I. The crystal structure of potassium bis(tricyanovinyl)amine. II. Nuclear magnetic resonance studies of alkali halide solutions. III. Elucidation of the intramolecular hydrogen bond in acetylacetone by the deuterium isotope effect on the chemical shift of the bridge hydrogen

Part I

Potassium bis-(tricyanovinyl) amine, K⁺N[C(CN)=C(CN)₂]₂^-, crystallizes in the monoclinic system with the space group Cc and lattice constants, a = 13.346 ± 0.003 Å, c = 8.992 ± 0.003 Å, B = 114.42 ± 0.02°, and Z = 4. Three dimensional intensity data were collected by layers perpendicular to b* and c* axes. The crystal structure was refined by the least squares method with anisotropic temperature factor to an R value of 0.064.

The average carbon-carbon and carbon-nitrogen bond distances in –C-CΞN are 1.441 ± 0.016 Å and 1.146 ± 0.014 Å respectively. The bis-(tricyanovinyl) amine anion is approximately planar. The coordination number of the potassium ion is eight with bond distances from 2.890 Å to 3.408 Å. The bond angle C-N-C of the amine nitrogen is 132.4 ± 1.9°. Among six cyano groups in the molecule, two of them are bent by what appear to be significant amounts (5.0° and 7.2°). The remaining four are linear within the experimental error. The bending can probably be explained by molecular packing forces in the crystals.

Part II

The nuclear magnetic resonance of ⁸¹Br and ¹²⁷I in aqueous solutions were studied. The cation-halide ion interactions were studied by studying the effect of the Li⁺, Na⁺, K⁺, Mg⁺⁺, Cs⁺ upon the line width of the halide ions. The solvent-halide ion interactions were studied by studying the effects of methanol, acetonitrile, and acetone upon the line width of ⁸¹Br and ¹²⁷I in the aqueous solutions. It was found that the viscosity plays a very important role upon the halide ions line width. There is no specific cation-halide ion interaction for those ions such as Mg⁺⁺, Di⁺, Na⁺, and K⁺, whereas the Cs⁺ - halide ion interaction is strong. The effect of organic solvents upon the halide ion line width in aqueous solutions is in the order acetone ˃ acetonitrile ˃ methanol. It is suggested that halide ions do form some stable complex with the solvent molecules and the reason Cs⁺ can replace one of the ligands in the solvent-halide ion complex.

Part III

An unusually large isotope effect on the bridge hydrogen chemical shift of the enol form of pentanedione-2, 4(acetylacetone) and 3-methylpentanedione-2, 4 has been observed. An attempt has been made to interpret this effect. It is suggested from the deuterium isotope effect studies, temperature dependence of the bridge hydrogen chemical shift studies, IR studies in the OH, OD, and C=O stretch regions, and the HMO calculations, that there may probably be two structures for the enol form of acetylacetone. The difference between these two structures arises mainly from the electronic structure of the π-system. The relative population of these two structures at various temperatures for normal acetylacetone and at room temperature for the deuterated acetylacetone were calculated.

Semiempirical method for the evaluation of bond covalency in complex crystals

We report a semiempirical method for the evaluation of bond covalency in complex crystals. This method is the extension of the dielectric description theory delivered by Phillips, Van Vechten, Levine, and Tanaka (PVLT) which is mainly suitable for binary crystals. Our method offers the advantage of applicability to a broad class of complex materials. The simplicity of the approach allows a broader class of researchers to access the method easily and to calculate not only the bond covalency but also other useful. properties such as bulk modulus. For a series study, a useful trend can be illustrated and often the prediction of the properties of the-missing one(s) among the series can be possible. Finally, examples are given to show how the method is applied and the procedure is transferable to other complex crystals.

Diet of auklet chicks in the Aleutian Islands, Alaska: similarity among islands, interspecies overlap, and relationships to ocean climate

Seabirds are effective samplers of the marine environment, and can be used to measure resource partitioning among species and sites via food loads destined for chicks. We examined the composition, overlap, and relationships to changing climate and oceanography of 3,216 food loads from Least, Crested, and Whiskered Auklets (Aethia pusilla, A. cristatella, A. pygmaea) breeding in Alaska during 1994–2006. Meals comprised calanoid copepods (Neocalanus spp.) and euphausiids (Thysanoessa spp.) that reflect secondary marine productivity, with no difference among Buldir, Kiska, and Kasatochi islands across 585 km of the Aleutian Islands. Meals were very similar among species (mean Least–Crested Auklet overlap C = 0.68; Least–Whiskered Auklet overlap C = 0.96) and among sites, indicating limited partitioning of prey resources for auklets feeding chicks. The biomass of copepods and euphausiids in Least and Crested Auklet food loads was related negatively to the summer (June–July–August) North Pacific Gyre Oscillation, while in Whiskered Auklet food loads, this was negatively related to the winter (December–January–February) Pacific Decadal Oscillation, both of which track basin-wide sea-surface temperature (SST) anomalies. We found a significant quadratic relationship between the biomass of calanoid copepods in Least Auklet food loads at all three study sites and summer (June–July) SST, with maximal copepod biomass between 3–6°C (r 2 = 0.71). Outside this temperature range, zooplankton becomes less available to auklets through delayed development. Overall, our results suggest that auklets are able to buffer climate-mediated bottom-up forcing of demographic parameters like productivity, as the composition of chick meals has remained constant over the course of our study.

New ways to break an old bond: the bacterial carbon-phosphorus hydrolases and their role in biogeochemical phosphorus cycling

Phosphonates are organophosphorus molecules that contain the highly stable C-P bond, rather than the more common, and more labile, C-O-P phosphate ester bond. They have ancient origins but their biosynthesis is widespread among more primitive organisms and their importance in the contemporary biosphere is increasingly recognized; for example phosphonate-P is believed to play a particularly significant role in the productivity of the oceans. The microbial degradation of phosphonates was originally thought to occur only under conditions of phosphate limitation, mediated exclusively by the poorly characterized C-P lyase multienzyme system, under Pho regulon control. However, more recent studies have demonstrated the Pho-independent mineralization by environmental bacteria of three of the most widely distributed biogenic phosphonates: 2-aminoethylphosphonic acid (ciliatine), phosphonoacetic acid, and 2-amino-3-phosphonopropionic acid (phosphonoalanine). The three phosphonohydrolases responsible have unique specificities and are members of separate enzyme superfamilies; their expression is regulated by distinct members of the LysR family of bacterial transcriptional regulators, for each of which the phosphonate substrate of the respective degradative operon serves as coinducer. Previously no organophosphorus compound was known to induce the enzymes required for its own degradation. Whole-genome and metagenome sequence analysis indicates that the genes encoding these newly described C-P hydrolases are distributed widely among prokaryotes. As they are able to function under conditions in which C-P lyases are inactive, the three enzymes may play a hitherto-unrecognized role in phosphonate breakdown in the environment and hence make a significant contribution to global biogeochemical P-cycling.

Learning curves, taking instructions, and patient safety:using a theoretical domains framework in an interview study to investigate prescribing errors among trainee doctors

ABSTRACT:

Offenders' Risk-Taking Attitude Inside and Outside the Prison Walls

It has long been assumed that risk taking is closely associated with criminal behavior. One reason for placing criminals behind bars-aside from punishment and protecting the public-is to prevent them from engaging in further risky criminal activities. Limited attention has been paid to whether being inside or outside prison affects offenders' risk-taking behaviors and attitudes. We compared risk-taking behaviors and attitudes in five risk domains (ethical, financial, health/safety, recreational, social) among 75 incarcerated offenders (i.e., offenders who are currently in prison) and 45 ex-offenders (i.e., offenders who have just been released from prison). Ex-offenders reported higher likelihood of engaging in risky behavior, driven largely by a willingness to take more risks in the recreational and ethical domains. Benefits attributed to risk taking as well as risk perception did not differ between incarcerated and ex-offenders, indicating that the opportunity to take risks might underlie behavioral risk intentions. Our results also indicate that risk-taking activities are better predicted by the expected benefits rather than by risk perception, aside from the health/safety domain. These results highlight the importance of studying the person and the environment and examining risk taking in a number of content domains.

Shared lives social impact bond feasibility study

Loneliness and isolation among the elderly is an enormous problem in Portugal. Interventions to tackle loneliness worldwide have had limited success, and new approaches are needed. Shared Lives is an adult foster placement service in the UK that shows significant promise in tackling both loneliness, isolation and other societal challenges linked with ageing. This feasibility study suggests that replicating a Shared Lives service in Portugal, using a Social Impact Bond (SIB), is viable and likely to create both social and financial value for all stakeholders involved. This study provides recommendations for how a Shared Lives SIB could be designed and implemented.

Effect of blood contamination on the shear bond strength at resin/dentin interface in primary teeth

Purpose: To assess in vitro the shear bond strength at the resin/dentin interface in primary teeth after contamination with fresh human blood. Methods: 75 crowns of primary molars were embedded in acrylic resin and mechanically ground to expose a flat dentin surface. The specimens were randomly assigned to five groups (n=15), according to the surface treatment. Group I (control) had no blood contamination. The other groups were blood-contaminated and subjected to different post-contamination protocols: in Group 2, the surfaces were rinsed with water; in Group 3, the surfaces were air-dried; in Group 4, the surfaces were rinsed and air-dried; and in Group 5, no post-contamination treatment was done. In all groups, a 3-mm dentin bonding site was demarcated, Single Bond adhesive system was applied and resin composite cylinders were bonded. After 24 hours in distilled water, shear bond strength was tested at a crosshead speed of 0.5 mm/minute. Results: Means (in MPa) were: Group 1: 7.1 (+/- 4.2); Group 2: 4.0 (+/- 1.8); Group 3: 0.9 (+/- 0.7); Group 4: 3.9 (+/- 2.2) and Group 5: 1.3 (+/- 1.5). Data were analyzed statistically by the Kruskal-Wallis test at 5% significance level. Groups 2 and 4 were similar to each other (P > 0.05) and both ware similar to Group 1 (P > 0.05). These groups (2, 3 and 4) had statistically significantly higher bond strengths than Groups 3 and 5 (P < 0.05). Blood contamination negatively affected the shear bond strength to primary tooth dentin. Among the blood-contaminated groups, water-rinsed specimens had higher bond strengths than those that were exclusively air-dried or not submitted to any post-contamination protocol before adhesive application.

Ether-Bond-Containing Ionic Liquids and the Relevance of the Ether Bond Position to Transport Properties

The ionic liquids (ILs) 1-ethoxyethyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide, [EtO-(CH(2))(2)MMI][Tf(2)N], and N-(ethoxyethyl)-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide, [EtO(CH(2))(2)MMor][Tf(2)N] were synthesized, and relevant properties, such as thermal stability, density, viscosity, electrochemical behavior, ionic conductivity, and self-diffusion coefficients for both ionic species, were measured and compared with those of their alkyl counterparts, 1-n-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide, [BMMI][Tf(2)N], and N-n-butyl-N-methylpiperidinium bis(trifluoromethanesulfonyl)imide,[BMP][Tf(2)N] and N-n-butyl-N-methylmorpholinium bis(trilfuoromethanesulfonyl)imide [BMMor][Tf(2)N][. This comparison was done to evaluate the effects caused by the presence of the ether bond in either the side chain or in the organic cation ring. The salt, LiTf(2)N, was added to the systems to estimate IL behavior with regard to lithium cation transport. Pure [EtO(CH(2))(2)MMI][Tf(2)N] and their LiTf(2)N solutions showed low viscosity and the highest conductivity among the ILs studied. The H(R) (AC conductivity/NMR calculated conductivity ratio) values showed that, after addition of LiTf(2)N, ILs containing the ether bond seemed to have a greater number of charged species. Structural reasons could explain these high observed HR values for [EtO(CH(2))(2)MMor][Tf(2)N].

Volatility linkages and spillovers in stock and bond markets : some international evidence

This study investigates the transmission of market-wide volatility between the equity markets and bond markets of Japan, Germany, the U. K., and the U. S. To measure the volatility transmission, the BEKK- a decomposition approach to the multivariate GARCH (1,1) model, is used to examine the cross-market contemporaneous effect of information arrival. Our results suggest that within the domestic cross markets, the volatility transmission is undirectional from the stock market to the bond market. Evidence from international cross-market analysis is mixed, with strong evidence on volatility spillover among these international stock markets, but weak evidence between international stock and bond markets. In addition, there are significant bi-directional volatility transmissions between stock markets in Germany and the U. K., and between Germany and the U. S. The volatility transmissions among these markets suggest that the international diversification of bonds is not prevalent.

Volatility transmissions between stock and bond markets : evidence from Japan and the U.S.

This study attempts to investigate the transmission of market-wide volatility between the equity markets and bond markets of Japan and the U.S. To measure the volatility transmission, the BEKK (Baba, Engle, Kraft and Kroner, 1990) method, a decomposition approach of the multivariate GARCH (1,1) model, is used to examine the cross-market contemporaneous effect of information arrival. The time series analysis provides evidence to the long-run phenomena of causality in conditional variances of paired assets within the local and international markets. Within various pairings, some evidence of bi-directional volatility transmissions such as informational linkages have been observed. Our empirical results suggest that within the domestic cross markets, the volatility transmission is unidirectional from the stock market to the bond market. Evidence from international cross-market analysis is mixed, with strong evidence on volatility spillover among these international stock markets, but weak evidence between international stock and bond markets. In addition, there are significant directional volatility transmissions between DJI index and FTSE100 index, and between DJI index and DAX200 index. The volatility transmission between these two markets indicates that the international diversification of bonds is not prevalent.

Projected socioeconomic disparities in the prevalence of obesity among Australian adults

Objective: To project prevalence of normal weight, overweight and obesity by educational attainment, assuming a continuation of the observed individual weight change in the 5-year follow-up of the national population survey, the Australian Diabetes, Obesity and Lifestyle study (AusDiab; 2000–2005).

Methods: Age-specific transition probabilities between BMI categories, estimated using logistic regression, were entered into education-level-specific, incidence-based, multi-state life tables. Assuming a continuation of the weight change observed in AusDiab, these life tables estimate the prevalence of normal weight, overweight and obesity for Australian adults with low (secondary), medium (diploma) and high (degree) levels of education between 2005 and 2025.

Results: The prevalence of obesity among individuals with secondary level educational attainment is estimated to increase from 23% in 2000 to 44% in 2025. Among individuals with a degree qualification or higher, it will increase from 14% to 30%. If all current educational inequalities in weight change could be eliminated, the projected difference in the prevalence of obesity by 2025 between the highest and lowest educated categories would only be reduced by half (to a 6 percentage point difference from 14 percentage points).

Conclusion: We predict that almost half of Australian adults with low educational status will be obese by 2025. Current trends in obesity have the potential to drive an increase in the absolute difference in obesity prevalence between educational categories in future years.

Implications: Unless obesity prevention and management strategies focus specifically on narrowing social inequalities in obesity, inequalities in health are likely to widen.

Economic implications of obesity among people with atherothrombotic disease

Objective: The purpose of this study was to ascertain the impact of obesity on the cost of disease management in people with or at high risk of atherothrombotic disease from a governmental perspective using a bottom-up approach to cost estimation. In addition, the aim was also to explore the causes of any differences found.

Method: The health-care costs of obesity were estimated from 2819 participants recruited into the nationwide Australian REACH Registry with established atherothrombotic disease or at least three risk factors for atherothrombosis. Enrollment was in 2004, through primary care general practices. Information was collected on the use of cardiovascular drugs, hospitalizations and ambulatory care services. Bottom-up costing was undertaken by assigning unit costs to each health-care item, based on Australian Government-reimbursed figures 2006-2007. Linear-mixed models were used to estimate associations between direct medical costs and body mass index (BMI) categories.

Results: Annual pharmaceutical costs per person increased with increasing BMI category, even after adjusting for gender, age, living place, formal education, smoking status, hypertension and diabetes. Adjusted annual pharmaceutical costs of overweight and obese participants were higher (7 (P0.004) and 144 (0.001), respectively) than those of the normal weight participants. This was due to participants in higher BMI categories receiving more pharmaceuticals than normal weight participants. There was no significant change across the BMI categories in annual ambulatory care costs and annual hospital costs.

Conclusion: In these participants with or at high risk of atherothrombotic disease, annual pharmaceutical costs were greater in participants of higher BMI category, but there was not such a gradient in the annual hospital or ambulatory care costs. The greater cardiovascular pharmaceutical costs for participants of higher BMI categories remained even after adjusting for a range of demographic factors and comorbidities. Our results suggest that these costs are explained by the higher number of drugs used among people with atherothrombotic disease. Further investigation is needed to understand the reasons for this level of drug use.

How organisations know what they know : a survey of knowledge identification methods among Australian organisations

Literature surrounding the Knowledge Management process of identifying what knowledge exists within an organisation is scarce. This research project set out to fill the research gaps surrounding that particular Knowledge Management process called Knowledge Identification. This paper reports on the findings of a survey sent to 973 Australian organisations to investigate their Knowledge Identification practices. The survey findings show that while organisations do perceive Knowledge Identification to be important, the practice of KI has not reached mainstream adoption yet. The reasons why and why not, and the range of methods organisations currently use to establish what knowledge exists within their four walls are identified. The survey findings also reveal two opposing approaches organisations take in practising KI: proactive KI and reactive KI.

Examples of regioselective anion recognition among a family of two-, three-, and four-"armed" bis-, tris-, and tetrakis(thioureido) [n]polynorbornane hosts

A family of conformationally preorganized, [n]polynorbornane-based anion hosts 1a,b–6a,b have been synthesized. The series includes receptors with 4, 8, and 12 H-bond donors. Using ¹H NMR titration techniques, evaluation of the new hosts against a series of alkyl and aryl dicarboxylates as well as a range of phosphoanionic species has revealed that the tris(thioureido) hosts (in particular 3a) are capable of regioselectively binding dicarboxylates and pyrophosphate (H₂PPi^2–).