A recyclable chiral Ru catalyst for enantioselective olefin metathesis. Efficient catalytic asymmetric ring-opening/cross metathesis in air

The synthesis and structure of a new chiral bidentate imidazolinylidene ligand and a derived chiral Ru-based carbene are disclosed. The Ru complex is stereogenic at the metal center; it can be prepared in >98% diastereoselectivity and purified by silica gel chromatography with undistilled solvents. The air-stable Ru complex efficiently catalyzes ring-closing and ring-opening metathesis and is recyclable. The chiral complex is highly effective (0.5-10 mol % loading) in promoting enantioselective ring-opening/cross metathesis reactions (up to >98% ee). These enantioselective transformations can be effected in air, with unpurified solvent and with substrates that would only polymerize with Mo-based catalysts.     

Spins of the levels and multipole mixing ratios of transitions in 125Sb determined from γ-γ directional correlation and polarization-directional correlation measurements

In order to resolve several discrepancies in spin assignments to levels in ¹²⁵Sb, directional correlations and polarization-directional correlations have been measured for several γ-γ cascades in ¹²⁵Sb populated from the decay of ¹²⁵Sn. Earlier results obtained from using NaI and Ge(Li) and NaI detectors were difficult to interpret due to the complex structure of the decay scheme. To improve the experimental situation, we have used two coaxial Ge(Li) detectors for the angular correlation measurements and a coaxial Ge(Li)-planar Ge(Li) combination for the polarization-directional correlations. Combination of the results of these measurements give unique spin assignments of $\text{11}\text{2}$^?, $\text{11}\text{2}$^?, $\text{9}\text{2}$⁺, $\text{11}\text{2}$⁺ and $\text{9}\text{2}$⁺ to the 1982 keV, 1890 keV, 1420 keV, 1089 keV and 1067 keV levels, respectively. The determined E2/M1 mixing ratios are : δ(470) = 0.010±0.027, δ(1067) = ?0.86±0.18, and δ(916) = ?0.02±0.01.     

Chiral Ru-based complexes for asymmetric olefin metathesis: enhancement of catalyst activity through steric and electronic modifications

Design, synthesis, characterization, and catalytic activity of six enantiomerically pure Ru-based metathesis catalysts are disclosed (3a-3f). The new chiral catalysts were prepared through steric and electronic alterations of the parent catalyst system (3). The present studies indicate that the effect of structural modifications of chiral complex 3 does not always correspond to those of the related achiral complexes. The present findings illustrate that modified Ru complexes (3e and 3f) deliver reactivity levels that are more than 2 orders of magnitude higher than 3. Reactivity and physical data are provided that shed light on the origin of activity differences. Some members of the new generation of chiral Ru catalysts promote asymmetric ring-opening (AROM) and ring-closing (ARCM) metatheses that cannot be effected by the first generation chiral catalyst (3).     

Synthesis and anticancer properties of gold(I) and silver(I) N-heterocyclic carbene complexes

Bis(1,3-dimethylimidazol-2-ylidene)silver(I) nitrate and bis(4,5-dichloro-1,3-dimethylimidazol-2-ylidene)silver(I) nitrate were prepared by reacting the corresponding imidazolium nitrate salts with silver oxide. Bis(1,3-dimethylimidazol-2-ylidene)gold(I) nitrate and bis(4,5-dichloro-1,3-dimethylimidazol-2-ylidene)gold(I) nitrate salts were prepared via transmetallation of their silver precursors with chloro dimethylsulfide gold. The anticancer properties were determined using NCI-H460 lung cancer cells. Efficacy was established by comparison of the gold and silver compounds with cisplatin.     

Analysis of amphetamine and methamphetamine as emerging pollutants in wastewater and wastewater-impacted streams

The identification and quantitation of the non-ecstasy amphetamine-type stimulants (ATSs) amphetamine and methamphetamine in lakes, rivers, wastewater treatment plant influents, effluents, and biosolids are reviewed. Neither monitoring nor reporting is required of these ATSs, which are considered emerging pollutants, but they have been identified in the environment. Amphetamine and methamphetamine enter our water supply by human excretion after legal or illegal consumption and via manufacturing in clandestine laboratories. Analytical methodology for sampling, sample preparation, separation, and detection of ATSs is discussed. Reported occurrences of ATSs in the environment and their use in municipal sewage epidemiology are noted. Future research needs that challenge applications of analytical techniques are discussed. The review focuses on research reported from 2004 to 2009.     

The gravity p-median model

In this paper we propose a new model for the p-median problem. In the standard p-median problem it is assumed that each demand point is served by the closest facility. In many situations (for example, when demand points are communities of customers and each customer makes his own selection of the facility) demand is divided among the facilities. Each customer selects a facility which is not necessarily the closest one. In the gravity p-median problem it is assumed that customers divide their patronage among the facilities with the probability that a customer patronizes a facility being proportional to the attractiveness of that facility and to a decreasing utility function of the distance to the facility.     

Genetic analysis of the GRIK2 modifier effect in Huntington's disease

Background  

In Huntington's disease (HD), age at neurological onset is inversely correlated with the length of the CAG trinucleotide repeat mutation, but can be modified by genetic factors beyond the HD gene. Association of a relatively infrequent 16 TAA allele of a trinucleotide repeat polymorphism in the GRIK2 3'UTR with earlier than expected age at neurological onset has been suggested to reflect linkage disequilibrium with a functional polymorphism in GRIK2 or an adjacent gene.     

Energy expenditure in cyclo-loading processes

A theoretical analysis of the energy expenditure in cyclo-loading vs. quasi-static processes is presented. The analysis refers to processes of a tool-soil interaction, such as implement penetration, cutting, crushing, shovelling etc. The analysis reaches a conclusion stating that no unilateral preference statement can be drawn, thus justifying the experimental results available. It is shown that the existence of an optimal cyclo-loading regime, challenging the quasi-static regime, strongly depends on the character of the loading-unloading curves defining the tool-soil system under consideration. A simple criterion providing an immediate answer to the question of the cyclic vs. quasi-static process preference is derived. The energy expenditure per unit displacement function is thoroughly investigated.