The functionalization of SBA-15 with mercaptopropyl trimethoxysilane leads to a material capable of absorbing Pd from organic and aqueous solutions. The resulting Pd-loaded material acts as a catalyst for the Suzuki-Miyaura and Mizoroki-Heck coupling reactions. Leaching studies show that the filtrate contains as little as 3 ppb Pd after reaction. Aminopropylated silica is an effective scavenger, and catalyst for the Mizoroki-Heck reaction, but leaching is significant (35 ppm), illustrating the importance of the thiol ligand to retain Pd on the surface. Heterogeneity tests such as hot filtration experiments and three-phase tests show that the reaction is occurring predominantly via surface-bound Pd.
Following the detection of bovine spongiform encephalopathy (BSE) in Canada, and subsequently in the United States, confidence in the safety of beef products remained high. Consumers actually increased their consumption of beef slightly after the news of an increased risk from mad cow disease, which has been interpreted as public support for beef farmers and confidence in government regulators. The Canadian public showed a markedly different reaction to the news of domestic BSE than the furious and panicked responses observed in the United Kingdom, Germany, and Japan. Using the social amplification of risk framework, we show that, while other countries displayed social amplification of risk, Canada experienced a social attenuation of risk. The attenuated reaction in Canada toward mad cow disease and increased human health risks from variant Creutzfeldt-Jakob disease (vCJD) was due to the social context at the time when BSE was discovered domestically. Mortality, morbidity, and psychosocial impacts resulting from other major events such as severe acute respiratory syndrome (SARS), West Nile virus (WNV), and the U.S.-Iraq war made the theoretical risks of BSE and vCJD a lower priority, reducing its concern as a risk issue.
Canadian immigrants have lower overall cancer risk than the Canadian-born population. Less is known about risks for immigrant subgroups and site-specific cancers. Linked administrative data sets were used to compare cancer incidence between subgroups of immigrants to Canada and the general Canadian population. The study involved 128,962 refugees and 241,010 non-refugees. Standardized incidence ratios (SIRs) were calculated for all-site and site-specific cancers by immigration categories and regions of birth. Relative to the general Canadian population, incidence of all-site cancer was lower among immigrants overall, by sex and refugee status (non-refugee SIRs 0.25: men, 0.24: women; refugee SIRs 0.31: both). Significantly higher SIRs resulted for liver, nasopharyngeal and cervical cancers, including liver cancer among South-East Asian and North-East Asian immigrants, and nasopharyngeal cancer among North-East Asian non-refugees. Hypothesized explanations for variation in cancer incidence include earlier viral infection in the country of origin.
The kinetics of methanolysis of six O-ethyl O-aryl methylphosphonates (6a-f) promoted by methoxide, La3+ and 1,5,9-triazacyclododecane complex of Zn2+(-OCH3) (5:Zn2+(-OCH3)) were studied as simulants for chemical warfare (CW) agents, and analyzed through the use of Brønsted plots. The beta(lg) values are, respectively, -0.76, -1.26 and -1.06, pointing to significant weakening of the P-OAr bond in the transition state. For the metal-catalyzed reactions the data are consistent with a concerted process where the P-OAr bond rupture has progressed to the extent of 84% in the La3+ reaction and ca. 70% in the Zn2+ catalyzed reaction. The catalysis afforded by the metal ions is remarkable, being about 10(6)-fold and 10(8)-fold for poor and good leaving groups, respectively, relative to the background reactions at pH 9.1. Solvent deuterium kinetic isotope studies for two of the substrates promoted by 5:Zn2+(-OCH3) give kH/kD = 1.0 +/- 0.1, consistent with a nucleophilic mechanism. A unified mechanism for the metal-catalyzed reactions is presented which involves pre-equilibrium coordination of the substrate to the metal ion followed by intramolecular delivery of a coordinated methoxide.
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