Determination of the stability constants of mercury(II) complexes of mixed donor macrobicyclic encapsulating ligands

The reactions of mercury(II) with the mixed donor encapsulating ligands 3,6,16-trithia-6,11,19-triazabicyclo[6.6.6]icosane (AMN(3)S(3)sar) and 1-amino-8-methyl-6,19-dithia-3,10,13,16-tetraazabicyclo[6.6.6]icosane (AMN(4)S(2)sar) have been studied. NMR ligand-ligand competition experiments with the ligands 1,4,8,11-tetraazaeyclotetradecane ([14]aneN(4)), 1-thia-4,7,10-triazacyclododecane ([12]aneN(3)S) and ethylenediaminetetraacetic acid (EDTA) with AMN(3)S(3)sar and Hg(II) indicated that [14]aneN(4) would be an appropriate competing ligand for the, determination of the Hg(II) stability constant. Calculations indicated the ratio of concentrations of AMN3S3sar, [14]aneN(4) and Hg(II) required for the determination of the stability constant ranged from 1:1:1 to 1:5:1. Refinement of the titration curves yielded log(10)K[Hg(AMN(3)S(3)sar)](2+) = 17.7. A similar competition titration resulted in the determination of the stability constant for the AMN(4)S(2)sar system as log(10)K[Hg(AMN(4)S(2)sar)](2+) = 19.5. The observed binding constants for the mixed N/S donor systems and the hexaaza analogues sar (3,6,10,13,16,19-hexaazabicyclo [6.6.6]icosane) and diamsar (1,8-diamino-3,6,10,13,16,19 -hexazabicyclo [6.6.6] icosane (log(10)K-[Hg(diamsar)](2+) = 26.4; log(10)K[Hg(sar)](2+) = 28.1) differ by approximately ten orders of magnitude. The difference is ascribed not to a cryptate effect but to a mismatch in the Hg-N and Hg-S bond lengths in the N/S systems.

Using the 6dF galaxy redshift survey to detect gravitationally-lensed quasars

It is possible to detect gravitationally-lensed quasars spectroscopically if the spectra obtained during galaxy surveys are searched for the presence of quasar emission lines. The up-coming 6 degree Field (6dF) redshift survey on the United Kingdom Schmidt Telescope will involve obtaining similar to 10(5) spectra of near-infrared selected galaxies to a magnitude limit of K = 13. Applying previously developed techniques implies that at least one lens should be discovered in the 6dF survey, but that as many as ten could be found if quasars typically have B-J - K similar or equal to 8. In this model there could be up to fifty lensed quasars in the, sample, but most of them could only be detected by infrared spectroscopy.

Cyclic octapeptides containing thiazole. Effect of stereochemistry and degree of flexibility on calcium binding properties

Solution conformation and calcium binding properties have been investigated for the two cyclic octapeptides cyclo(-D-Thr-D-Val(Thz)-Ile-)(2) (4) and cyclo(-Thr-Gly(Thz)-Ile-Ser-Gly(Thz)-Ile-)(5) and the results are compared to those for the cyclic octapeptides previously studied; ascidiacyclamide (1), patellamide D (2), cyclo(-Thr-D-Val(Thz)-Ile-)(2) (3), and cyclo(-Thr-D-Val-alphaAbu-Ile-)2 (6). Both 4 and 5 contain two heterocyclic thiazole ring constraints but the latter has a larger degree of flexibility as a consequence of the glycine residues within the cyclic framework. The solution conformation of 4 and 5 was determined from H-1 NMR spectra and found to be a twisted figure of eight similar to that for 2. Complexation studies using H-1 NMR and CD spectroscopy yielded 1 : 1 calcium-peptide binding constants (logK) for the two peptides (2.3 (4) and 5.7 (5)). For 5 the magnitude of the binding constant was verified by a competition titration using CD. The different calcium-binding affinities of 3 (logK = 4.0) and 4 is attributed to the stereochemistry of the threonine residue. The magnitude of the binding constant for 5 compared to 3 and 4 (all peptides containing two thiazole ring constrains) demonstrates that the increase in flexibility of the cyclic peptide has a dramatic effect on the Ca2+ binding ability. The affinity for Ca2+ thus decreases in the order (6 similar to 5 > 3 > 2 similar to 1 > 4). The number of carbonyl donors available on each peptide has only a limited effect on calcium binding. The most important factor is the flexibility, which allows for a conformation of the peptide capable of binding calcium efficiently.

The spectra of red quasars

We measure the spectral properties of a representative sub-sample of 187 quasars, drawn from the Parkes Half-Jansky, Flat-radio-spectrum Sample (PHFS). Quasars with a wide range of rest-frame optical/UV continuum slopes are included in the analysis: their colours range over 2 < B-K < 7. We present composite spectra of red and blue sub-samples of the PHFS quasars. and tabulate their emission line properties. The median Hbeta and [0 111] emission line equivalent widths of the red quasar sub-sample are a factor of ten weaker than those of the blue quasar sub-sample. No significant differences are seen between the equivalent width distributions of the C IV, C III] and Mg 11 lines. Both the colours and the emission line equivalent widths of the red quasars can be explained by the addition of a featureless red synchrotron continuum component to an otherwise normal blue quasar spectrum. The red synchrotron component must have a spectrum at least as red as a power-law of the form F-nu proportional to nu(-2.8). The relative strengths of the blue and red components span two orders of magnitude at rest-frame 500 nm. The blue component is weaker relative to the red component in low optical luminosity sources. This suggests that the fraction of accretion energy going into optical emission from the jet is greater in low luminosity quasars. This correlation between colour and luminosity may be of use in cosmological distance scale work. This synchrotron model does not, however, fit similar to10% of the quasars, which have both red colours and high equivalent width emission lines. We hypothesise that these red, strong-lined quasars have intrinsically weak Big Blue Bumps. There is no discontinuity in spectral properties between the BL Lac objects in our sample and the other quasars. BL Lac objects appear to be the red, low equivalent width tail of a continuous distribution. The synchrotron emission component only dominates the spectrum at longer wavelengths, so existing BL Lac surveys will be biased against high redshift objects. This will affect measurements of BL Lac evolution. The blue PHFS quasars have significantly higher equivalent width C IV, Hbeta and [0 111] emission than a matched sample of optically selected QSOs.

The Las Campanas/AAT Rich Cluster Survey - II. The environmental dependence of galaxy colours in clusters at z similar to 0.1

We present a photometric investigation of the variation in galaxy colour with environment in 11 X-ray-luminous clusters at 0.07 less than or equal to z less than or equal to 0.16 taken from the Las Campanas/AAT Rich Cluster Survey. We study the properties of the galaxy populations in individual clusters, and take advantage of the homogeneity of the sample to combine the clusters together to investigate weaker trends in the composite sample. We find that modal colours of galaxies lying on the colour-magnitude relation in the clusters become bluer by d(B - R)/dr(p) = -0.022 +/- 0.004 from the cluster core out to a projected radius of r(p) = 6 Mpc, further out in radius than any previous study. We also examine the variation in modal galaxy colour with local galaxy density, 2, for galaxies lying close to the colour-magnitude relation, and find that the median colour shifts bluewards by d(B - R)/d log(10)(Sigma) = -0.076 +/- 0.009 with decreasing local density across three orders of magnitude. We show that the position of the red envelope of galaxies in the colour-magnitude relation does not vary as a function of projected radius or density within the clusters, suggesting that the change in the modal colour results from an increasing fraction of bluer galaxies within the colour-magnitude relation, rather than a change in the colours of the whole population. We show that this shift in the colour-magnitude relations with projected radius and local density is greater than that expected from the changing morphological mix based on the local morphology-density relation. We therefore conclude that we are seeing a real change in the properties of galaxies on the colour-magnitude relation in the outskirts of clusters. The simplest interpretation of this result (and similar constraints in local clusters) is that an increasing fraction of galaxies in the lower density regions at large radii within clusters exhibit signatures of star formation in the recent past, signatures which are not seen in the evolved galaxies in the highest density regions.

The Fornax Cluster Spectroscopic Survey: a sample of confirmed cluster dwarfs

The Fornax Cluster Spectroscopic Survey (FCSS) project utilizes the Two-degree Field (2dF) multi-object spectrograph on the Anglo-Australian Telescope (AAT). Its aim is to obtain spectra for a complete sample of all 14 000 objects with 16 5 less than or equal to b(j) less than or equal to 19 7 irrespective of their morphology in a 12 deg(2) area centred on the Fornax cluster. A sample of 24 Fornax cluster members has been identified from the first 2dF field (3.1 deg(2) in area) to be completed. This is the first complete sample of cluster objects of known distance with well-defined selection limits. Nineteen of the galaxies (with -15.8 < M-B < 12.7) appear to be conventional dwarf elliptical (dE) or dwarf S0 (dS0) galaxies. The other five objects (with -13.6 < M-B < 11.3) are those galaxies which were described recently by Drinkwater et al. and labelled 'ultracompact dwarfs' (UCDs). A major result is that the conventional dwarfs all have scale sizes alpha greater than or similar to 3 arcsec (similar or equal to300 pc). This apparent minimum scale size implies an equivalent minimum luminosity for a dwarf of a given surface brightness. This produces a limit on their distribution in the magnitude-surface brightness plane, such that we do not observe dEs with high surface brightnesses but faint absolute magnitudes. Above this observed minimum scale size of 3 arcsec, the dEs and dS0s fill the whole area of the magnitude-surface brightness plane sampled by our selection limits. The observed correlation between magnitude and surface brightness noted by several recent studies of brighter galaxies is not seen with our fainter cluster sample. A comparison of our results with the Fornax Cluster Catalog (FCC) of Ferguson illustrates that attempts to determine cluster membership solely on the basis of observed morphology can produce significant errors. The FCC identified 17 of the 24 FCSS sample (i.e. 71 per cent) as being 'cluster' members, in particular missing all five of the UCDs. The FCC also suffers from significant contamination: within the FCSS's field and selection limits, 23 per cent of those objects described as cluster members by the FCC are shown by the FCSS to be background objects.

Analysis of steady-state heat transfer through mid-crustal vertical cracks with upward throughflow in hydrothermal systems

We conduct a theoretical analysis of steady-state heat transfer problems through mid-crustal vertical cracks with upward throughflow in hydrothermal systems. In particular, we derive analytical solutions for both the far field and near field of the system. In order to investigate the contribution of the forced advection to the total temperature of the system, two concepts, namely the critical Peclet number and the critical permeability of the system, have been presented and discussed in this paper. The analytical solution for the far field of the system indicates that if the pore-fluid pressure gradient in the crust is lithostatic, the critical permeability of the system can be used to determine whether or not the contribution of the forced advection to the total temperature of the system is negligible. Otherwise, the critical Peclet number should be used. For a crust of moderate thickness, the critical permeability is of the order of magnitude of 10(-20) m(2), under which heat conduction is the overwhelming mechanism to transfer heat energy, even though the pore-fluid pressure gradient in the crust is lithostatic. Furthermore, the lower bound analytical solution for the near field of the system demonstrates that the permeable vertical cracks in the middle crust can efficiently transfer heat energy from the lower crust to the upper crust of the Earth. Copyright (C) 2002 John Wiley Sons, Ltd.

Ultra-compact dwarf galaxies: a new class of compact stellar system discovered in the Fornax Cluster

We have used the 2dF spectrograph on the Anglo-Australian Telescope to obtain a complete spectroscopic sample of all objects in the magnitude range, 16.5 < bj < 19.8, regardless of morphology, in an area centred on the Fornax Cluster of galaxies. Among the unresolved targets are five objects which are members of the Fornax Cluster. They are extremely compact stellar systems with scale lengths less than 40 parsecs. These ultra-compact dwarfs are unlike any known type of stellar system, being more compact and significantly less luminous than other compact dwarf galaxies, yet much brighter than any globular cluster.

Global trajectories of the long-term decline of coral reef ecosystems

Degradation of coral reef ecosystems began centuries ago, but there is no global summary of the magnitude of change. We compiled records, extending back thousands of years, of the status and trends of seven major guilds of carnivores, herbivores, and architectural species from 14 regions. Large animals declined before small animals and architectural species, and Atlantic reefs declined before reefs in the Red Sea and Australia, but the trajectories of decline were markedly similar worldwide. All reefs were substantially degraded long before outbreaks of coral disease and bleaching. Regardless of these new threats, reefs will not survive without immediate protection from human exploitation over large spatial scales.

Can I have your attention please: Repressors and enhanced P3 to emotional stimuli

In four experiments ERPs to emotional (negative and positive) and neutral stimuli were examined as a function of participants’ trait anxiety and repressivedefensiveness. The experiments investigated the time course of attentional bias in the processing of such stimuli. Pictures of angry, happy, and neutral faces were used in two of the experiments and pictures ofmutilated, happy, and neutral faces were used in the others. ERP’s to emotional and neutral stimuli were recorded from parietal, temporal, and frontal sites. Analysis of the P3 component indicated that the peak magnitude of the P3 at the parietal and temporal sites reflected an interactive function of trait anxiety and defensiveness. Repressors (low reported anxiety, high defensiveness) showed a consistent pattern of greater P3 magnitude at the parietal and temporal sites for emotional faces (angry, happy, and mutilated) than did high-anxious and low-anxious participants. Participants did not differ in P3 magnitude when ERPs to neutral stimuli were investigated (e.g., a fixation cross). The findings indicate that Repressors dedicate greater processing resources to emotional material, as compared to neutral material, than either the high-anxious or low-anxious individuals. Results of the four experiments are discussed within the theoretical framework of Derakshan and Eysenck (1998). The importance of understanding the role of differences in information processing, in the experience and avoidance of emotional information, as a function of trait anxiety and defensiveness is emphasized.

Vitamin D receptor expression in the embryonic rat brain

We are interested in determining whether low maternal vitamin D-3 affects brain development in utero. Whilst the vitamin D receptor (VDR) has been identified in embryonic rat brains, the timing and magnitude of its expression across the brain remains unclear. In this study we have quantitated VDR expression during development as well correlated the timing of its appearance with two vital developmental events, apoptosis and mitosis. Brains from embryonic rats (embryonic days 15-23) were examined. We show that the well-described increase in apoptotic cells and decrease in mitotic cells during development correlates with the appearance of the VDR in brain tissue. Given that vitamin D-3 regulates mitosis and apoptosis in non-neuronal tissue we speculate that the timing of VDR expression in embryonic brain may directly or indirectly mediate features of neuronal apoptosis and mitosis.

Quantum control and quantum entanglement

We discuss quantum error correction for errors that occur at random times as described by, a conditional Poisson process. We shoo, how a class of such errors, detected spontaneous emission, can be corrected by continuous closed loop, feedback.

Patterns of variation within self-incompatibility loci

Diverse self-incompatibility (SI) mechanisms permit flowering plants to inhibit fertilization by pollen that express specificities in common with the pistil. Characteristic of at least two model systems is greatly reduced recombination across large genomic tracts surrounding the S-locus, which regulates SI. In three angiosperm families, including the Solanaceae, the gene that controls the expression of gametophytic SI in the pistil encodes a ribonuclease (S-RNase). The gene that controls pollen SI expression is currently unknown, although several candidates have recently been proposed. Although each candidate shows a high level of polymorphism and complete allelic disequilibrium with the S-RNase gene, such properties may merely reflect tight linkage to the S-locus, irrespective of any functional role in SI. We analyzed the magnitude and nature of nucleotide variation, with the objective of distinguishing likely candidates for regulators of SI from other genes embedded in the S-locus region. We studied the S-RNase gene of the Solanaceae and 48A, a candidate for the pollen gene in this system, and we also conducted a parallel analysis of the regulators of sporophytic SI in Brassica, a system in which both the pistil and pollen genes are known. Although the pattern of variation shown by the pollen gene of the Brassica system is consistent with its role as a determinant of pollen specificity, that of 48A departs from expectation. Our analysis further suggests that recombination between 48A and S-RNase may have occurred during the interval spanned by the gene genealogy, another indication that 48A may not regulate SI expression in pollen.

The effect of nutrient enrichment on growth, photosynthesis and hydraulic conductance of dwarf mangroves in Panama

1. Dwarf stands of the mangrove Rhizophora mangle L. are extensive in the Caribbean. We fertilized dwarf trees in Almirante Bay, Bocas del Toro Province, north-eastern Panama with nitrogen (N) and phosphorus (P) to determine (1) if growth limitations are due to nutrient deficiency; and (2) what morphological and/or physiological factors underlie nutrient limitations to growth. 2. Shoot growth was 10-fold when fertilized with P and twofold with N fertilization, indicating that stunted growth of these mangroves is partially due to nutrient deficiency. 3. Growth enhancements caused by N or P enrichment could not be attributed to increases in photosynthesis on a leaf area basis, although photosynthetic nutrient-use efficiency was improved. The most dramatic effect was on stem hydraulic conductance, which was increased sixfold by P and 2.5-fold with N enrichment. Fertilization with P enhanced leaf and stem P concentrations and reduced C : N ratio, but did not alter leaf damage by herbivores. 4. Our findings indicate that addition of N and P significantly alter tree growth and internal nutrient dynamics of mangroves at Bocas del Toro, but also that the magnitude, pattern and mechanisms of change will be differentially affected by each nutrient.

Attenuation of perceptual asymmetries in patients with early-onset schizophrenia: Evidence in favour of reduced hemispheric differentiation in schizophrenia?

Lateral biases in visual perception have been demonstrated in normal individuals and in patients with unilateral brain lesions. It has been suggested that the absence of structural and functional asymmetries in schizophrenia could be due to a failure in lateralisation that may be most pronounced in those patients whose illness onset is at an early age. Here we examined lateral biases in patients with schizophrenia of an early onset (N = 21) and a late onset.(N = 19), and their respective age-matched control groups, using the greyscales task, a sensitive measure of asymmetries in visual processing. The stimuli consisted of two rectangles, one above the other, shaded in opposite directions and matched overall for darkness. Participants judged which of the two rectangles looked darker overall. Previous studies using this task in healthy participants have reported a reliable bias, such that the rectangle with the darker end on the left is selected preferentially. Whereas the late-onset patients in this study exhibited a perceptual bias of similar direction and magnitude to that of controls, this was not the case for the early-onset patients, who exhibited significantly less bias than their control group. The reduced perceptual bias seen in the early-onset group, but not the late-onset group, suggests an attenuation of right hemisphere mechanisms dedicated to processing vistiospatial information. The attenuated perceptual asymmetry in the early-onset group only may be consistent with the view that (i) an earlier illness onset reflects a greater loss of hemispheric differentiation and (ii) reduced functional asymmetries in the early-onset group are a manifestation of a failure to allocate functions to one or the other hemisphere.