Tetraazamacrocyclic ligands and their copper complexes

The preparation and characterisation of several new types of tetraazamacrocycles and their copper(ll) complexes are described. Condensations of 4,8-diaza-2,3:9,10-dibenzoundecane-1,11-dione with a range of aliphatic and aromatic diamines has allowed the isolation of metal-free diimine macrocycles without recourse to metal template' or 'high dilution' techniques. In several cases these diimines were successfully reduced to yield the related tetraamine macrocycles. For the 15-membered macrocycle, 18,19,20,21-tetrahydro-17-H-tribenzo(f,j,n)(1,5,9,12)tetraazacyclopentadecine, derivatives bearing different substituents in one of the benzene rings were prepared. For the diimine ligands of this type both cationic and neutral copper(II) complexes were isolated and characterised; (the latter type result from loss of anilino protons on complex formation.) Compounds which are structurally related to the above tetraazamacrocycles are described. C-alkylation of the diimines using organolithium reagents appears to proceed regioselectively. An X-ray structure determination of the copper complex of 5,12-dimethyl-5,6,11,12, 18,19,20,21-octahydro-17-H-tribenzo (f,j,n)(1,5,9,12) tetraazacyclopentadecine shows this to be meso-dimethyl isomer. Condensation of 2,2 '-(oxalyldiimino)bisbenzophenone with diamines in the presence of copper(ll) acetate yields macrocyclic neutral copper(ll) complexes which contain a dioxo linkage between the anilino nitrogen atoms. An X-ray structure determination of [5,12-diphenyl-18,19-dioxo-9,10,17,18,19,20-hexahydrodibenzo (e,m) (1,4,8,11) tetraazacyclotetradecinato(2-)]-dimethylformamidocopper II dihydrate indicates steric crowding for the phenyl substituents on the imine carbon atoms. Polycyclic tetraza compounds result from the condensation of the cyclic tetraamines with glyoxal. A group of 20,21 and 22-membered sexadentate ligands having N402 donor sets, and 20-membered ligands with N4S2 and N6 donor sets have also been studied; e.g.: 12,13,25,26,27,28-Hexahydrotetrabenzo (e,i,o,s) (11,14,1,4,8,17) dithiatetraazacycloeicosine. Reduction of the azomethine linkages was achieved for all these ligands and cationic copper(ll) complexes have been prepared and characterised. An X-ray structure determination showed that one of the N402 tetraamine ligands uses only three of its nitrogen atoms in forming a complex with copper(II)

Data management of on-line partial discharge monitoring using wireless sensor nodes integrated with a multi-agent system

On-line partial discharge monitoring has been the subject of significant research in previous years but little work has been carried out with regard to the management of on-site data. To date, on-line partial discharge monitoring within a substation has only been concerned with single plant items, so the data management problem has been minimal. As the age of plant equipment increases, so does the need for condition monitoring to ensure maximum lifespan. This paper presents an approach to the management of partial discharge data through the use of embedded monitoring techniques running on wireless sensor nodes. This method is illustrated by a case study on partial discharge monitoring data from an ageing HVDC reactor

Scattering and absorption of ultracold atoms by nanotubes

We investigate theoretically how cold atoms, including Bose-Einstein condensates, are scattered from, or absorbed by nanotubes with a view to analysing recent experiments. In particular we consider the role of potential strength, quantum reflection, atomic interactions and tube vibrations on atom loss rates. Lifshitz theory calculations deliver a significantly stronger scattering potential than that found in experiment and we discuss possible reasons for this. We find that the scattering potential for dielectric tubes can be calculated to a good approximation using a modified pairwise summation approach, which is efficient and easily extendable to arbitrary geometries. Quantum reflection of atoms from a nanotube may become a significant factor at low temperatures, especially for non-metallic tubes. Interatomic interactions are shown to increase the rate at which atoms are lost to the nanotube and lead to non-trivial dynamics. Thermal nanotube vibrations do not significantly increase loss rates or reduce condensate fractions, but lower frequency oscillations can dramatically heat the cloud.Comment: 7 pages, 4 figure

Detecting periodicity in experimental data using linear modeling techniques

Fourier spectral estimates and, to a lesser extent, the autocorrelation function are the primary tools to detect periodicities in experimental data in the physical and biological sciences. We propose a new method which is more reliable than traditional techniques, and is able to make clear identification of periodic behavior when traditional techniques do not. This technique is based on an information theoretic reduction of linear (autoregressive) models so that only the essential features of an autoregressive model are retained. These models we call reduced autoregressive models (RARM). The essential features of reduced autoregressive models include any periodicity present in the data. We provide theoretical and numerical evidence from both experimental and artificial data, to demonstrate that this technique will reliably detect periodicities if and only if they are present in the data. There are strong information theoretic arguments to support the statement that RARM detects periodicities if they are present. Surrogate data techniques are used to ensure the converse. Furthermore, our calculations demonstrate that RARM is more robust, more accurate, and more sensitive, than traditional spectral techniques.Comment: 10 pages (revtex) and 6 figures. To appear in Phys Rev E. Modified styl

Comparative power demand of mechanical and aeration imposed shear in an immersed membrane bioreactor

The power demanded for the application of mechanically-imposed shear on an immersed flat sheet (iFS) membrane bioreactor (MBR) has been compared to that of conventional membrane air scouring. Literature correlations based on the Ostwald model were used to define the rheological characteristics of an MBR sludge. The correlation of specific power demand (, in Watts per m2 membrane area) with shear rate γ in s-1 was developed from first principles through a consideration of the force balance on the system in the case of mechanically-imposed shear. The corresponding aeration imposed shear correlation was interpreted from literature information. The analysis revealed the energy required to impose a shear mechanically through oscillation (or reciprocation) of the membrane to be between 20 and 70% less than that demanded for providing the same shear by conventional aeration of the immersed membrane. The energy saving increases with decreasing shear in accordance with a power demand ratio (aeration:mechanical) of 1400γ-1.4 for a specific sludge rheology. Whilst the absolute value is dependent on the sludge rheology, the aeration:mechanical power demand ratio is determined by the difference in the two exponents in the respective correlations between and γ. Consequently, aeration-imparted shear becomes energetically favoured beyond some threshold shear rate value (∼180 s-1, based on the boundary conditions applied in the current study). The outcomes qualitatively corroborate findings from the limited practical measurement of energy demand in MBRs fitted with reciprocating immersed membranes

Dynamical modeling of collective behavior from pigeon flight data: flock cohesion and dispersion

Several models of flocking have been promoted based on simulations with qualitatively naturalistic behavior. In this paper we provide the first direct application of computational modeling methods to infer flocking behavior from experimental field data. We show that this approach is able to infer general rules for interaction, or lack of interaction, among members of a flock or, more generally, any community. Using experimental field measurements of homing pigeons in flight we demonstrate the existence of a basic distance dependent attraction/repulsion relationship and show that this rule is sufficient to explain collective behavior observed in nature. Positional data of individuals over time are used as input data to a computational algorithm capable of building complex nonlinear functions that can represent the system behavior. Topological nearest neighbor interactions are considered to characterize the components within this model. The efficacy of this method is demonstrated with simulated noisy data generated from the classical (two dimensional) Vicsek model. When applied to experimental data from homing pigeon flights we show that the more complex three dimensional models are capable of predicting and simulating trajectories, as well as exhibiting realistic collective dynamics. The simulations of the reconstructed models are used to extract properties of the collective behavior in pigeons, and how it is affected by changing the initial conditions of the system. Our results demonstrate that this approach may be applied to construct models capable of simulating trajectories and collective dynamics using experimental field measurements of herd movement. From these models, the behavior of the individual agents (animals) may be inferred

Low-energy excitations of a linearly Jahn-Teller coupled orbital quintet

The low-energy spectra of the single-mode h x (G+H) linear Jahn-Teller model is studied by means of exact diagonalization. Both eigenenergies and photoemission spectral intensities are computed. These spectra are useful to understand the vibronic dynamics of icosahedral clusters with partly filled orbital quintet molecular shells, for example C60 positive ions.Comment: 14 pages revte

An efficient approach for spin-angular integrations in atomic structure calculations

A general method is described for finding algebraic expressions for matrix elements of any one- and two-particle operator for an arbitrary number of subshells in an atomic configuration, requiring neither coefficients of fractional parentage nor unit tensors. It is based on the combination of second quantization in the coupled tensorial form, angular momentum theory in three spaces (orbital, spin and quasispin), and a generalized graphical technique. The latter allows us to calculate graphically the irreducible tensorial products of the second quantization operators and their commutators, and to formulate additional rules for operations with diagrams. The additional rules allow us to find graphically the normal form of the complicated tensorial products of the operators. All matrix elements (diagonal and non-diagonal with respect to configurations) differ only by the values of the projections of the quasispin momenta of separate shells and are expressed in terms of completely reduced matrix elements (in all three spaces) of the second quantization operators. As a result, it allows us to use standard quantities uniformly for both diagona and off-diagonal matrix elements

Sum Rules for Multi-Photon Spectroscopy of Ions in Finite Symmetry

Models describing one- and two-photon transitions for ions in crystalline environments are unified and extended to the case of parity-allowed and parity- forbidden p-photon transitions. The number of independent parameters for characterizing the polarization dependence is shown to depend on an ensemble of properties and rules which combine symmetry considerations and physical models.Comment: 16 pages, Tex fil

Clogging vs. fouling in immersed membrane bioreactors

Whilst the fouling of MBR membrane surfaces has been very extensively explored by the academic community, there is an increasingly widespread recognition by practitioners of the issue of clogging of membrane channels with sludge solids, sometimes termed “sludging”. The study undertaken has quantified this phenomenon using a bespoke test cell allowing a flat sheet membrane channel to be viewed directly during operation and the accumulated solids determined by digital image processing. Sludging behaviour has then been correlated both with the sludge properties, from sludge samples taken from both an industrial and municipal MBR, and the permeability decline rate data. The work has revealed the expected trends in fouling propensity, as quantified by the exponent n of the Δp/Δt = m.exp(nJ) correlation from classical flux-step tests. With zero membrane aeration the industrial samples exhibited sludging, the filling of the complete thickness of the membrane channel with sludge solids, whereas for municipal sludge the solids formed a cake layer which did not fill the channel. In the absence of sludging the permeability decline followed the expected pattern of increasing at the elevated soluble COD and capillary suction time values of the industrial sludge, compared with municipal sludge at the same solids concentration range (8–12 g.L−1). However, there was no evident correlation between fouling (permeability decline without sludging) and sludging: incipient sludging did not appear to influence permeability, though can be assumed to negatively impact on long-term operation, or relate to the sCOD concentration. Sludging instead appeared to depend on the sludge physical properties, and primarily the viscosity: sludge samples at high viscosities were found to exhibit a different air-scour pattern to that at normal MLSS concentrations. Outcomes suggest that sludging is caused by rheological conditions promoting bubble coalescence and bubble stream constriction, reducing the exposure of the membrane surface to scouring air