1-Naphthyl- and mesityltellurium(IV,II) derivatives of small bite chelating organic ligands: effect of steric bulk and intramolecular secondary bonding interaction on molecular geometry and supramolecular association

The synthesis and characterization of unsymmetric diorganotellurium compounds containing a sterically demanding I-naphthyl or
mesitylligand and a small bite chelating organic ligand capable of 1,4-Te···N(O) intramolecular interaction is described. The reaction
of ArTeCl₃ (Ar = I-C_lOH₇, Np; 2,4,6-Me₃C₆H_2' Mes) with (SB)HgCI [SB = the Schiff base, 2-(4,4'-N0₂C₆H₄CH=NC₆H₃-Me)] or a methyl ketone (RCOCH₃) afforded the corresponding dichlorides (SB)ArTeCI₂ (Ar = Np, 1Aa; Mes, 1Ba) or (RCOCH₂)ArTeCl₂ (Ar = Np; R = Ph (2Aa), Me (3Aa), Np (4Aa); Ar = Mes, R = Ph (2Ba)). Reduction of 1Aa and 1Ba by Na₂S₂0₅ readily gave the tellurides (SB)ArTe (Ar = Np (1A), Mes, (1B) but that of dichlorides derived from methylketones was complicated due to partial decomposition to tellurium powder and diarylditelluride (Ar₂Te₂), resulting in poor yields of the corresponding tellurides 2A, 2B and 3A. Oxidation of the isolated tellurides with S0₂Cl₂, Br₂ and I₂ yielded the corresponding dihalides. All the synthesized compounds have been characterized with the help of IR, ¹H, ^l3C, and ¹²⁵Te NMR and in the case of 2Aa, and 2Ba by X-ray crystallography. Appearance of only one ¹²⁵Te signal indicated that the unsymmetric derivatives were stable to disproportionation to symmetric species. Intramolecular 1,4-Te· . ·0 secondary bonding interactions (SBIs) are exhibited in the crystal structures of both the tellurium(IV) dichlorides, 2Aa, and 2Ba. Steric repulsion of the mesityl group in the latter dominates over lone pair-bond pair repulsion, resulting in significant widening of the equatorial C-Te-C angle. This appears to be responsible for the lack of Te· . ·CI involved supramolecular associations in the crystal structure of 2Ba.

A new perspective of storm bite on sandy beaches using unmanned aerial vehicles

Aerial imagery collected before and after major storm events is ideal for the assessment of coastal landscape change driven by individual high-magnitude events. Using traditional satellite sensors and manned aerial systems can be challenging due to issues related to cloud cover, mobilization expenses and resolution. Rapid advances in unmanned aerial vehicle (UAV) technology allow for the cost-effective collection of aerial imagery and topography at centimetre resolution suitable for assessing change in coastal ecosystems. In this study we demonstrate the utility of UAV-based photogrammetry to quantify storm-driven sediment dynamics on a sandy beach on the open-coast shoreline of Victoria, Australia. UAV-based aerial photography was collected before and after a major storm event. High-resolution (< 5 cm) aerial imagery and digital surface models were acquired and change-detection techniques were applied to quantify changes in the beachface. An average beach erosion of 12.24 m3/m with a maximum of 28.05 m3/m was observed, and the volume of sand cut from the beachface and retreat of the foredune are clearly illustrated. Following the storm event, erosion was estimated at 7259.94 ± 503.69 m3 along 550 m of beach. By combining the aerial imagery and derived topographic datasets we demonstrate the advantage of UAV-based photogrammetry techniques for rapid high-resolution data collection in semi-remote locations. Its utility in setting unlimited virtual vantage points is also illustrated and the valuable perspective it provides for tracking landscape change discussed.

Mediatizing educational policy : the journalistic field, science policy, and cross-field effects

This paper is concerned to demonstrate the usefulness of the theory of Bourdieu, including the concepts of field, logics of practice and habitus, to understanding relationships between media and policy, what Fairclough has called the 'mediatization' of policy. Specifically, the paper draws upon Bourdieu's accessible account of the journalistic field as outlined in On television and journalism. The usefulness of this work is illustrated through a case study of a recent Australian science policy, The chance to change. As this policy went through various iterations and media representations, its naming and structure became more aphoristic. This is the mediatization of contemporary policy, which often results in policy as sound bite. The case study also shows the cross-field effects of this policy in education, illustrating how today educational policy can be spawned from developments in other public policy fields.

Longer guts and higher food quality increase energy intake in migratory swans

1.  Within the broad field of optimal foraging, it is increasingly acknowledged that animals often face digestive constraints rather than constraints on rates of food collection. This therefore calls for a formalization of how animals could optimize food absorption rates.

2.  Here we generate predictions from a simple graphical optimal digestion model for foragers that aim to maximize their (true) metabolizable food intake over total time (i.e. including nonforaging bouts) under a digestive constraint.

3.  The model predicts that such foragers should maintain a constant food retention time, even if gut length or food quality changes. For phenotypically flexible foragers, which are able to change the size of their digestive machinery, this means that an increase in gut length should go hand in hand with an increase in gross intake rate. It also means that better quality food should be digested more efficiently.

4.  These latter two predictions are tested in a large avian long-distance migrant, the Bewick's swan (Cygnus columbianus bewickii), feeding on grasslands in its Dutch wintering quarters.

5.  Throughout winter, free-ranging Bewick's swans, growing a longer gut and experiencing improved food quality, increased their gross intake rate (i.e. bite rate) and showed a higher digestive efficiency. These responses were in accordance with the model and suggest maintenance of a constant food retention time.

6.  These changes doubled the birds’ absorption rate. Had only food quality changed (and not gut length), then absorption rate would have increased by only 67%; absorption rate would have increased by only 17% had only gut length changed (and not food quality).

7.  The prediction that gross intake rate should go up with gut length parallels the mechanism included in some proximate models of foraging that feeding motivation scales inversely to gut fullness. We plea for a tighter integration between ultimate and proximate foraging models.

Synthesis, X-ray structure and electrochemical characterization of palladium(II) bearing ferrocenyldiphenylphosphine complexes

Four new complexes, [PdX(κ2-2-C6R4PPh2)(PPh2Fc)] [X = Br, R = H (1), R = F (2); X = I, R = H (3), R = F (4)], containing ferrocenyldiphenylphosphine (PPh2Fc) have been prepared and fully characterised. The X-ray structures of complexes trans-1, cis-2 and cis-4, and that of a decomposition product of 4, [Pd(κ2-2-C6F4PPh2)(μ-I)(μ-2-C6F4PPh2)PdI(PPh2Fc)] (5), have been determined. These complexes show a distorted square planar geometry about the metal atom, the bite angles of the chelate ligands being about 69°, as expected. The cis/trans ratio of 1–4 in solution is strongly dependent on solvent. The new complexes and the uncoordinated PPh2Fc ligand were electrochemically characterised by cyclic and rotating disk voltammetry, UV-visible spectroelectrochemistry, and bulk electrolysis in dichloromethane and acetonitrile. In both cases, oxidation occurs at both the ferrocene and phosphine centres, but the complexes oxidise at more positive potentials than uncoordinated PPh2Fc; subsequently, the metal–phosphorus bond is cleaved, leading to free PPh2Fc+, which undergoes further chemical and electrochemical reactions.

Cafe urgency

The idea of Cafe urgency was to create a loose and social atmosphere in which performers, audience and everyone present explored the ideas of the evening together. What Urgency do we have in our lives? Which pressing ideas, compelling needs, burning desires fill a day? Which insistent thoughts, driving wishes, forceful longings span a lifetime? Our delectable menu of musings, meditations and magnificent imaginations will provide bite-sized morsels and overlapping slabs of creative sustenance to suit all tastes: song, sound, spoken word, dance, music, live art, installation.

Incorporating domain knowledge with video and voice data analysis in news broadcasts

This paper addresses the area of video annotation, indexing and retrieval, and shows how a set of tools can be employed, along with domain knowledge, to detect narrative structure in broadcast news. The initial structure is detected using low-level audio visual processing in conjunction with domain knowledge. Higher level processing may then utilize the initial structure detected to direct processing to improve and extend the initial classification.

The structure detected breaks a news broadcast into segments, each of which contains a single topic of discussion. Further the segments are labeled as a) anchor person or reporter, b) footage with a voice over or c) sound bite. This labeling may be used to provide a summary, for example by presenting a thumbnail for each reporter present in a section of the video. The inclusion of domain knowledge in computation allows more directed application of high level processing, giving much greater efficiency of effort expended. This allows valid deductions to be made about structure and semantics of the contents of a news video stream, as demonstrated by our experiments on CNN news broadcasts.

Sex, androgens, and whole-organism performance in an Australian lizard

Understanding underlying physiological differences between the sexes in circulating androgens and how hormonal variation affects morphology-performance relationships may help clarify the evolution of sexual dimorphism in diverse taxa. Using a widely distributed Australian lizard (Eulamprus quoyii) with weak sexual dimorphism and no dichromatism, we tested whether circulating androgens differed between the sexes and whether they covaried with morphological and performance traits (bite force, sprint speed, endurance). Males had larger head dimensions, stronger bite force, faster sprint speed, and longer endurance compared to females. We found that the sexes did not differ in androgen concentrations and that androgens were weakly associated with both morphological and performance traits. Interestingly, high circulating androgens showed a nonlinear relationship with bite force in males and not females, with this relationship possibly being related to alternative male reproductive tactics. Our results suggest that androgens are not strongly correlated with most performance and morphological traits, although they may play an important organizational role during the development of morphological traits, which could explain the differences in morphology and thus performance between the sexes. Differences in performance between the sexes suggest differential selection on these functional traits between males and females. © 2014 The Linnean Society of London.

Assessment of eating rate and food intake in spoon versus fork users in a laboratory setting

Accumulating evidence show positive relationships between eating rate and body weight. Acute food intake is affected by eating rate, bite size, and palatability. The objective was to assess differences between participants who chose to use a spoon vs. fork in eating rate and food intake of four meals that differ in palatability (low vs. high salt) and in energy density (low vs. high fat). Forty-eight healthy adults (16 males, 18-54 y, BMI: 17.8-34.4 kg/m2) were recruited. Participants attended four lunch time sessions after a standardised breakfast. Meals were either (1) low-fat/low-salt, (2) low-fat/high-salt, (3) high-fat/low-salt, or (4) high-fat/high-salt. Nineteen participants (6 males) consistently used a fork and 21 (8 males) used a spoon, 8 participants were inconsistent in cutlery use and excluded from analyses. Spoon users had on average a higher BMI than fork users (p=0.006). Effects of cutlery use, BMI status (BMI<25 vs. BMI>25), salt, and fat, and their interactions were assessed in a General Linear Model. Spoon users consumed faster (fork: 53±2.8g/min; spoon: 62±2.1g/min, p=0.022) and tended to consume more (p=0.09), whereas the duration of the meals were similar (fork: 6.9±0.3min; spoon: 6:7±0.2min, p=0.55). BMI status affected both eating rate and food intake (p=0.005). There were no significant two-way or three-way interactions between salt, fat, and cutlery use on eating rate or food intake. In conclusion, participants who chose to consume with forks ate slower compared to spoon users.