Total Synthesis of the Potent HIF-1 Inhibitory Antitumor Natural Product, (8R)-Mycothiazole, via Baldwin–Lee CsF/CuI sp3–sp2-Stille Cross-Coupling. Confirmation of the Crews Reassignment

A convenient asymmetric total synthesis of the potent HIF-1 inhibitory antitumor natural product, (−)- or (+)-(8R)-mycothiazole (1), is described. Not only does our synthesis confirm the 2006 structural reassignment made by Crews (Crews, P., et al. J. Nat. Prod. 2006, 69, 145), it revises the [α]_D data previously reported for this molecule in MeOH from −13.7° to +42.3°. The newly developed route to (8R)-1 sets the C(8)–OH stereocenter via Sharpless AE/2,3-epoxy alcohol reductive ring opening and utilizes two Baldwin–Lee CsF/cat. CuI Stille cross-coupling reactions with vinylstannanes 8 and 3 to efficiently elaborate the C(1)–C(4) and C(14)–C(18) sectors.

Highly resolved absolute cross-sections for dissociative electron attachment to SF5CF3

Using two complementary experimental methods, we have measured partial (mass-resolved) cross-sections for dissociative electron attachment to the molecule trifluoromethyl sulfurpentafluoride (SF5CF3) at the gas temperature T-G = 300 K over a broad range of electron energies (E = 0.001-12 eV). The absolute scale for these cross-sections was obtained with reference to the thermal (T = 300 K) rate coefficient for anion formation (8.0(3) x 10(-8) cm(3) s(-1)). Below 1 eV, SF5- is the dominant product anion and formed through the lowest anion state which cuts the neutral SF5CF3 potential close to the S-C equilibrium distance. The highly resolved laser photoelectron attachment data exhibit a downward Wigner cusp at 86meV, indicating that the nu(4)(alpha(1)) vibrational mode is important for the primary attachment dynamics. Both SF5- and F- anions are formed with similar yields through the first excited resonance located near 3.6eV. Towards higher energies, the anions CF3-, SF4-, and SF3- are also produced. Summation of the partial cross-sections yields a total absolute cross-section for anion formation over the energy range 0.001-12 eV. This is used to calculate the dependence of the rate coefficient for dissociative electron attachment over a broad range of electron temperatures for the fixed gas temperature T-G = 300 K; good agreement is found between the calculated values and those obtained in a drift tube experiment. In addition to the experimental work, semiempirical R-matrix calculations have been Carried out for the energy dependence of the cross-section for SF5- formation. The experimental findings are semi-quantitatively recovered. (C) 2008 Elsevier B.V. All rights reserved.

Economic globalization, inequality and body mass index:a cross-national analysis of 127 countries

This article investigates to what extent the worldwide increase in body mass index (BMI) has been affected by economic globalization and inequality. We used time-series and longitudinal cross-national analysis of 127 countries from 1980 to 2008. Data on mean adult BMI were obtained from the Global Burden of Metabolic Risk Factors of Chronic Diseases Collaborating Group. Globalization was measured using the Swiss Economic Institute (KOF) index of economic globalization. Economic inequality between countries was measured with the mean difference in gross domestic product per capita purchasing power parity in international dollars. Economic inequality within countries was measured using the Gini index from the Standardized World Income Inequality Database. Other covariates including poverty, population size, urban population, openness to trade and foreign direct investment were taken from the World Development Indicators (WDI) database. Time-series regression analyses showed that the global increase in BMI is positively associated with both the index of economic globalization and inequality between countries, after adjustment for covariates. Longitudinal panel data analyses showed that the association between economic globalization and BMI is robust after controlling for all covariates and using different estimators. The association between economic inequality within countries and BMI, however, was significant only among high-income nations. More research is needed to study the pathways between economic globalization and BMI. These findings, however, contribute to explaining how contemporary globalization can be reformed to promote better health and control the global obesity epidemic. © 2013 Copyright Taylor and Francis Group, LLC.

Mitigating Cross-Network Interference in Cognitive Spectrum Sharing with Opportunistic Relaying

We examine the impact of primary and secondary interference on opportunistic relaying in cognitive spectrum sharing networks. In particular, new closed-form exact and asymptotic expressions for the outage probability of cognitive opportunistic relaying are derived over Rayleigh and Nakagami-m fading channels. Our analysis presents revealing insights into the diversity and array gains, diversity-multiplexing tradeoff, impact of primary transceivers' positions, and the optimal position of relays. We highlight that cognitive opportunistic relaying achieves the full diversity gain which is a product of the number of relays and the minimum Nakagami-m fading parameter in the secondary network. Furthermore, we confirm that the diversity gain reduces to zero when the peak interference constraint in the secondary network is proportional to the interference power from the primary network.

The influence of market deregulation on fast food consumption and body mass index:A cross-national time series analysis

Objective
To investigate the effect of fast food consumption on mean population body mass index (BMI) and explore the possible influence of market deregulation on fast food consumption and BMI.

Methods
The within-country association between fast food consumption and BMI in 25 high-income member countries of the Organisation for Economic Co-operation and Development between 1999 and 2008 was explored through multivariate panel regression models, after adjustment for per capita gross domestic product, urbanization, trade openness, lifestyle indicators and other covariates. The possible mediating effect of annual per capita intake of soft drinks, animal fats and total calories on the association between fast food consumption and BMI was also analysed. Two-stage least squares regression models were conducted, using economic freedom as an instrumental variable, to study the causal effect of fast food consumption on BMI.

Findings
After adjustment for covariates, each 1-unit increase in annual fast food transactions per capita was associated with an increase of 0.033 kg/m2 in age-standardized BMI (95% confidence interval, CI: 0.013–0.052). Only the intake of soft drinks – not animal fat or total calories – mediated the observed association (β: 0.030; 95% CI: 0.010–0.050). Economic freedom was an independent predictor of fast food consumption (β: 0.27; 95% CI: 0.16–0.37). When economic freedom was used as an instrumental variable, the association between fast food and BMI weakened but remained significant (β: 0.023; 95% CI: 0.001–0.045).

Conclusion
Fast food consumption is an independent predictor of mean BMI in high-income countries. Market deregulation policies may contribute to the obesity epidemic by facilitating the spread of fast food.

Synthesis of , of α,β-unsaturated aldehydes and nitriles via cross-metathesis reactions using Grubbs’ catalysts

A series of alpha,beta-unsaturated aldehydes and nitriles of significant interest in the fragrance industry have been prepared using Grubbs' catalysts in cross-metathesis reactions of electron-deficient olefins (i.e., acrolein, crotonaldehyde, methacrolein, and acrylonitrile) with various 1-alkenes, including 1-decene, 1-octene, 1-hexene and 2-allyloxy-6-methylheptane. The latter is of particular interest, as it has not previously being used as a substrate in cross-metathesis reactions and allows access to valuable intermediates for the synthesis of new fragrances. Most reactions gave good selectivity of the desired CM product (>= 90%). Detailed optimisation and mechanistic studies have been performed on the cross-metathesis of acrolein with 1-decene. Recycling of the catalyst has been attempted using ionic liquids. 

Bond quality of cross-laminated timber from Irish Sitka spruce

The potential use of Irish-grown Sitka spruce for cross-laminated timber (CLT) manufacture is investigated as this would present new opportunities and novel products for Irish timber in the home and export markets. CLT is a prefabricated multilayer engineered wood product made of at least three orthogonally bonded layers of timber. In order to increase rigidity and stability, successive layers of boards are placed cross-wise to form a solid timber panel. Load-bearing CLT wall and floor panels are easily assembled on site to form multi-storey buildings. This improves construction and project delivery time, reduces costs,
and maximises efficiency on all levels.

The paper addresses the quality of the interface bond between the laminations making up the panels, which is of fundamental importance to the load bearing capacity. Therefore, shear tests were carried out on nine test bars of three glue lines each. Moreover, delamination tests were performed on samples subjected to accelerated aging, in order to assess the durability of bonds subjected to severe environmental conditions. In addition, this paper gives an indication on thickness tolerances of planed Irish Sitka spruce lamellas, which is likely to be a critical factor for bonding quality and adhesive selection. The test results of bond quality presented in this study were within requirements of prEN 16351:2013.