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Abstract: A mild and practical Barbier–Negishi coupling of secondary alkyl bromides with aryl and alkenyl triflates and nonaflates has been developed. This challenging reaction was enabled by the use of a very bulky imidazole‐based phosphine ligand, which resulted in good yields as well as good chemo‐ and site selectivities for a broad range of substrates at room temperature and under non‐aqueous conditions. This reaction was extended to primary alkyl bromides by using an analogous pyrazole‐based ligand. [ABSTRACT FROM AUTHOR]

The production and use of engineered nanomaterials (ENMs) are increasing rapidly, and therefore, the need to assess their environmental exposure and associated risks has become increasingly important. Only a handful of studies have quantified the release and environmental concentrations of ENMs, but much work has been done to investigate the effects of these materials on organisms. The aim of the present study was to quantify probabilistically the environmental risks of ENMs, producing species sensitivity distributions that were then compared with probability distributions of predicted environmental concentrations. Five nanomaterials (nano-Ag, nano-TiO2, nano-ZnO, carbon nanotubes [CNTs], and fullerenes) and 4 environmental compartments (surface water, sewage treatment plant effluents, soils, and sludge-treated soils) were considered. From 60 ecotoxicological studies, the authors extracted 112 single values to work with (25 values in 13 studies for nano-Ag, 17 values in 10 studies for CNTs, 7 values in 7 studies for fullerenes, 34 values in 23 studies for nano-TiO2, and 29 values in 17 studies for nano-ZnO). The results indicate there is only a marginal risk for these metal-based nanomaterials in surface water (0.7% risk for nano-Ag and <0.1% for nano-TiO2) and some risk in sewage treatment plant effluents (nano-Ag 39.7%, nano-TiO2 18.7%, and nano-ZnO 1.1%). Apart from a marginal value of <0.1% for nano-TiO2 in sludge-treated soils, no risk from the other evaluated ENMs in terrestrial compartments is currently predicted. The discussion of the results considers the influence of the effects of different forms of 1 ENM (coating, agglomeration state, and mineralogy), the test conditions (dissolution and agglomeration), and transformation reactions. Environ Toxicol Chem 2013;32:1278-1287. © 2013 SETAC [ABSTRACT FROM AUTHOR]

This article presents a method of probabilistically computing species sensitivity distributions (SSD) that is well-suited to cope with distinct data scarcity and variability. First, a probability distribution that reflects the uncertainty and variability of sensitivity is modeled for each species considered. These single species sensitivity distributions are then combined to create an SSD for a particular ecosystem. A probabilistic estimation of the risk is carried out by combining the probability of critical environmental concentrations with the probability of organisms being impacted negatively by these concentrations. To evaluate the performance of the method, we developed SSD and risk calculations for the aquatic environment exposed to triclosan. The case studies showed that the probabilistic results reflect the empirical information well, and the method provides a valuable alternative or supplement to more traditional methods for calculating SSDs based on averaging raw data and/or on using theoretical distributional forms. A comparison and evaluation with single SSD values (5th-percentile [HC5]) revealed the robustness of the proposed method. Integr Environ Assess Manag 2013; 9: 79-86. © 2012 SETAC [ABSTRACT FROM AUTHOR]

Protein acetylation has been implicated in playing an important role during mitotic progression. Aurora B kinase is known to play a critical role in mitosis. However, whether Aurora B is regulated by acetylation is not known. Using IP with an anti-acetyl lysine antibody, we identified Aurora B as an acetylated protein in PC3 prostate cancer cells. Knockdown of HDAC3 or inhibiting HDAC3 deacetylase activity led to a significant increase (P<0.01 and P<0.05, respectively) in Aurora B acetylation as compared to siLuc or vehicle-treated controls. Increased Aurora B acetylation is correlated with a 30% reduction in Aurora B kinase activity in vitro and resulted in significant defects in Aurora B-dependent mitotic processes, including kine-tochore-microtubule attachment and chromosome con-gression. Furthermore, Aurora B transiently interacts with HDAC3 at the kinetochore-microtubule interface of congressing chromosomes during prometaphase. This window of interaction corresponded with a transient but significant reduction (P=0.02) in Aurora B acetylation during early mitosis. Together, these results indicate that Aurora B is more active in its deacetylated state and further suggest a new mechanism by which dynamic acetylation/deacetylation acts as a rheostat to fine-tune Aurora B activity during mitotic progression. [ABSTRACT FROM AUTHOR]

Information on environmental concentrations is needed to assess the risks that engineered nanomaterials (ENM) may pose to the environment. In this study, predicted environmental concentrations (PEC) were modeled for nano-TiO2, carbon nanotubes (CNT) and nano-Ag for Switzerland. Based on a life-cycle perspective, the model considered as input parameters the production volumes of the ENMs, the manufacturing and consumption quantities of products containing those materials, and the fate and pathways of ENMs in natural and technical environments. Faced with a distinct scarcity of data, we used a probabilistic material flow analysis model, treating all parameters as probability distributions. The modeling included Monte Carlo and Markov Chain Monte Carlo simulations as well as a sensitivity and uncertainty analysis. The PEC values of the ENMs in the different environmental compartments vary widely due to different ENM production volumes and different life cycles of the nanoproducts. The use of ENM in products with high water relevance leads to higher water and sediment concentrations for nano-TiO2 and nano-Ag, compared to CNTs, where smaller amounts of ENM reach the aquatic compartments. This study also presents a sensitivity analysis and a comprehensive discussion of the uncertainties of the simulation results and the limitations of the used approach. To estimate potential risks, the PEC values were compared to the predicted-no-effect concentrations (PNEC) derived from published data. The risk quotients (PEC/PNEC) for nano-TiO2 and nano-Ag were larger than one for treated wastewater and much smaller for all other environmental compartments (e.g., water, sediments, soils). We conclude that probabilistic modeling is very useful for predicting environmental concentrations of ENMs given the current lack of substantiated data. Environ. Toxicol. Chem. 2010;29:1036–1048. © 2010 SETAC [ABSTRACT FROM AUTHOR]

The thermodynamic properties of three halocarbon molecules relevant in atmospheric and public health applications are presented from ab initio calculations. Our technique makes use of a reaction path-like Hamiltonian to couple all the vibrational modes to a large-amplitude torsion for 1,2-difluoroethane, 1,2-dichloroethane, and 1,2-dibromoethane, each of which possesses a heavy asymmetric rotor. Optimized ab initio energies and Hessians were calculated at the CCSD(T) and MP2 levels of theory, respectively. In addition, to investigate the contribution of electronically excited states to thermodynamic properties, several excited singlet and triplet states for each of the halocarbons were computed at the CASSCF/MRCI level. Using the resulting potentials and projected frequencies, the couplings of all the vibrational modes to the large-amplitude torsion are calculated using the new STAR-P 2.4.0 software platform that automatically parallelizes our codes with distributed memory via a familiar MATLAB interface. Utilizing the efficient parallelization scheme of STAR-P, we obtain thermodynamic properties for each of the halocarbons, with temperatures ranging from 298.15 to 1000 K. We propose that the free energies, entropies, and heat capacities obtained from our methods be used to supplement theoretical and experimental values found in current thermodynamic tables. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2008 [ABSTRACT FROM AUTHOR]