Trivalent scandium, yttrium and lanthanide complexes with thia-oxa and selena-oxa macrocycles and crown ether coordination

Complexes of the oxa-thia macrocycles [18]aneO4S2, [15]aneO3S2 and the oxa-selena macrocycle [18]aneO4Se2 (L) of types [MCl2(L)]FeCl4 (M = Sc or Y) were prepared from [ScCl3(thf)3] or [YCl2(THF)5][YCl4(THF)2] and the ligand in anhydrous MeCN, using FeCl3 as a chloride abstractor. The [MI2(L)]I, [LaI3(L)] and [LuI2(L)]I have been prepared from the ligands and the appropriate anhydrous metal triiodide in MeCN. Complexes of type [LaI3(crown)] and [LuI2(crown)]I (crown = 18-crown-6, 15-crown-5) were made for comparison. Use of the metal iodide results in complexes with high solubility compared to the corresponding chlorides, although also with increased sensitivity to moisture. All complexes were characterised by microanalysis, IR, (1)H, (45)Sc and (77)Se NMR spectroscopy as appropriate. X-ray crystal structures are reported for [ScCl2([18]aneO4S2)][FeCl4], [ScI2([18]aneO4S2)]I, [YCl2(18-crown-6)]3[Y2Cl9], [YCl2([18]aneO4S2)][FeCl4], [LaI3(15-crown-5)], [LaI2(18-crown-6)(MeCN)]I, [LuI(18-crown-6)(MeCN)2]I2, [Lu(15-crown-5)(MeCN)2(OH2)]I3, [LaI3([18]aneO4S2)], [LaI([18]aneO4S2)(OH2)]I2, [LaI3([18]aneO4Se2)] and [LuI2([18]aneO4Se2)]I. In each complex all the neutral donor atoms of the macrocycles are coordinated to the metal centre, showing very rare examples of these oxophilic metal centres coordinated to thioether groups, and the first examples of coordinated selenoether donors. In some cases MeCN or adventitious water displaces halide ligands, but not the S/Se donors from La or Lu complexes. A complex of the oxa-tellura macrocycle [18]aneO4Te2, [ScCl2([18]aneO4Te2)][FeCl4] was isolated, but is unstable in MeCN solution, depositing elemental Te. YCl3 and 18-crown-6 produced [YCl2(18-crown-6)]3[Y2Cl9], the asymmetric unit of which contains two cations with a trans-YCl2 arrangement and a third with a cis-YCl2 group

Design of a microwave radiometer for monitoring high voltage insulator contamination level

Microwave radiometry is a novel method for monitoring contamination levels on high voltage insulators. The microwave radiometer described measures energy emitted from the contamination layer and could provide a safe, reliable, contactless monitoring method that is effective under dry conditions. The design of the system has focused on optimizing accuracy, stability and sensitivity using a relatively low cost architecture. Experimental results demonstrate that the output from the radiometer is able to clearly distinguish between samples with different contamination levels under dry conditions. This contamination monitoring method could potentially provide advance warning of the future failure of wet insulators in climates where insulators can experience dry conditions for extended periods

The influence of alcohol content variation in UK packaged beers on the uncertainty of calculations using the Widmark equation

It is common for forensic practitioners to calculate an individual's likely blood alcohol concentration following the consumption of alcoholic beverage(s) for legal purposes, such as in driving under the influence (DUI) cases. It is important in these cases to be able to give the uncertainty of measurement on any calculated result, for this reason uncertainty data for the variables used for any calculation are required. In order to determine the uncertainty associated with the alcohol concentration of beer in the UK the alcohol concentration (%v/v) of 218 packaged beers (112 with an alcohol concentration of ≤5.5%v/v and 106 with an alcohol concentration of >5.5%v/v) were tested using an industry standard near infra-red (NIR) analyser. The range of labelled beer alcohol by volume (ABV's) tested was 3.4%v/v – 14%v/v. The beers were obtained from a range of outlets throughout the UK over a period of 12 months. The root mean square error (RMSE) was found to be ±0.43%v/v (beers with declared %ABV of ≤5.5%v/v) and ±0.53%v/v (beers with declared %ABV of >5.5%v/v) the RMSE for all beers was ±0.48%v/v. The standard deviation from the declared %ABV is larger than those previously utilised for uncertainty calculations and illustrates the importance of appropriate experimental data for use in the determination of uncertainty in forensic calculations

Neutral thioether and selenoether macrocyclic coordination to Group 1 cations (Li–Cs) – synthesis, spectroscopic and structural properties

The complexes [M(L)][BArF] (BArF = tetrakis{3,5-bis(trifluoromethyl)-phenyl}borate), L = [18]aneO4S2 (1,4,10,13-tetraoxa-7,16-dithiacyclooctadecane): M = Li–Cs; L = [18]aneO2S4 (1,10-dioxa-4,7,13,16-tetrathiacyclooctadecane): M = Li, Na, K; L = [18]aneO4Se2 (1,4,10,13-tetraoxa-7,16-diselenacyclooctadecane): M = Na, K, as well as [Na(18-crown-6)][BArF], are obtained in good yield as crystalline solids by reaction of M[BArF] with the appropriate macrocycle in dry CH2Cl2. X-ray crystallographic analyses of [Li([18]aneO4S2)][BArF] and [Li([18]aneO2S4)][BArF] show discrete distorted octahedral cations with hexadentate coordination to the macrocycle. The heavier alkali metal complexes all contain hexadentate coordination of the heterocrown, supplemented by M?F interactions via the anions, producing extended structures with higher coordination numbers; Na: CN = 7 or 8; K: CN = 8; Rb: CN = 9; Cs: CN = 8 or 10. Notably, all of the structures exhibit significant M–S/Se coordination. The crystal structures of the potassium and rubidium complexes show two distinct [M(heterocrown)]+ cations, one with M?F interactions to two mutually cis [BArF]? anions, and the other with mutually trans [BArF]? anions, giving 1D chain polymers. Solution multinuclear (1H, 13C, 7Li, 23Na, 133Cs) NMR data show that the macrocyclic coordination is retained in CH2Cl2 solution

Rough set theory applied to pattern recognition of partial discharge in noise affected cable data

This paper presents an effective, Rough Set (RS) based, pattern recognition method for rejecting interference signals and recognising Partial Discharge (PD) signals from different sources. Firstly, RS theory is presented in terms of Information System, Lower and Upper Approximation, Signal Discretisation, Attribute Reduction and a flowchart of the RS based pattern recognition method. Secondly, PD testing of five types of artificial defect in ethylene-propylene rubber (EPR) cable is carried out and data pre-processing and feature extraction are employed to separate PD and interference signals. Thirdly, the RS based PD signal recognition method is applied to 4000 samples and is proven to have 99% accuracy. Fourthly, the RS based PD recognition method is applied to signals from five different sources and an accuracy of more than 93% is attained when a combination of signal discretisation and attribute reduction methods are applied. Finally, Back-propagation Neural Network (BPNN) and Support Vector Machine (SVM) methods are studied and compared with the developed method. The proposed RS method is proven to have higher accuracy than SVM and BPNN and can be applied for on-line PD monitoring of cable systems after training with valid sample data

Decadal fluctuations in North Atlantic water inflow in the North Sea between 1958-2003: impacts on temperature and phytoplankton populations

The circulation of Atlantic water along the European continental slope, in particular the inflow into the North Sea, influences North Sea water characteristics with consequent changes in the environment affecting plankton community dynamics. The long-term effect of fluctuating oceanographic conditions on the North Sea pelagic ecosystem is assessed. It is shown that (i) there are similar regime shifts in the inflow through the northern North Sea and in Sea Surface Temperature, (ii) long-term phytoplankton trends are influenced by the inflow only in some North Sea regions, and (iii) the spatial variability in chemicophysical and biological parameters highlight the influence of smaller scale processes

Radio Planetary Nebulae in the Magellanic Clouds

We present preliminary results of our deep Australia Telescope Compact Array (ATCA) radio-continuum survey of the Magellanic Clouds Planetary Nebulae.Comment: 2 pages 1 figure, to appear in Planetary Nebulae an Eye to the Future Proceedings IAU Symposium No. 28

The relationship between the location of western mackerel spawning, larval drift and recruit distributions: A modelling study

Summary: Mackerel spawning distributions have changed over the last 20 years. From 1977-1995 there has been a progressive westerly shift in the distribution of spawning in May/June (peak spawning), with a resultant increase in the proportion of spawning west of the shelf break. Also during this time period there has been a marked increase in the proportion of spawning in the north of the spawning area. This shift occurred most obviously between the surveys carried out in 1986 and 1989. At the same time it is shown that there has been a northerly shift in the distribution of first winter juveniles. These observations are derived from data collected on the ICES coordinated winter bottom trawl surveys. This study used data on mackerel egg distributions during May, derived from the ICES triennial mackerel egg surveys as input to the NORWECOM transport model, using real weather fields. The outputs from the model indicated that most eggs and larvae could expect to be transported south after spawning and that there had been no significant change in this transport pattern during the period studied. The combination of more northerly spawning and the prevailing transport pattern may explain, in part, the increase in the recruit population in the northern nursery areas. It is concluded that passive transport can explain the juvenile distribution in some areas, but that active migration must also play a role in the area of the Celtic Sea. The interactions between the modelled transport patterns and the real egg distribution data are discussed with reference to these topics and to the potential survival of larvae in the first weeks after hatching

Anomalous Chromomagnetic Moments of Quarks and Large Transverse Energy Jets

We consider the jet cross sections for gluons coupling to quarks with an anomalous chromomagnetic moment. We then apply this to the deviation and bounds from QCD found in the CDF and D0 Fermilab data, respectively, to find a range of possible values for the anomalous moments. The quadratic and quartic terms in the anomalous moments can fit to the rise of a deviation with transverse energy. Since previous analyses have been done on the top quark total cross section, here we assume the same moment on all quarks except the top and find the range $|\kappa'| \equiv |\kappa/(2 m_q)| = 1.0\pm 0.3$ TeV$^{-1}$ for the CDF data. Assuming the anomalous moment is present only on a charm or bottom quark which is pair produced results in a range $|\kappa'_{b,c}| = 3.5 \pm 1.0$ TeV$^{-1}$. The magnitudes here are compared with anomalous magnetic moments that could account for $R_b$ and found to be in the same general range, as well as not inconsistent with LEP and SLD bounds on $\Delta \Gamma_{\text{had}}$.Comment: REVTeX, 11 pages, 2 postscript figure