Reviews

John Bowden and Ference Marton, The University of Learning: Beyond Quality and Competence in Higher Education, London: Kogan Page, 1998. ISBN: 0–7494–2292–0. Hardback, x310 pages, £35.00

A spectroscope study of some semiquinone radical ions

The effect of substituents on the value of the oxidation potential of quinones is reviewed and attempts to prepare substituted diphenoquinones with high oxidation potentials are reported. Attempts to characterise the mechanism of addition and substitution in diphenoquinones by identifying the products of the Thiele acetylation of diphenoquinone are reported. The reaction proved most efficient when the incoming acetylinium ion is directed by substituents in the diphenoquinone. A 1,8-addition to diphenoquinone is reported and characterised by isolating the products of the reaction between acetyl chloride and diphenoquinone, with perchloric acid as catalyst. The alternating linewidth effects observed in e.s.r.spectra are discussed and applied to account for such effects observed in the e.s.r.spectra of diphenosemiquinone anion and cation radicals. The spectra are analysed and the intramolecular processes producing these effects are discussed. A dianion diradical where intramolecular rotation about the 1 - 1' bond is restricted is produced by the oxidation of 2,2' ,4,4' -tetra hydroxybiphenyl. Previous studies of diphenosemiquinone anions are reviewed and alkylated diphenosemiquinone anion are produced by the reduction of the parent quinone with potassium hydroxide solution, the resulting radical being stabilised by the presence of pyridine. A qualitative interpretation of the solvent-ion effect in alkylated diphenosemiquinone anions is given. Diphanosemiquinone cation radicals are reviewed and previous studies are re-examined

New broad 8Be nuclear resonances

Energies, total and partial widths, and reduced width amplitudes of 8Be resonances up to an excitation energy of 26 MeV are extracted from a coupled channel analysis of experimental data. The presence of an extremely broad J^pi = 2^+ ``intruder'' resonance is confirmed, while a new 1^+ and very broad 4^+ resonance are discovered. A previously known 22 MeV 2^+ resonance is likely resolved into two resonances. The experimental J^pi T = 3^(+)? resonance at 22 MeV is determined to be 3^-0, and the experimental 1^-? (at 19 MeV) and 4^-? resonances to be isospin 0.Comment: 16 pages, LaTe

Drip water electrical conductivity as an indicator of cave ventilation at the event scale

The use of speleothems to reconstruct past climatic and environmental change through chemical proxies is becoming increasingly common. Speleothem chemistry is controlled by hydrological and atmospheric processes which vary over seasonal time scales. However, as many reconstructions using speleothem carbonate are now endeavouring to acquire information about precipitation and temperature dynamics at a scale that can capture short term hydrological events, our understanding of within cave processes must match this resolution. Monitoring within Cueva de Asiul (N. Spain) has identified rapid (hourly resolution) changes in drip water electrical conductivity (EC), which is regulated by the pCO2 in the cave air. Drip water EC is therefore controlled by different modes of cave ventilation. In Cueva de Asiul a combination of density differences, and external pressure changes control ventilation patterns. Density driven changes in cave ventilation occur on a diurnal scale at this site irrespective of season, driven by fluctuations in external temperature across the cave internal temperature threshold. As external temperatures drop below those within the cave low pCO2 external air enters the void, facilitating the deposition of speleothem carbonate and causing a reduction in measured drip water EC. Additionally, decreases in external pressure related to storm activity act as a secondary ventilation mechanism. Reductions in external air pressure cause a drop in cave air pressure, enhancing karst air draw down, increasing the pCO2 of the cave and therefore the EC measured within drip waters. EC thereby serves as a first order indicator of cave ventilation, regardless of changes in speleothem drip rates and karst hydrological conditions. High resolution monitoring of cave drip water electrical conductivity reveals the highly sensitive nature of ventilation dynamics within cave environments, and highlights the importance of this for understanding trace element incorporation into speleothem carbonate at the event scale

Experimental evidence for competitive N-O and O-C bond homolysis in gas-phase alkoxyamines

The extensive use of alkoxyamines in controlled radical polymerisation and polymer stabilisation is based on rapid cycling between the alkoxyamine (R1R2NO-R3) and a stable nitroxyl radical (R1R2NO•) via homolysis of the labile O-C bond. Competing homolysis of the alkoxyamine N-O bond has been predicted to occur for some substituents leading to production of aminyl and alkoxyl radicals. This intrinsic competition between the O-C and N-O bond homolysis processes has to this point been difficult to probe experimentally. Herein we examine the effect of local molecular structure on the competition between N-O and O-C bond cleavage in the gas phase by variable energy tandem mass spectrometry in a triple quadrupole mass spectrometer. A suite of cyclic alkoxyamines with remote carboxylic acid moieties (HOOC-R1R2NO-R3) were synthesised and subjected to negative ion electrospray ionisation to yield [M − H]− anions where the charge is remote from the alkoxyamine moiety. Collision-induced dissociation of these anions yield product ions resulting, almost exclusively, from homolysis of O-C and/or N-O bonds. The relative efficacy of N-O and O-C bond homolysis was examined for alkoxyamines incorporating different R3 substituents by varying the potential difference applied to the collision cell, and comparing dissociation thresholds of each product ion channel. For most R3 substituents, product ions from homolysis of the O-C bond are observed and product ions resulting from cleavage of the N-O bond are minor or absent. A limited number of examples were encountered however, where N-O homolysis is a competitive dissociation pathway because the O-C bond is stabilised by adjacent heteroatom(s) (e.g. R3 = CH2F). The dissociation threshold energies were compared for different alkoxyamine substituents (R3) and the relative ordering of these experimentally determined energies is shown to correlate with the bond dissociation free energies, calculated by ab initio methods. Understanding the structure-dependent relationship between these rival processes will assist in the design and selection of alkoxyamine motifs that selectively promote the desirable O-C homolysis pathway

Validity of a self-report survey tool measuring the nutrition and physical activity environment of primary schools

Background: Valid tools measuring characteristics of the school environment associated with the physical activity and dietary behaviours of children are needed to accurately evaluate the impact of initiatives to improve school environments. The aim of this study was to assess the validity of Principal self-report of primary school healthy eating and physical activity environments. Methods: Primary school Principals (n = 42) in New South Wales, Australia were invited to complete a telephone survey of the school environment; the School Environment Assessment Tool – SEAT. Equivalent observational data were collected by pre-service teachers located within the school. The SEAT, involved 65 items that assessed food availability via canteens, vending machines and fundraisers and the presence of physical activity facilities, equipment and organised physical activities. Kappa statistics were used to assess agreement between the two measures. Results: Almost 70% of the survey demonstrated moderate to almost perfect agreement. Substantial agreement was found for 10 of 13 items assessing foods sold for fundraising, 3 of 6 items assessing physical activity facilities of the school, and both items assessing organised physical activities that occurred at recess and lunch and school sport. Limited agreement was found for items assessing foods sold through canteens and access to small screen recreation. Conclusions: The SEAT provides researchers and policy makers with a valid tool for assessing aspects of the school food and physical activity environment

Nutritional and Demographic Consequences of Varying Elk Migratory Behaviors

Elk (Cervus elaphus) populations in the American West exhibit wide variation in migratory behavior. The traditional view of elk migration holds that migratory elk move from winter range in order to track growth of highly nutritious fresh vegetation into higher elevation areas. Non-migratory elk forego this seasonal movement, typically foraging in lower elevation winter range areas throughout the summer. Although the effect of summer nutrition on elk body condition and reproductive success is well known, the nutritional and demographic consequences of these differing migratory behaviors remain unclear. We developed a predictive model of summer forage quality to compare the nutrition available to migrants and non-migrants in a partially migratory population of elk in western Montana. Non-migratory elk had access to significantly higher forage quality than their migratory counterparts; the lower forage quality available to migrants is predicted to result in reduced reproductive success based on published studies linking nutrition with elk demographic rates. We therefore expect non-migrants to have higher fecundity rates and to comprise a higher proportion of the population relative to migrants. Harvest management actions that reduce survival rates of non-migrants or increase survival rates of migrants may be an effective tool for maintaining migratory behavior in partially migratory populations

Millennial scale control of European climate by the North Atlantic Oscillation from 12,500 BP: the Asiul speleothem record

Contemporary climate in Europe is strongly influenced by the North Atlantic Oscillation (NAO), the atmospheric pressure dipole between Iceland and the Azores1. Under positive NAO conditions winter storm tracks associated with the Atlantic Westerly Jet (AWJ) migrate northwards, leading to wetter and warmer winter conditions in north-western Europe and dry conditions in southern Europe; including the Iberian Peninsula. Under the negative NAO phase, storm tracks weaken and shift southwards reversing the pattern1. Existing proxy records of the NAO suggest that this atmospheric process only began to dominate European climate at approximately 8000 years BP, related to the final breakup of the Laurentide ice shelf2. However, here we present evidence of precipitation changes from a high-resolution speleothem δ18O record from northern Iberia, which indicates NAO-like forcing extending throughout the Holocene and into the Younger Dryas (YD) at 12,500 years BP. These variations in precipitation delivery relate to an underlying millennial scale cycle in NAO dynamics. The speleothem δ18O is strongly correlated to existing records of North Atlantic Ocean ice rafted debris (IRD)3, indicating an NAO-like connection with oceanic circulation during the Holocene2. These large-scale atmospheric processes have dramatically influenced the delivery of precipitation to northern Iberia and may have played a decisive role in environmental and human development in the region, throughout the Holocene