field-amplified stacking of the reagents into a tight reaction zone. In addition, the complexity of simultaneously overlapping three reagent zones is considered, and experimental results validate the predictions made by the simulation. The simulations, however, do not appear to predict all of the observed experimental behavior. Overall, by combining experiment with simulation, an enhanced appreciation for the local field effects in EMMA is realized, and general guidelines for an advantageous sample matrix can be established for categories of EMMA analyses.     

Track-terrain modelling and traversability prediction for tracked vehicles on soft terrain

Skid-steered tracked vehicles are the favoured platform for unmanned ground vehicles (UGVs) in poor terrain conditions. However, the concept of skid-steering relies largely on track slippage to allow the vehicle to conduct turning manoeuvres potentially leading to overly high slip and immobility. It is therefore important to predict such vulnerable vehicle states in order to prevent their occurrence and thus paving the way for improved autonomy of tracked vehicles. This paper presents an analytical approach to track-terrain modelling and a novel traversability prediction simulator for tracked vehicles conducting steady-state turning manoeuvres on soft terrain. Traversability is identified by predicting the resultant track forces acting on the track-terrain interface and the adopted models are modified to provide an analytical generalised solution. The validity of the simulator has been verified by comparison with available data in the literature and through an in-house experimental study. The developed simulator can be employed as a traversability predictor and also as a design tool to test the performance of tracked vehicles with different vehicle geometries operating on a wide range of soil properties.     

Electrical and structural studies of a LiBOB-based gel polymer electrolyte

A series of gel polymer electrolytes (GPEs) containing lithium bis(oxalato)borate (LiBOB), propylene carbonate (PC), and ethylene carbonate (EC) have been investigated. Poly(ethylene oxide) (PEO) was used as the polymer. First, a series of liquid electrolytes was prepared by varying the Li:O ratio and obtained the best composition giving the highest conductivity of 7.1?×?10^?3 S cm^?1 at room temperature. Then, the PEO-based GPEs were prepared by adding different amounts of LiBOB and PEO into a mixture of equal weights of EC and PC (40 % of each from the total weight). The gel electrolyte comprises of 12.5 % of LiBOB, 7.5 % of PEO, 40 % of EC, and 40 % of PC gave the highest ionic conductivity of 5.8?×?10^?3 S cm^?1 at room temperature. From the DC polarization measurements, ionic nature of the gel electrolyte was confirmed. Fourier transform infrared (FTIR) spectra of electrolytes showed the Li⁺ ion coordination with EC and PC molecules. These interactions were exhibited in the peaks corresponding to ring breathing of EC at 893 cm^?1 and ring bending of EC and symmetric ring deformation of PC at 712 and 716 cm^?1 respectively. The presence of free Li⁺ ions and ion aggregates is evident in the peaks due to the symmetric stretching of O–B–O at 985 cm^?1.     

Sensitization of nanostructured TiO2 by electrostatic coupling of ionic dyes to ionic absorbates

It is shown that an ionic dye Y can be electrostatically bonded to an ionic molecule X of opposite charge anchored to a TiO2 surface via suitable ligands. Dye-sensitized solid-state photovoltaic cells of the configuration n-TiO2/X-Y/p-CuSCN were constructed with X = trihydroxybenzoic acid or mercurochrome and Y = methyl violet. Cells of this configuration were found to be more efficient and delivered higher short-circuit photocurrents and open-circuit photovoltages compared to the cells based only on methyl violet or mercurochrome. It is suggested that this technique would be a means of extending the spectral response of dye-sensitized photovoltaic devices. The formation of a wider barrier by coupling of anionic and cationic species also improves the cell performance by suppression of recombination.     

Sol-gel materials for the solid phase extraction of metals from aqueous solution

Silica that was prepared by sol-gel chemistry to have pore widths in the microporous and in the mesoporous domains was evaluated as the host for performing solid phase extraction (SPE). Selective SPE of Ni(II) was accomplished with dimethylglyoxime (DMG)-doped silica, but the pore width was demonstrated to influence the chemistry of the material. With microporous silica as the host, the stoichiometry of the Ni(II)-DMG complex was 1:1 rather than 1:2, which is the value observed in aqueous solution. A green shift in the visible absorption spectrum was the primary evidence for the difference in stoichiometry; the alternative explanation of a rigidochromic effect on the spectrum was eliminated. The capacity of the DMG-doped mesoporous silica was only 9 mumol Ni g(-1) because of leaching of the complexing agent. The microporous material showed no loss of DMG, but low permeability lowered the capacity. An alternative, albeit not selective, approach was to employ a mesoporous host to which a complexing agent, diethylenetriamine (DTA), was covalently bound. In this case, a capacity of 0.156 mmol Cu g(-1), was achieved.