Comparative study of diastereoisomer interconversion in chiral BINOL-ate and diamine platinum complexes of conformationally flexible NUPHOS diphosphines

A thorough and detailed study of diastereointerconversion in the chiral platinum complexes [(NUPHOS)Pt{(S)-BINOL}] (3a-e) has been undertaken and compared with the results of a similar study with [(BIPHEP)Pt{(S)-BINOL}]. Rate data revealed that this process obeys first-order relaxation kinetics, and rate constants for conversion of the minor to the major diastereoisomer have been obtained. Eyring analysis of the data gave DeltaH(double dagger) and DeltaS(double dagger) values of 22-25 kcal mol(-1) and -1 to -16 eu, respectively. In combination with computational analysis, these studies indicate that atropinversion most likely occurs via an on-metal pathway involving a planar seven-membered transition state. Substitution of (S)-BINOL for (S,S)-DPEN results in a marked reduction in the barrier to atropinversion; a DeltaH(double dagger) value of 17 kcal mol(-1) has been determined for the conversion of delta-[(Ph-4-NUPHOS)Pt{(S,S)-DPEN}]Cl-2 to lambda-[(Ph-4-NUPHOS)Pt{(S,S)-DPEN}]Cl-2, which could indicate that an alternative mechanism operates.

Was It Something I Ate? Implementation of the FDA Seafood HACCP Program

We develop a theoretical model of enforcement and compliance under HACCP regulation and use the FDA's seafood inspection records to examine: (1) if the FDA has targeted its inspections under HACCP regulation; (2) the effects of inspections on compliance with HACCP and plant sanitation standards; and (3) the relationship between compliance with HACCP and preexisting sanitation standards. There is some evidence of targeting based on product risk, but not on past compliance performance. The threat of an inspection increases the likelihood of compliance, but only for sanitation inspections, not for HACCP. HACCP compliance does not improve compliance with sanitation standards. © 2008 American Agricultural Economics Association.

‘Who Ate All the Pride?’:Patriotic Sentiment and English National Football Support.

The growing popularity of English national insignia in international football tournaments has been widely interpreted as evidence of the emergence of a renewed English national consciousness. However, little empirical research has considered how people in England actually understand football support in relation to national identity. Interview data collected around the time of the Euro 2000 and the 2002 World Cup tournaments fail to substantiate the presumption that support for the England football team maps onto claims to patriotic sentiment in any straightforward way. People with far-right political affiliations did generally use national football support to symbolise a general pride in English national identity. However, other people either claimed not to support the England national team precisely because of its associations with nationalism, or else bracketed the domain of football support from more general connotations of English patriotism.

Fast heating of ultrahigh-density plasma as a step towards laser fusion ignition

ate studies(2) and fusion energy research(3,4). Laser-driven implosions of spherical polymer shells have, for example, achieved an increase in density of 1,000 times relative to the solid state(5). These densities are large enough to enable controlled fusion, but to achieve energy gain a small volume of compressed fuel (known as the 'spark') must be heated to temperatures of about 10(8) K (corresponding to thermal energies in excess of 10 keV). In the conventional approach to controlled fusion, the spark is both produced and heated by accurately timed shock waves(4), but this process requires both precise implosion symmetry and a very large drive energy. In principle, these requirements can be significantly relaxed by performing the compression and fast heating separately(6-10); however, this 'fast ignitor' approach(7) also suffers drawbacks, such as propagation losses and deflection of the ultra-intense laser pulse by the plasma surrounding the compressed fuel. Here we employ a new compression geometry that eliminates these problems; we combine production of compressed matter in a laser-driven implosion with picosecond-fast heating by a laser pulse timed to coincide with the peak compression. Our approach therefore permits efficient compression and heating to be carried out simultaneously, providing a route to efficient fusion energy production.

Sorption behavior of cationic and anionic dyes from aqueous solution on different types of activated carbons

The effect of dye molecular charges on their adsorption from solution was investigated by using different types of activated carbon adsorbents. Two types of model systems were used representing cationic and anionic dyes. Screening investigations using single point tests were used throughout the study. Cationic dyes, of which Methylene Blue is an example, showed a higher adsorption tendency towards activated carbon over anionic dyes represented by an ate-type reactive compound. Of the number of activated carbons tested, only one of the adsorbents showed an exception to this behavior, and a good relation was observed between Methylene Blue capacity and activated carbon performance. The high capacity of cationic dyes in comparison to anionic dyes was also evident in the results obtained by a preliminary kinetic study carried out on the selected systems. Surface net charge of activated carbon and the nature of attractions between the molecules were suggested to be one of the reasons attributed for this behavior.

Claw removal and feeding ability in the edible crab, Cancer pagurus: Implications for fishery practice

Feeding ability and motivation were assessed in the edible crab, Cancer pagurus, to investigate how the fishery practice of de-clawing may affect live crabs returned to the sea. Crabs were either induced to autotomise one claw, or were only handled, before they were offered food. Initially, autotomised and handled crabs were offered mussels, Mytilis edulis, a large part of their natural diet. After 3 days, both autotomised and handled crabs were then offered fish, a more readily handled food source. Autotomy induced crabs consumed significantly fewer mussels and less mussel mass, but ate significantly more mass of fish. This indicates that the effect of autotomy was a reduction of ability to feed on mussels rather than a general reduction of feeding motivation. The discontinuation of claw removal needs to be considered, both for the sustainability of the fishery and animal welfare concerns. (C) 2008 Elsevier B.V. All rights reserved.

Differential physico-chemical tolerances and intraguild predation among native and invasive amphipods (Crustacea); a field study

We used field surveys and transplant experiments to elucidate the relative roles of physico-chemical regime and intraguild predation in determining the generally mutually exclusive distributions of native and invader freshwater amphipod species. Field surveys showed that the native Gammarus duebeni celticus dominates the shoreline of Lough Neagh, N. Ireland, with some co-occurrence with the N. American invader G. tigrinus. However, the latter species dominates the deeper areas of the mid-Lough. Transplant experiments showed no difference in survival of the native and invader in single species 'bioassay tubes' placed along the shoreline. However, there was significantly higher survival of the invader compared with the native in single species tubes placed in the mid-Lough. In mixed species tubes on the shoreline, the native killed and ate the invader, with no reciprocal interaction, leading to significant reductions of the invader. However, the invader had significantly higher survival than the native in mixed species tubes in the mid-Lough, with no evidence. of predation between the two species. These results indicate that, whereas differential intraguild predation may determine domination of the shoreline by the native, differential physico-chemical tolerances may be major determinants of the domination of the mid-Lough by the invader. This study emphasises the need to consider the habitat template in conjunction with biotic interactions before attempting to draw conclusions about mechanisms determining relative distribution patterns of native and invasive species.

Factors influencing eating a varied diet in old age

OBJECTIVE:
To investigate the influences of resources and food-related goals on the variety of food choice among older people.
DESIGN:
A questionnaire-based survey in eight European countries: Poland, Portugal, United Kingdom, Germany, Sweden, Denmark, Italy and Spain.
SUBJECTS:
Participants (n 3200) were above 65 years of age and living in their own homes. The samples were quota samples, eight groups of fifty in each country, based on gender, age and living circumstances, reflecting the diversity of each of the national populations based on education, income and urbanization of living environment.
RESULTS:
Hierarchical multiple regression analysis showed that income, health status, access to a car and living arrangement affected the level of dietary variety. The perceived level of different food-related resources impacted the consumption of a varied diet over and above actual resource levels. Food-related goals contributed to variety of food intake that was not accounted for by the amount of material resources possessed or the social and other resources perceived to be possessed.
CONCLUSIONS:
Older people's variety of food intake depended on material resources (e.g. monthly income, access to a car, living arrangement, physical and mental health). However, in addition to these variables, the way older people perceived other resources, such as their level of appetite, their food knowledge, their perception of the distance to the shops, access to high-quality products, having better kitchen facilities, access to good service providers and support from friends and neighbours, all contributed to how varied a diet they ate.

The comparative solvatochromism of arylazo and heteroarylazo compounds based on N,N-diethyl-m-acetylaminoaniline and N,N-diethyl-m-toluidine

Azobenzene dyes derived from various anilines and aminothiaheterocycles ate-coupled with commercially important N,N-diethyl-m-toluidine (T series) and iv,N-diethyl-m-acetylaminoaniline (A series) are positively solvatochromic. The visible spectra of 16 pairs of derivatives have been measured in up to 22 solvents, and the transition energies related to Kamlet-Taft solvent polarity parameters. In general, A-series dyes are more bathochromic than their T-series counterparts in nonpolar solvents, consistent with colour chemistry tradition, However, in more dipolar solvents the more bathochromic T-series representatives unexpectedly become more bathochromic than their A-series partners. The relative solvatochromic shifts of the A and T series are related to their respective dipole moments, These in turn are distinguished by the effect of the anilide carbonyl group dipole moment, which is antiparallel to, and thus reduces, the dipole moment of the chromogen.

An examination of the thermorheological and drug release properties of zinc tetraphenylporphyrin-containing thermoresponsive hydrogels, designed as light activated antimicrobial implants

This study describes the thermorheological, mechanical and drug release properties of novel, light-activated antimicrobial implants. Hydrogels, based on N-isopropylacrylamide (NIPAA) and hydroxyethyl methacryl ate (HEMA) and either devoid of or containing zinc tetraphenylporphyrin, were prepared by free radical polymerisation and characterised using oscillatory rheometry and texture profile analysis. Drug release was studied at both 20 and 37 degrees C. Hydrogels containing NIPAA exhibited a sol-gel temperature (Tin), which increased as the proportion of HEMA increased and was

Relationships between lameness and feeding behaviour in cubicle-housed Holstein-Friesian dairy cows

The relationship between lameness and feeding behaviour in dairy cows is not yet fully understood. This study examined the effect of lameness on feeding behaviour at two points during lactation. Forty-five Holstein–Friesian dairy cows (average parity 3.3) were housed in cubicle accommodation after calving and fed a total mixed ration (TMR). At approximately 60 and 120 days post partum, 48 h of information on feeding behaviour (including number of meals eaten, meal duration, meal size and feeding rate) was collected for each animal using feed boxes fitted to a data recording system. At the same time points, locomotion scores were recorded for each cow as a measure of lameness (1.0-sound to 4.5-severely lame). Relationships between feeding behaviour and locomotion score were analysed using Residual Maximum Likelihood (REML) analysis. At both time points, cows with higher locomotion scores ate fewer (P < 0.001), larger meals (P < 0.001) and had a shorter total feeding time (P < 0.001). At day 60 post partum, an increase in locomotion score was associated with a decrease in dry matter intake (P < 0.05), but at day 120 post partum no relationship was found between locomotion score and DMI. No relationship was found at either time point between locomotion score and mean meal duration or rate of feeding. The results of this study suggest that the effect of lameness on feeding behaviour in dairy cows does not remain constant across lactation.

Long-term flavor recognition in humans with prenatal garlic experience

The human fetus learns about its chemosensory environment and this influences its behavior at birth and during the nursing period. This study examined whether prenatal experience could influence behavior much later in life. The dietary preference of two groups of children (8- to 9-years old) was examined. Mothers of one group had consumed garlic during pregnancy, mothers of the control group had not. Children received two tests, 1 month apart, of a meal containing two portions of potato gratin, one flavored with garlic. The total amount of potato, and the percentage of garlic flavored potato, eaten was calculated and examined separately by ANOVA for factors of prenatal exposure, the child's sex, and trial. Children prenatally exposed to garlic ate significantly more garlic flavored potato and a significantly greater overall amount of potato on trial 2, compared to controls. The results demonstrate prenatal experience may affect behavior well into childhood. © 2012 Wiley Periodicals, Inc.

Marginalization, deprivation, and fatalism in the Republic of Ireland. Class and underclass perspectives

The emergence of large-scale long-term unemployment in the Republic of Ireland suggests that it might provide an interesting case to which to apply the concept of an 'underclass'. In this paper we explore the relationship between labour-market marginality, deprivation, and fatalism. The available evidence in relation to both social isolation and milieu effects suggests that the term 'underclass' can have only a very limited applicability in the Irish case. Instead, what we ate confronted with is different types of working-class marginalization arising from the rapid and uneven nature of class transformation in Ireland and changing patterns of emigration. In relation to what we have termed 'pervasive marginalization' the costs of economic change have been borne disproportionately by those members of the younger cohorts originating in the lower working class rather than by those in particular locations. The evidence relating to the social and psychological consequences of labour-market detachment, rather than providing support for the value of an 'underclass' perspective, confirms the continued relevance of class analysis.

Climate change and decadal to centennial-scale periodicities recorded in a late Holocene NE Pacific marine record: Examining the role of solar forcing

We present a decadal-scale late Holocene climate record based on diatoms, biogenic silica, and grain size from a 12-m sediment core (VEC02A04) obtained from Frederick Sound in the Seymour-Belize Inlet Complex of British Columbia, Canada. Sediments are characterized by graded, massive, and laminated intervals. Laminated intervals are most common between c. 2948–2708 cal. yr BP and c. 1992–1727 cal. yr BP. Increased preservation of laminated sediments and diatom assemblage changes at this time suggest that cli- mate became moderately drier and cooler relative to the preceding and succeeding intervals. Spectral and wavelet analyses are used to test for statistically significant periodicities in time series of proxies of primary production (total diatom abundance, biogenic silica) and hydrology (grain size) preserved in the Frederick Sound record. Periodicities of c. 42–53, 60–70, 82–89, 241–243, and 380 yrs are present. Results are com- pared to reconstructed sunspot number data of Solanki et al. (2004) using cross wavelet transform to evalu- ate the role of solar forcing on NE Pacific climate. Significant common power of periodicities between c. 42– 60, 70–89, 241–243, and of 380 yrs occur, suggesting that celestial forcing impacted late Holocene climate at Frederick Sound. Replication of the c. 241–243 yr periodicity in sunspot time series is most pronounced be- tween c. 2900 cal. yr BP and c. 2000 cal. yr BP, broadly correlative to the timing of maximum preservation of laminated sedimentary successions and diatom assemblage changes. High solar activity at the Suess/de Vries band may have been manifested as a prolonged westward shift and/or weakening of the Aleutian Low in the mid-late Holocene, which would have diverted fewer North Pacific storms and resulted in the relatively dry conditions reconstructed for the Seymour-Belize Inlet Complex.